EP0373382A1 - Silberhalogenid enthaltendes lichtempfindliches Farbmaterial - Google Patents

Silberhalogenid enthaltendes lichtempfindliches Farbmaterial Download PDF

Info

Publication number
EP0373382A1
EP0373382A1 EP89121350A EP89121350A EP0373382A1 EP 0373382 A1 EP0373382 A1 EP 0373382A1 EP 89121350 A EP89121350 A EP 89121350A EP 89121350 A EP89121350 A EP 89121350A EP 0373382 A1 EP0373382 A1 EP 0373382A1
Authority
EP
European Patent Office
Prior art keywords
silver halide
halide emulsion
speed
emulsion layer
sensitive silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP89121350A
Other languages
English (en)
French (fr)
Inventor
Hideki Fuji Photo Film Co. Ltd. Naito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0373382A1 publication Critical patent/EP0373382A1/de
Withdrawn legal-status Critical Current

Links

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
    • G03C7/3029—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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • G03C2007/3039—Yellow filter

Definitions

  • the present invention relates to a high-speed photographic color photosensitive material and, more particularly, to a photographic color photosensitive material which can be rapidly processed and has good storage stability.
  • JP-B means examined Japanese patent application
  • JP-A means unexamined published Japanese patent application
  • DIR coupler or DIR compound as described in, e.g., U.S.
  • Patents 3,227,554 and 3,632,435 use of a coupler capable of releasing a mobile dye as described in British Patent 2,083,640; and use of a silver halide having a high average silver iodide content as described in JP-A-60-128443.
  • Patent 4,184,876 discloses a technique in which high-speed green- and red-sensitive layers are combined into a single high-speed unit, low-speed green- and red-­sensitive layers are combined into a single low-­sensitive unit, and the high-speed unit is located outside the low-speed unit, thereby increasing the sensitivity. Since, however, these techniques are un­satisfactory although they have partially achieved the above object, many other patent applications have been applied, in which improved techniques are disclosed.
  • West German Patent 3,410,639 discloses a technique in which a high-speed portion in a blue-­sensitive layer is incorporated in a high-speed unit; and West German Patent 3,411,966, EP 155814, EP 124861, JP-A-59-177552 and JP-A-59-180556 disclose techniques in which a high-speed unit comprising blue-, green-, and red-sensitive layers is combined with another technique.
  • U.S. Patent 4,129,446 describes a positional relationship between a high-speed unit and a yellow filter
  • U.S. Patent 4,186,016 describes a connec­tion relationship between high- and low-speed units
  • U.S. Patent 4,267,264 describes a relationship between a green-sensitive layer and a high-speed red-sensitive layer
  • British Patent 1,560,965 and U.S. Patent 4,186,011 define an interlayer.
  • a silver halide color photosensitive material comprising: a support; and a layer arrangement which is supported on the support and includes at least one blue-sensitive silver halide emulsion layer, a high-speed red-sensitive silver halide emulsion layer, a high-speed green-sensitive silver halide emulsion layer, at least one low-speed green-sensitive silver halide emulsion layer, and at least one low-speed red-sensitive silver halide emulsion layer sequentially arranged adjacent to each other, from the farthest side from the support, in the order named, optionally with a non-photosensitive layer being inter­posed between the adjacent color-sensitive emulsion layers.
  • the layer arrangement may include a yellow fil­ter layer between the blue-sensitive silver halide emul­sion layer and the high speed red-sensitive silver halide emulsion layer.
  • a photosensitive material of the present invention comprises a color photosensitive material coated on a support.
  • five essential color-sensitive emulsion layers i.e., at least one blue-­sensitive silver halide emulsion layer, a high-speed red-sensitive silver halide emulsion layer, a high-speed green-sensitive silver halide emulsion layer, at least one low-speed green-sensitive silver halide emulsion layer, and at least one low-speed red-sensitive silver halide emulsion layer are coated in the layer arrange­ment as defined above.
  • a yellow filter layer may be provided between the blue-sensitive silver halide emul­sion layer and the high-speed red-sensitive silver halide emulsion layer, or no yellow filter layer is provided.
  • the above layer arrangement includes at least one blue-sensitive silver halide emulsion layer (to be also referred to as a "blue-sensitive emulsion layer” hereinafter) located farthest from the support of the five essential color-­sensitive layers.
  • the layer arrangement includes two or three blue-sensitive emulsion layers having substantially the same color sensitivity.
  • layers having "substantially the same color sensitivity" are those having maximum sensitivities falling within the range of 400 to 500 nm and having the same or approximate spectral sensitivity distributions.
  • a layer having higher sensitivity is pre­ferably arranged farther from a support.
  • high-speed or low-speed used for the red-sensitive silver halide emulsion layer (to be also referred to as a "red-sensitive emulsion layer” herein­after) and the green-sensitive silver halide emulsion layer (to be also referred to as a “green-sensitive emulsion layer” hereinafter) is a relative concept.
  • a toe speed difference between these emulsion layers having relatively high and low speeds is preferably 0.1 to 1.0, and more preferably, 0.2 to 0.7 in common logarithm expression of an exposure amount.
  • a high- or low-speed red- or green-emulsion layer may consist of two layers having different sen­sitivities or speeds, as will be described later. In this case, the preferable value of a relative speed difference is the same as described above.
  • red- or green-sensitive emulsion layers having "substan­tially the same color sensitivity" are those having maximum sensitivities falling within the range of 600 to 700 nm or 500 to 600 nm, respectively, and the similar spectral sensitivity distributions.
  • each of the blue-, green-, and red-sensitive emulsion layer preferably con­tains at least one yellow, magenta, and cyan coupler, respectively.
  • the present invention is preferably formulated into a negative color photosensitive material.
  • a transparent flexible support is used as the support for the layer arrangement and the material has a specified photographic sensitivity of 320 to 6400 (to be described later).
  • the sensitivity can be obtained by the techniques well known in the art, including selection of grain sizes.
  • the yellow filter layer is a layer of a yellow-­colored non-photosensitive material and contains yellow colloidal silver or yellow dye.
  • the yellow filter layer is decolored after development.
  • each of emulsion layers having different color sensitivities is constituted by L, M, and H layers having different speed sensitivities.
  • Each emulsion layer may be constituted by only L and H layers.
  • the blue-­sensitive layer may be constituted by only one layer.
  • a layer (Ref) which reflects light may be formed immediately below a high-speed layer to obtain a structure in which BL, BM, Ref, and BH are arranged in this order from the support.
  • a non-photosensitive fine grain emulsion layer may be formed as a non­photosensitive interlayer adjacent to the high-speed layers.
  • a medium-speed layer is arranged adjacent to a low-speed layer.
  • a medium-speed layer may be arranged adjacent to a high-speed layer.
  • An interlayer e.g., IL in an arrangement of GL, GM, IL, and GH of the arrangement (2)
  • intervening emulsion layers of the same color sensitivity may contain a compound (so-called sca­venger) for trapping an oxide of a developing agent.
  • an emulsion may be added to an interlayer.
  • the protective layer PL need not be a single layer but may consist of two or more layers. In this case, the outermost layer preferably contains a mat agent.
  • the protective layer contains oil drops in order to adjust film physical properties
  • it is preferably constituted by two or more layers.
  • the outermost layer has a smaller oil/binder (weight) ratio than that of the adjacent inside layer.
  • An antihalation layer and, if necessary, an interlayer formed on the antihalation layer are normally formed between the low-­speed red-sensitive emulsion layer and the support.
  • the protective layer or various interlayers described above may contain couplers and DIR compounds as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038.
  • the color photosensitive material of the present invention has blue-, green-, and red-sensitive silver halide emulsion layers. Of these layers, at least each of the green- and red-sensitive layers is constituted by two or more layers having different sensitivities. In order to improve graininess of the green- or red-­sensitive layer and, if necessary, that of the blue-­sensitive layer, an arrangement in which each color-­sensitive layer is constituted by three layers is most preferably. This technique is different from a three-­layered arrangement of color-sensitive emulsion layers having the same sensitivity described in JP-B-49-15495 because a particularly good effect is obtained by the technique in combination with the layer arrangement in a reversed order in accordance with the present invention.
  • a non-photosensitive layer may be formed between the photosensitive emulsion layers.
  • This non-­photosensitive layer may be interposed between two or more emulsion layers having the same color sensitivity.
  • a non-photosensitive layer is preferably formed between such layers.
  • Such a non-photosensitive interlayer may contain a scavenger substance for a color developing agent oxide. It is also preferable to form a non-­photosensitive reflecting layer below a photosensitive emulsion layer to improve the sensitivity as described in JP-A-59-160135. Although this is not always necessary, the color photosensitive material of the present invention normally contains a yellow filter layer.
  • This yellow filter layer mainly serves to shield unnecessary blue sensitivity of the red- or green-­sensitive emulsion layer and is normally formed between the high-sensitive red-sensitive silver halide emulsion layer and a blue-sensitive silver halide layer closest to the support. Effective sensitivity, however, can be improved without degrading the color reproducibility by forming the yellow filter layer at a side adjacent to the high-speed red-sensitive silver halide emulsion layer and close to the support.
  • a tabular grain in which color sensitization sensitivity (minus blue sensitivity) is relatively higher than specific sensitivity (blue sensitivity) is preferably used in the high-speed red-sensitive emulsion layer RH.
  • the photosensitive material of the present inven­tion preferably has a specified photographic sensitivity of 320 or more and a total amount of silver contained in the photosensitive material of 3.0 to 13.0 g/m2. If the specified photographic sensitivity is less than 320, the layer arrangement according to the present invention need not be adopted. If the total silver amount is more than 13 g/m2, it is difficult to reduce a desilverizing time since bleaching requires a long time.
  • the specified photographic sensitivity is a photo­graphic sensitivity obtained by a method according to JIS K 7614-1981 for measuring an ISO sensitivity. That is, the specified photographic sensitivity is obtained by exposing a photosensitive material for sensitometry and developing the exposed material one hour, not five days defined by JIS, after exposure by a negative pro­cessing prescription CN-16 available from Fuji Photo Film Co., Ltd. The number of storage days defined in the JIS test method is reduced in order to quickly obtain a result. Since it is defined that development is performed by a method designated by each company, a storage time is specified as one hour. Therefore, this photographic sensitivity is called herein as the speci­fied photographic sensitivity.
  • JP-A-63-226650 Japanese Patent Application No. 62-159115 which claimed domestic priority based on Japanese Patent Application No. 61-201756
  • JP-A-63-226650 Japanese Patent Application No. 62-159115 which claimed domestic priority based on Japanese Patent Application No. 61-201756
  • the specified photographic sensitivity of the color photosensitive material of the present invention is lower than 320, an effect of a combination of an improvement in an arrangement order of layers of the multilayered color negative photosensitive material of the present invention and a silver content is not signi­ficantly achieved.
  • the specified photographic sensi­tivity is preferably 400 or more, and more preferably, 800 or more.
  • any of silver bromide, silver iodobro­mide, silver iodochlorobromide, silver chlorobromide, and silver chloride can be used as a silver halide.
  • a preferable silver halide is silver iodobromide con­taining 30 mol% or less of silver iodide.
  • a most pre­ferable silver halide is silver iodobromide containing 2 to 20 mol% of silver iodide.
  • an average silver iodide content of a silver halide in all the emulsion layers is preferably set to 8 mol% or more as described in JP-A-60-128443. It is known that when the average silver iodide content of a silver halide is increased, the graininess is significantly improved. If, however, the silver iodide content exceeds a certain level, a development speed is decreased, or a desilverizing or fixing speed is decreased. In the pre­sent invention, however, these drawbacks hardly occur even if the silver iodide content is increased, resulting in a great advantage.
  • a silver halide grain for use in the photographic emulsion layers of the silver halide photographic photo­sensitive material of the present invention preferably has a double structure constituted by a core which consists essentially of silver iodobromide containing 5 mol% or more of silver iodide and a shell which covers the core and consists essentially of silver iodobromide or silver bromide having a lower silver iodide content than that of the core.
  • the silver iodide content of the core is more preferably 10 mol% or more, and most pre­ferably, 20 to 44 mol%.
  • the silver iodide content of the shell is preferably 5 mol% or less.
  • the core may uniformly contain silver iodide or may have a multi-phase structure consisting of silver iodobromide phases having different silver iodide con­tents.
  • a silver iodide content of a phase having the highest silver iodide content is 5 mol% or more, and preferably, 10 mol% or more.
  • a silver iodide content of the shell is lower than that of a phase having the highest silver iodide content.
  • the expression "consists essentially of silver iodobromide” means that the core or shell mainly con­sists of silver iodobromide but can contain up to about 1 mol% of another component (e.g., silver chloride).
  • a more preferable silver halide grain for use in the photographic emulsion layers of the silver halide photographic photosensitive material of the present invention has a structure in which when a diffraction intensity-vs-diffraction angle curve of a (220) face of a silver halide is obtained within a diffraction angle (2 ⁇ ) range of 38° to 42° by using a Kß line of Cu, two diffraction maximum peaks appear corresponding to core and shell portions, with one diffraction minimum peak appearing therebetween, and the diffraction intensity corresponding to the core portion becomes 1/10 to 3/1 that of the shell portion.
  • the diffraction intensity ratio is 1/5 to 3/1 or 1/3 to 3/1.
  • a silver iodobromide emulsion having a high iodide content can be used without decreasing the development speed. Therefore, a photosensitive material having excellent graininess can be achieved with a small coating silver amount.
  • an average grain size (which is a grain diameter if a grain is spherical or almost spherical and is an edge length if a grain is cubic, and is repre­sented by an average value based on a projected surface area) of silver halide grains in the photographic emulsion is not particularly limited, it is preferably 0.05 to 10 ⁇ m.
  • An average size of silver halide grains in an emulsion layer having the highest sensitivity is preferably 0.5 to 4 ⁇ m, and more preferably, 0.6 to 2.5 ⁇ m.
  • a grain size distribution may be narrow or wide.
  • the silver halide grain in the photographic emulsion may be a regular crystal such as a cubic or octahedral crystal, may be an irregular crystal such as a spherical or tabular crystal, or may be a combination of these crystals. Alternatively, a mixture of grains having various crystal forms may be used.
  • a tabular grain having an aspect ratio of 5 or more because a color sensitization efficiency obtained by a sensitizing dye is increased.
  • Such a tabular grain can be easily prepared by methods described in, e.g., Gutoff, "Photographic Science and Engineering", Vol. 14, PP. 248 to 257, (1970); and U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520 and British Patent 2,112,157.
  • the photographic emulsion for use in the present invention can be prepared by using methods described in, e.g., P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967; G.F. Duffin, "Photographic Emulsion Chemistry", The Focal Press, 1966; and V.L. Zelikman et al., “Making and Coating Photographic Emulsion", The Focal Press, 1964. That is, the photographic emulsion can be prepared by, e.g., an acid method, a neutralization method, and an ammonia method. As a system for reacting a soluble silver salt and a soluble halide, a single mixing method, a double mixing method, or a combination thereof can be used.
  • a so-called back mixing method for forming silver halide grains in the presence of excessive silver ions can be used.
  • a so-called controlled double jet method wherein a pAg of a liquid phase in which a silver halide is formed is kept at a constant value can be used. According to this method, a silver halide emulsion having a regular crystal form and almost uniform grain sizes is obtained.
  • Two types or more of independently prepared silver halide emulsions may be mixed and used in a single emulsion layer.
  • a silver halide grain having a crystal face defined by Miller indices (nnl) (n ⁇ 2, n is a natural number) on its outer surface as described in Journal of Technical Disclosure No. 86-9598 is preferably used.
  • a silver halide grain having an internal hollow communication portion from its surface as described in JP-A-61-75337 is also preferably used.
  • Such a silver halide grain having a large specific surface area can be effectively used in combination with the present inven­tion because the sensitivity is increased higher than that obtained by a solid silver halide grain of the same volume upon color sensitization.
  • a composite grain of a combination of a host grain and a silver salt having a different composition epitaxially grown on the host grain as disclosed in JP-A-57-133540, JP-A-58-108526, or JP-A-59-162540 may be preferably used.
  • Such a grain is preferably used in combination with the present invention since it exhibits high-speed, high-contrast photographic property.
  • a silver halide emulsion grown in the presence of tetrazaindene as described in JP-A-61-14630 and JP-A-60-122935 has a high silver iodide content and good monodispersion properties and therefore exhibits high sensitivity and excellent graininess. Therefore, this silver halide emulsion can be preferably used in the present invention.
  • a silver halide emulsion subjected to a gold-plus-­sulfur sensitization or gold-plus-selenium sensitization in the presence of a nitrogen-containing heterocyclic compound as disclosed in JP-A-58-126526 has a low fogging density and high sensitivity. Therefore, this silver halide emulsion can be preferably used in the present invention.
  • a slightly rounded cubic or tetradecahedral crystal described in JP-A-59-149345 or JP-A-59-149344 is pre­ferable as a silver halide emulsion for use in the pre­sent invention since a high sensitivity can be obtained.
  • a cadmium salt In a process of formation or physical ripening of silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or an iri­dium complex salt, a rhodium salt or a rhodium complex salt, or an iron salt or an iron complex salt may be used.
  • a silver halide emulsion whose grains are formed in the presence of iridium has high sensitivity (JP-B-43-4935 or JP-B-45-32738) and therefore is most preferably used in the present invention.
  • soluble salts are normally removed from an emulsion.
  • a conventional Nudel washing method in which gelatin is gelled can be used.
  • a sedimentation method utilizing an inorganic salt consisting of a multivalent anion such as sodium sulfate, an anionic surfactant, an anionic polymer (e.g., polystyrenesulfonic acid) or a gelatin derivative (e.g., an aliphatic acylated gelatin, aromatic acylated gelatin, or aromatic car­bamoylated gelatin) can be performed.
  • a silver halide emulsion is normally subjected to chemical sensitization.
  • chemical sensitization a method described in H. Frieser ed., "Die Grundlagen der Photographischen Sawe mit Silber-Halogeniden” (Akademische Verlagsgesellschaft, 1968) PP. 675 to 734 can be used.
  • a sulfur sensitization method using active gelatin or a compound containing sulfur which can react with silver e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines
  • a reduction sensitization method using a reducing substance e.g., stannous salt, amines, a hydrazine derivative, formamidinesulfinic acid, a silane compound
  • a noble metal sensitiza­tion method using a noble metal compound e.g., a gold complex salt or a complex salt of Group VIII metals of the periodic table such as Pt, Ir, and Pd
  • a noble metal compound e.g., a gold complex salt or a complex salt of Group VIII metals of the periodic table such as Pt, Ir, and Pd
  • a selenium sensitization method using a compound containing selenium which can react with active gelatin or silver can be preferably used in com­bination with another sensitization method because a high-speed emulsion can be obtained.
  • This technique is described in, e.g., U.S. Patents 1,574,944, 1,602,592, and 1,623,499, JP-B-52-38408, JP-B-57-22090, JP-A-59-180536, U.S. Patent 4,565,778, JP-A-59-185329 and JP-A-60-150046.
  • the photographic emulsion for use in the present invention can be spectrally sensitized with, e.g., methine dyes.
  • the dye include a cyanine dye, merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and hemioxonol dye.
  • Most effective dyes are those belonging to a cyanine dye, a merocyanine dye, and a composite merocyanine dye. These dyes can contain any nucleus normally contained as a basic heterocyclic nucleus in cyanine dyes.
  • nucleus examples include pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus; a nucleus having an alicyclic hydrocarbon ring fused to each of the above nuclei; and a nucleus having an aromatic hydrocarbon ring fused to each of the above nuclei, e.g., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadole nucleus, a naphthooxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselen
  • a merocyanine dye or composite merocyanine dye can contain, as a nucleus having a ketomethylene structure, a 5- or 6-membered heterocyclic nucleus, e.g., a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus.
  • a nucleus having a ketomethylene structure e.g., a 5- or 6-membered heterocyclic nucleus, e.g., a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a
  • Examples of an effective sensitizing dye are described in, e.g., West German Patent 929,080, U.S. Patents 2,231,658, 2,493,748, 2,503,776 2,519.001. 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349, and 4,046,572, British Patent 1,242,588, and JP-B-44-14030 and JP-B-52-24844.
  • sensitizing dyes can be used singly or in a combination of two or more thereof.
  • a combination of the sensitizing dyes is often used especially in order to perform supersensitization.
  • Typical examples of the combination are described in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, and 4,026,707, British Patents 1,344,281 and 1,507,803, JP-B-43-4936 and JP-B-53-12375, and JP-A-52-110618 and JP-A-52-109925.
  • the emulsion may contain, in addition to the sen­sitizing dye, a dye not having a spectral sensitizing effect or a substance substantially not absorbing visible light and having supersensitization.
  • the emulsion may contain aminostyl compounds substituted with a nitrogen-containing heterocyclic group (described in, e.g., U.S. Patents 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde con­densate (described in, e.g., U.S. Patent 3,743,510), cadmium salt, and an azaindene compound.
  • a nitrogen-containing heterocyclic group described in, e.g., U.S. Patents 2,933,390 and 3,635,721
  • an aromatic organic acid formaldehyde con­densate described in, e.g., U.S. Patent 3,743,510
  • cadmium salt e.g., cadmium salt
  • Photographic additives for use in this invention are described in Research Disclosures (RD), Nos. 17643 and 18716 and they are summarized in the following table.
  • Additives RD No.17643 RD No.18716 1. Chemical sensitizers page 23 page 648, right column 2. Sensitivity increasing agents do. 3. Spectral sensitizers, supersensitizers pages 23-24 page 648, right column to page 649, right column 4. Brighteners page 24 5. Antifoggants and stabilizers pages 24-25 page 649, right column pages 24-25 6. Light absorbent, filter dye, ultraviolet absorbents pages 25-26 page 649, right column to page 650, left column 7. Stain preventing agents page 25, right column page 650, left to right columns 8.
  • Dye image stabilizer page 25 9. Hardening agents page 26 page 651, left column 10. Binder page 26 do. 11. Plasticizers, lubricants page 27 page 650, right column 12. Coating aids, surface active agents pages 26-27 do. 13. Antistatic agents page 27 do.
  • a compound capable of reacting with and setting formaldehyde described in U.S. Patent 4,411,987 or 4,435,503 is preferably added to the photosensitive material.
  • a yellow coupler Preferred examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023, and 4,511,649, and EP 249,473A.
  • magenta coupler examples are preferably 5-pyrazolone and pyrazoloazole compounds, and more pre­ferably, compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, RD No. 24220 (June 1984) JP-A-60-33552, RD No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, and U.S. Patents 4,500,630, 4,540,654, and 4,556,630.
  • Examples of a cyan coupler are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, EP 121,365A and 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A-61-42658.
  • a colored coupler for correcting additional, undesirable absorption of a colored dye are those described in RD No. 17643, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
  • a coupler capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
  • Couplers releasing a photographically useful resi­due upon coupling are preferably used in the present invention.
  • DIR couplers i.e., couplers releasing a development inhibitor are described in the patents cited in the above-described RD No. 17643, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and JP-A-63-37346, and U.S. Patent 4,248,962.
  • a coupler imagewise releasing a nucleating agent or a development accelera­tor upon development are those described in British Patent 2,097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840.
  • Examples of a coupler which can be used in the pho­tosensitive material of the present invention are com­peting couplers described in, e.g., U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S.
  • Patents 4,283,472, 4,338,393, and 4,310,618 a DIR redox compound releasing coupler or DIR coupler releasing coupler, or a DIR coupler releasing redox compound or DIR redox compound releasing redox described in, e.g., JP-A-60-185950, JP-A-62-24252, and JP-A-62-291645; couplers releasing a dye which turns to a colored form after being released described in EP 173,302A; bleaching accelerator releasing couplers described in, e.g., RD. Nos. 11449 and 24241 and JP-A-61-201247; and a legand releasing coupler described in, e.g., U.S. Patent 4,553,477.
  • Examples of a color coupler usable in the present invention are listed in Table A.
  • a usable coupler is not limited to those couplers.
  • the couplers for use in this invention can be introduced in the photosensitive materials by various known dispersion methods.
  • a high-boiling organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175°C or more at normal pressure examples include phthalate esters (e.g., dibutylphthalate, dicyclo­hexylphthalate, di-2-ethylhexylphthalate, decylphtha­late, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, and bis(1,1-diethylpropyl)phthalate), phophate or phospho­nate esters (e.g., triphenylphosphate, tricresylpho­sphate, 2-ethylhexyldiphenylphosphate, tricyclohexyl­phosphate, tri-2-ethylhexylphosphate, tridodecylphos­phate, tributyoxy
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as a co-solvent.
  • Typical examples of the co-solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylfor­mamide.
  • the present invention can be applied to various color photosensitive materials.
  • Representative examples of the material are a color negative film for a general purpose or a movie, and a color reversal film for a slide or a television.
  • the color photographic photosensitive materials of this invention can be developed and processed by the ordinary processes as described, for example, in the above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left to right columns.
  • a color developer used in developing of the photo­sensitive material of the present invention is an aqueous alkaline solution mainly consisting of, pre­ferably, an aromatic primary amine-based color develop­ing agent.
  • an aromatic primary amine-based color develop­ing agent As the color developing agent, although an aminophenol-based compound is effective, a p-­phenylenediamine-based compound is preferably used.
  • Typical examples of the p-phenylenediamine-based compound are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-methanesulfonamidoethylan­iline, 3-methyl-4-amino-N-ethyl-N-ß-methoxyehtylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof. These compounds can be used in a combination of two or more thereof in accordance with applications.
  • the color developer contains a pH buf­fering agent such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • a pH buf­fering agent such as a carbonate, a borate or a phosphate of an alkali metal
  • a development restrainer or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diehtylhydroxyla­mine, a hydrazine sulfite, a phenylsemicarbazide, triethanolamine, a catechol sulfonic acid or a triethylenediamine(1,4-diazabicyclo[2,2,2]octane); an organic solvent such as ethyleneglycol or diethylenegly­col; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye forming coupler; a competing coupler; a fogging agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid or a phosphonocarboxylic acid
  • chelating agent examples include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine­tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N′,N′-tetramethylenephosphonic acid and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
  • black-­and-white development is performed and then color development is performed.
  • black-and-white deve­loper well-known black-and-white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in a combination of two or more thereof.
  • the pH of the color and black-and-white developers is generally 9 to 12.
  • a replenishment amount of the developer depends on a color photographic photo­sensitive material to be processed, it is generally 3 liters or less per m2 of the photosensitive material.
  • the replenishment amount can be decreased to be 500 ml or less by decreasing a bromide ion concentration in a replenishing solution.
  • a contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air.
  • the replenishment amount can be decreased by using a means capable of suppressing an accumulation amount of bromide ions in the developer.
  • a sample 101 as a multilayered color photosensitive material consisting of layers having the following compositions were formed, in the order mentioned below, on an undercoated triacetylcellulose film support.
  • the coating amount of a silver halide and colloid silver are represented in units of g/m2 of silver, that of additives and gelatin is represented in units of g/m2, and that of sensitizing dye is represented by the number of mols per mol of the silver halide in the same layer.
  • a sample 102 was prepared by switching the layers 9 and 11 in the sample 101, and a sample 103 was prepared by removing the layer 12 of the sample 102.
  • a silver amount and a compound coating amount of each sample are represented by an increased/decreased amount with respect to the sample 101.
  • silver amount + 0.1 g of the layer 9 in the sample 102 is based on the layer GH in the sample 101
  • silica amount - 0.5 g of the layer 11 in the sample 102 is based on the layer RH in the sample 101.
  • An amount of a sensitizing dye was changed in proportional to the silver amount.
  • the samples 101 to 103 were imagewise exposed and then subjected to the following processing.
  • the color development process was performed at 38°C in accordance with the following process steps. Color Development 3 min. 15 sec. Bleaching 6 min. 30 sec. Washing 2 min. 10 sec. Fixing 4 min. 20 sec. Washing 3 min. 15 sec. Stabilization 1 min. 05 sec.
  • the processing solution compositions used in the respective steps were as follows. Color Development Solution Diethylenetriaminepentaacetic Acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium Sulfite 4.0 g Potassium Carbonate 30.0 g Potassium Bromide 1.4 g Potassium Iodide 1.3 mg Hydroxylamine Sulfate 2.4 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylanilinesulfate 4.5 g Water to make 1.0 l pH 10.0 Bleaching Solution Ferric Ammonium Ethylenediaminetetraacetate 100.0 g Disodium Ethylenediaminetetraacetate 10.0 g Ammonium Bromide 150.0 g Ammonium Nitrate 10.0 g Water to make 1.0 l pH 6.0 Fixing Solution Disodium Ethylenediaminetetraacetate 1.0 g Sodium Sulfite 4.0 g Ammonium Thi
  • each of the samples 102 to 103 according to the present invention has higher sensitivity and better graininess of the red-­sensitive layer than those of the sample 101 regardless of its small silver amount. That is, the present invention is proved to be effective.
  • a sample 201 was prepared as sample 102 except that the layer 9 in the sample 102 was removed and the coating amount of layer 11 was decreased by 15%.
  • Example 1 The samples 101 and 102 of Example 1 were subjected to uniform exposure of 5 CMS and then to the processing of Example 1. In this processing, a bleaching time was changed such that a remaining silver amount became 6 ⁇ g/cm2 or less by a fluorescent X-ray method. As a result, a time required for the sample 101 was four minutes and ten second, while it was three minutes and thirty seconds for the sample 102. That is, the processing time can be reduced by the sample of the present invention.
  • desired photographic sensitivity can be achieved by a smaller coating silver amount than that of silver halide color photographic material according to the conventional layer arrangement (a support, RL, RM, GL, GM, RH, GH, YF, BL, BM, BH, and PL) assumed to be preferable to obtain high sensitivity. Therefore, since a desilverizing load after color development can be reduced, high-speed processing is achieved. In addition, since predetermined high sensitivity is realized with a small coating silver amount, a decrease in sensitivity caused by natural radiation upon storage of a raw photosensitive material or an increase in fogging density can be suppressed. As a result, a photographic color photosensitive material with good storage stability can be obtained.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP89121350A 1988-11-18 1989-11-17 Silberhalogenid enthaltendes lichtempfindliches Farbmaterial Withdrawn EP0373382A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP29196588A JPH02136853A (ja) 1988-11-18 1988-11-18 ハロゲン化銀カラー感光材料
JP291965/88 1988-11-18

Publications (1)

Publication Number Publication Date
EP0373382A1 true EP0373382A1 (de) 1990-06-20

Family

ID=17775756

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89121350A Withdrawn EP0373382A1 (de) 1988-11-18 1989-11-17 Silberhalogenid enthaltendes lichtempfindliches Farbmaterial

Country Status (2)

Country Link
EP (1) EP0373382A1 (de)
JP (1) JPH02136853A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661591A2 (de) 1993-12-29 1995-07-05 Eastman Kodak Company Photographische Elemente die Ultraviolett absorbierendes beladenes Polymerlatex enthalten
EP0695968A2 (de) 1994-08-01 1996-02-07 Eastman Kodak Company Viskositätsverminderung in einer photographischen Schmelze

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH304742A (de) * 1944-04-15 1955-01-31 Agfa Ag Verfahren zur Herstellung von photographischem Positivmaterial für die Zwecke der Mehrfarbenphotographie und -kinematographie.
FR2352323A1 (fr) * 1976-05-21 1977-12-16 Agfa Gevaert Ag Materiau pour la photographie en couleur
DE3420173A1 (de) * 1984-05-30 1985-12-05 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH304742A (de) * 1944-04-15 1955-01-31 Agfa Ag Verfahren zur Herstellung von photographischem Positivmaterial für die Zwecke der Mehrfarbenphotographie und -kinematographie.
FR2352323A1 (fr) * 1976-05-21 1977-12-16 Agfa Gevaert Ag Materiau pour la photographie en couleur
DE3420173A1 (de) * 1984-05-30 1985-12-05 Agfa-Gevaert Ag, 5090 Leverkusen Farbfotografisches aufzeichnungsmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 13, no. 27 (P-815)[3375], 20th January 1989; & JP-A-63 226 650 (FUJI) 21-09-1988 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661591A2 (de) 1993-12-29 1995-07-05 Eastman Kodak Company Photographische Elemente die Ultraviolett absorbierendes beladenes Polymerlatex enthalten
EP0695968A2 (de) 1994-08-01 1996-02-07 Eastman Kodak Company Viskositätsverminderung in einer photographischen Schmelze

Also Published As

Publication number Publication date
JPH02136853A (ja) 1990-05-25

Similar Documents

Publication Publication Date Title
US4775617A (en) Silver halide color photographic material containing monodispersed tabular silver halide grains
US5112733A (en) Silver halide photographic emulsion
EP0348934A2 (de) Silberhalogenidemulsion und farbfotografisches Material, das diese verwendet
EP0369424A1 (de) Lichtempfindliches photographisches Silberhalogenidmaterial
EP0431585B1 (de) Photographische Silberhalogenidemulsion, Verfahren zur Herstellung derselben und photographisches lichtempfindliches Material
US5011767A (en) Silver halide photographic emulsion
US4977074A (en) Silver halide emulsion comprising substantially circular monodisperse tabular silver halide grains and photographic material using the same
EP0435355B1 (de) Silberhalogenidemulsion und photographisches, lichtempfindliches, diese verwendendes Silberhalogenidmaterial
EP0371338B1 (de) Lichtempfindliches photographisches Silberhalogenidmaterial
EP0369491A1 (de) Methode zur Herstellung einer Silberhalogenidemulsion
EP0482599B1 (de) Photographisches lichtempfindliches Silberhalogenidmaterial
US5830633A (en) Silver halide emulsion
EP0435270B1 (de) Verfahren zur Herstellung einer Silberiodobromid- Emulsion und diese verwendendes photographisches lichtempfindliches Silberhalogenidmaterial
US5169746A (en) Silver halide color photographic photosensitive material
US5437972A (en) Silver halide photographic material
US5238796A (en) Silver halide photographic emulsion and photographic light-sensitive material
EP0373382A1 (de) Silberhalogenid enthaltendes lichtempfindliches Farbmaterial
EP0509519B1 (de) Farbphotographisches Silberhalogenidmaterial
EP0438791B1 (de) Lichtempfindliches photographisches Silberhalogenidmaterial
US5426023A (en) Silver halide photographic emulsion containing epitaxial silver halide grains and silver halide photographic light-sensitive material using the same
US5514534A (en) Silver halide photographic light-sensitive material
US5439788A (en) Method of manufacturing silver halide emulsion
EP0573649B1 (de) Photographisches silberhalogenidmaterial
JP2699006B2 (ja) ハロゲン化銀カラー写真感光材料
US5538835A (en) Silver halide color photographic material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19900807

17Q First examination report despatched

Effective date: 19930422

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19930903