EP0108250B1

EP0108250B1 - Silver halide multilayer reversal color photographic material

Info

Publication number: EP0108250B1
Application number: EP19830109913
Authority: EP
Inventors: Yuichi Ohashi; Nobuaki Miyasaka; Koji Takahashi
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1982-10-05
Filing date: 1983-10-04
Publication date: 1987-01-14
Also published as: DE3369203D1; JPH0160135B2; JPS5964843A; EP0108250A1

Description

The present invention relates to a silver halide multilayer reversal color photographic material, comprising a support having coated thereon a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein at least one of these emulsion layers is comprised of a plurality of sublayers of differing photographic sensitivity.
It is impossible to improve the color reproducibility of a reversal color photographic material by using a development inhibitor releasing (DIR) compound. Therefore, the interimage effect due to iodine is important. In known reversal color photographic materials, a high sensitivity emulsion and a low sensitivity emulsion are coated separately to form a double (or multiple) layer, thereby improving granularity. However, the proportion of iodine to total halogen (which is referred to as "iodine content" hereinafter) in the high sensitivity emulsion layer is generally the same as in the low sensitivity emulsion layer. With respect to the interimage effect of a layer on another layer, it becomes necessary to increase the iodine content in the layer in question. However, desirable reproduction of green, red and skin colors with high saturations cannot be obtained only by equally increasing both iodine contents in the high sensitivity and the low sensitivity layers.
The higher the iodine content is in the layer in question, the greater the interimage effect becomes which the layer in question has on another layer, but the more difficult it becomes for the interimage effect of another layer to be received by the layer in question. Accordingly, if an increase of an interimage effect from a certain layer; e.g., a red-sensitive layer, upon another layer; e.g., a green-sensitive layer, is intended, the iodine contents in emulsions of the whole sublayers of the red-sensitive layer are increased, and the interimage effect of the green-sensitive layer on the red-sensitive layer is reduced to result in lowering of the saturation of green color.
When a photographic material is exposed to green monochromatic light, its red-sensitive layer also responds to the light because of imperfections in the spectral sensitivity distribution. Such a phenomenon lowers the green color saturation. However, response of the red-sensitive layer to green monochromatic light to such an extent that perceivable gradation is produced takes place only in its high sensitivity sublayer or in both its high sensitivity sublayer and its medium sensitivity sublayer because the responsivity of the red-sensitive layer to green monochromatic light is considerably lower. Accordingly, it will suffice for suppressing color formation in the red-sensitive layer to enhance the interimage effect on the high sensitivity sublayer or on both the high sensitivity and the medium sensitivity sublayers of the red-sensitive layer and thereby, to inhibit the development from taking place in the red-sensitive layer. Decreasing the iodine content in the high sensitivity sublayer or that in the high sensitivity and the medium sensitivity sublayers will lead to the above-described purpose. Even if iodine contents are decreased in the above-described manner, reduction of the reverse interimage effect, from the red-sensitive layer on the green-sensitive layer, which is ascribed to such a decrease in the iodine content, is atended only by negligible small, adverse effects. It consists in a lowering of red color saturation to be ascribed to a decrease in magenta dye formation which is caused by response of the green-sensitive layer to red monochromatic light. Such a phenomenon attracts much attention only when the exposure is carried out with such intensity that even the low sensitivity sublayer of the red-sensitive layer can respond, and the interimage effect from the red-sensitive layer on the green-sensitive layer can be fully produced by increasing the iodine content in the emulsion for the low sensitivity sublayer of the red-sensitive layer.
The above is also valid for both the green-sensitive layer and the blue-sensitive layer and, thus, has lead to the subject matter of the present invention.
It is the object of the present invention to provide a silver halide multilayer reversal color photographic material which has an improved color reproducibility.
Said object is achieved by a material according to claim 1. The photographic material comprises at least one emulsion layer having two or three sublayers, which have different photographic sensitivities but the same spectral sensitivities, wherein the sublayer, which is made of a silver halide emulsion having a low iodine content, contains 40 to 80% by weight, preferably 45 to 70% by weight, of the total silver ions in the emulsion layer. The iodine content of the sublayer having a low iodine content is by at least 0.3 mole %, preferably by 0.5 to 3.0 mole %, lower than the iodine content of the sublayer having a high iodine content. In addition, it is desirable that the sublayer having a low iodine content comprises silver halide having a halide composition containing 0.5 to 5.7, preferably 1.5 to 4.5, mole % iodide, while the sublayer having a high iodine content comprises silver halide having a halide composition containing 0.8 to 6, preferably 2.0 to 5.0 mole % iodide.
Further, the silver halide emulsion layer having a low iodine content may have one sublayer or two sublayers.
In case of two sublayers, emulsions to form them may have the same iodine content or different ones. If the emulsions have different iodine contents, it is desirable that the emulsion having higher sensitivity has a lower iodine content.
As described above, the present invention is embodied in a silver halide multilayer reversal color photographic material which has three emulsion layers, a blue-sensitive, a green-sensitive and a red-sensitive, silver halide emulsion layer. Further at least one of the emulsion layers consists of two or three sublayers differing in photographic sensitivity.
The material of the present invention is improved in blue, red and green saturations. In known materials an increase in saturation of e.g., green color leads to a decrease in saturation of e.g., red color, whereas the photographic material of this invention provides a clear reversal color image of high color purities.
The most preferred layer to be employed in this invention as the layer in which its high sensitivity sublayer and its low sensitivity sublayer differ in their iodine contents is a green-sensitive layer or a red-sensitive layer.
Examples of silver halides which may be present in the silver halide emulsions of this invention include silver iodobromide and silver iodochlorobromide.
The mean grain size of the silver halide grains in the photographic emulsions, wherein diameters of spherical or nearly spherical grains and edge lengths of cubic grains are employed as grain size, which are averaged on the basis of the projection area method, is not particularly limited. However, a mean grain size of 3 ^pm or less is preferable.
The grain size distribution may be narrow or broad.
The silver halide grains in the photographic emulsions of this invention may have a regular crystal form such as a cube or an octahedron, an irregular crystal form such as a sphere, or a plate, or a composite form thereof. A mixture of various crystal forms of silver halide grains may also be present.
The interior and the surface of the silver halide grains may differ, or the silver halide grains may be uniform throughout. Further, either silver halide grains which form a latent image predominantly at the surface of the grains, or silver halide grains which mainly form a latent image inside the grains can be used.
Photographic emulsions to be employed in this invention can be made using methods as described in, for example, P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966) or V. L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1964). For example, the acid process, the neutral method or the ammonia process may be employed. As a method for reacting a water-soluble silver salt with a water-soluble halide, a single jet method, a double jet method, or a combination thereof may be employed.
Also, a method wherein silver halide grains are produced in the presence of excess silver ions (the so-called reverse jet method) can be employed in this invention. The so-called controlled double jet method, in which the pAg of the liquid phase wherein silver halide grains are to be precipitated is maintained constant, may also be employed in this invention.
According to the above-described method; silver halide emulsions having a regular crystal form and a nearly uniform grain size, so-called monodisperse emulsions, can be obtained.
Two or more silver halide emulsions separately produced may be used in the form of a mixture.
In a process of producing silver halide grains or allowing the produced silver halide grains to ripen physically, cadmium salts, zinc salts, thallium salts, iridium salts or complexes, rhodium salts or complexes, iron salts or complexes may be present.
The removal of the soluble salts from the silver halide emulsion is, in general, carried out after the formation of the silver halide or after physical ripening. The removal can be effected using the noodle washing method which comprises gelling the gelatin or using a sedimentation process (thereby causing flocculation in the emulsion) taking advantage of a sedimenting agent such as a polyvalent anion- containing inorganic salt (e.g., sodium sulfate), an anionic surface active agent or an anionic polymer (e.g., polystyrene sulfonic acid), or a gelatin derivative (e.g., an aliphatic acylated gelatin, an aromatic acylated gelatin or an aromatic carbamoylated gelatin.
The removal of soluble salts from the silver halide emulsion may be omitted.
The silver halide emulsion of this invention can be a so-called unripened emulsion (e.g., a primitive emulsion), which is a chemically unsensitized emulsion. However, it is usual and preferred for the emulsion of this invention to also be chemically sensitized. Chemical sensitization can be carried out using processes described in P. Glafkides, supra, V. L. Zelikman et al, supra or H. Frieser, Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden, Akademische Verlagsgesellschaft (1968).
More specifically, sulfur sensitization using compounds containing sulfur capable of reacting with silver ions or active gelatin, reduction sensitization using reducing materials, sensitization with gold or other noble metal compounds can be employed individually or as a combination thereof. Examples of suitable sulfur sensitizers which can be used include thiosulfates, thioureas, thiazoles, rhodanines and other sulfur-containing compounds. Specific examples of sulfur sensitizers are described in U.S. Patents 1,574,944; 2,410,689; 2,278,947; 2,728,668; 3,656,955; 4,032,928 and 4,067,740. Examples of reducing sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, saline compounds and specific examples of these sensitizers are described in U.S. Patents 2,487,850; 2,419,974; 2,518,698; 2,983,609; 2,983,610; 2,694,637; 3,930,867 and 4,054,458. Group VIII metal complexes such as those of platinum, iridium or palladium, other than gold metal complexes, can be employed for the purpose of sensitization with a noble metal. Specific examples of these metal complexes are disclosed in U.S. Patents 2,399,083 and 2,448,060; and British Patent 618,061.
The photographic emulsions to be employed in this invention can contain a wide variety of compounds for purposes of preventing fogging or stabilizing photographic functions during production, storage or processing. Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro or halogen substituted ones); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-described heterocyclic mercapto compounds containing water soluble groups such as carboxylic group or sulfonyl group; thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acids, and many other compounds known as an antifoggant or a stabilizer can be added to the photographic emulsion of this invention.
The photographic emulsion layers or other hydrophilic colloidal layers of the photographic material of this invention can contain dispersions of water insoluble or slightly soluble synthetic polymers for the purpose of improving the dimensional stability. For example, polymers having as monomer components alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (e.g., vinyl acetate), acrylonitrile, olefin or styrene individually or in combination of two or more thereof, or combinations of the above-described monomers with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxy-alkyl (meth) acrylate, sulfoalkyl (meth) acrylate, or styrenesulfonic acid can be used. Specific examples of these polymers are described in U.S. Patents 2,376,005; 2,739,137; 2,853,457; 3,062,674; 3,411,911; 3,488,708,3,&25,620; 3,607,290; 3,635,715 and 3,645,740 and British Patents 1,186,699 and 1,307,373.
The photographic emulsion layers or other hydrophilic colloidal layers of the photographic material of this invention can contain inorganic or organic hardeners. Specific examples of the hardener which can be employed include chromium salts (e.g., chrome alum, chromium acetate), aldenydes (e.g. formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (e.g., dimethylol urea, methylol dimethylhydantoin), dioxane derivatives (e.g., 2,3 - dihydroxydioxane), active vinyl-containing compounds (e.g., 1.3.5 - triacryloyl - hexahydro - S - triazine, 1,3 - vinylsulfonyl - 2 - propanol), active halogen-containing compounds (e.g., 2,4 - dichloro - 6 - hydroxy - S - triazine), mucohalogenic acids (e.g., mucochloric acid, mucophenoxychloric acid). Such hardeners may be added. individually or in a combination of two or more thereof.
Specific examples of the above-described hardeners and other hardeners which can be employed are described in U.S. Patents 1,870,354; 2,080,019; 2,726,162; 2,870,013; 2,983,611; 2,992,109; 3,047,394; 3,057,723; 3,103,437; 3,321,313; 3,325,287; 3,362,827 and 3,543,292: British Patents 676,628; 825,544 and 1,270,578: German Patents 872,153 and 1,090,427: published examined Japanese Patent Applications 7133/'57 and 1872/'71 and Research Disclosure vol. 176, p. 26 (Dec. 1978).
The photographic material of this invention may contain as a color fog preventing agent a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative or an ascorbic acid derivative.
Specific examples of the color fog preventing agent include those described in U.S. Patents 2,360,290; 2,336,327; 2,403,721; 2,418,613; 2,675,314; 2,701,197; 2,728,659; 2,732,300 and 2,735,365: published unexamined Japanese Patent Applications 92988/'75, 92989/'75, 93928/'75,110337/'75 and 146235/'77: and published examined Japanese Patent Application 23813/'75.
Hydrophilic colloidal layers of the photographic material of this invention may contain an ultraviolet absorbing agent. For example, aryl group-substituted benzotriazole compounds, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds and further, ultraviolet absorbing polymers can be employed in the hydrophilic colloidal layers. These ultraviolet absorbing agents may be fixed in the hydrophilic colloidal layer to which they are added.
Specific examples of the ultraviolet absorbing agent are described in U.S. Patents 3,533,794; 3,314,794 and 3,352,681: published unexamined Japanese Patent Application 2784/'71: U.S. Patents 3,705,805; 3,707,375; 4,045,229; 3,700,455 and 3,499,762: and West German Patent Publication 1,547,863.
The photographic material of this invention may contain water soluble dyes as a filter dye or for preventing irradiation. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these dyes, oxonol dyes, hemioxonal dyes and merocyanine dyes are preferably used. Specific examples of these dyes which can be used in this invention are described in British Patents 546,708; 584,609: 1,265,842 and 1,410,488: and U.S. Patents 2,274,782; 2,286,714; 2,526,632; 2,606,833; 2,956,879; 3,148,187; 3,247,127; 3,481,927; 3,575,704; 3,653,905 and 3,718,472.
Preferable couplers which can be added to hydrophilic colloidal layers of the photographic material of this invention are oil soluble couplers. In addition, polymeric couplers may be incorporated therein.
Magenta couplers which can preferably be used are those of the 5-pyrazolone type, and specific examples thereof are described in U.S. Patents 2,600,788; 2,983,608; 3,062,653; 3,127,269; 3,311,476; 3,419,391; 3,519,429; 3,558,319; 3,582,322; 3,615,506; 3,834,908 and 3,891,445: West German Patent 1,810,464: DE-A-2,408,665; 2,417,945; 2,418,959 and 2,424,467: published examined Japanese Patent Application 6031/'65: published unexamined Japanese Patent Applications 20826/'76, 58922/'77, 129538/ '74, 74027/'74, 159336/'75, 42121/'77, 74028/'74, 60233/'75, 26541/'76, 55122/'78, 94752/'82 and 35858/'82: U.S. Patents 3,163,625, 3,211,553; 3,370,952, 3,451,820; 3,926,436; 4,080,211 and 4,128,427: British Patent 1,247,688: Research Disclosure, No. 18815 and No. 19033: and Japanese Patent Applications 68978/'81, 60264/'81, 89115/'81., 109056/'81, 140667/'81, 2419/'82 and 29683/'82.
Yellow couplers which can be used are compounds of the benzoyl acetanilide type and those of the pivaloyl acetanilide type, and specific examples thereof are described in U.S. Patents 2,875,057; 3,265,506; 3,408,194; 3,551,155; 3,582,322; 3,725,072 and 3,891,445: West German Patent 1,547,868: DE-A-2,219,917; 2,261,361 and 2,414,006: British Patent 1,425,020: published examined Japanese Patent Application 10783/'76: published unexamined Japanese Patent Applications 26133/'72, 73147/'73, 102636/ '76, 6341/'75, 123342/'75, 130442/'75, 21827/'76, 87650/'75, 82424/'77 and 115219/'77: U.S. Patents 3,211,552; 3,370,952; 3,451,820; 3,926,436; 4,080,211 and 4,128,427: Research Disclosure, No. 19033 and No. 21728: and Japanese Patent Application 140667/'81.
Cyan couplers which can be preferably used are compounds of the phenol type and the naphthol type, and specific examples thereof are described in U.S. Patents 2,369,929; 2,434,272; 2,474,293; 2,521,908; 2,895,826; 3,034,892; 3,311,476; 3,458,315; 3,476,563; 3,583,971; 3,591,383; 3,767,411 and 4,004,929: DE-A-2,414,830 and 2,454,329: published unexamined Japanese Patent Applications 59838/'73, 26034/ '76, 5055/'73,146828/'76, 69624/'77 and 90932/'77: U.S. Patents 3,211,552; 3,370,952; 3,451,820; 3,926,436; 4,080,211 and 4,128,427: Research Disclosure No. 21728; and Japanese Patent Application 140667/'81.
Photographic emulsions to be employed in this invention may be spectrally sensitized with methine dyes and others.
Suitable examples of sensitizing dyes which can be used include those described in German Patent 929,080: U.S. Patents 2,493,748; 2,503,776; 2,519,001; 2,912,329; 3,656,959; 3,672,897 and 4,025,349: British Patent 1,242,588: and published examined Japanese Patent Application 14030/'69.
These sensitizing dyes may be employed individually or in combination. Combinations of sensitizing dyes are often employed for the purpose of supersensitization. Typical examples of supersensitizing combinations 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; 3,814,609 and 4,026,707: British Patent 1,344,281: published examined Japanese Patent Applications 4936/'68 and 12375/'78: and published unexamined Japanese Patent Applications 110618/'77 and 109,925/'77.
Hydrophilic colloidal layers of the photographic material of this invention can contain a so-called gas fog preventing agent for the purpose of preventing deterioration of photographic properties, e.g., lowering of developed color density, increase in color stain and fog, from being caused by harmful gases like formaldehyde. Suitable examples of such an agent include amines (including alkylamines, arylamines and heterocyclic amines), amides, cyclic or acyclic ureas, sulfinic acids, imides, active methylenes, hydroxybenzenes, and sulfites.
Specific examples of such compounds are described in published examined Japanese Patent Applications 34675/'71, 38418/'73 and 23908/'76: published unexamined Japanese Patent Applications 473351'73, 43923/'75 and 87028/'75: Japanese Patent Application 177989/'76: U.S. Patent 3,770,431 and 3,811,891: U.S. Defensive Publication T900028: and Research Disclosure vol. 101, RD-10133.
Typical examples of the gas fog preventing agents which can be preferably used include urea, ethylenediurea, ethyleneurea, melamine, hydantoin, allantoin, urazol, parabanic acid, biuret, glycoluril, 1-methylglycoluril, phthalimide, succinimide, benzenesulfinic acid, styrenesulfinic acid polymer, malonic acid, cyanoacetic acid, dimedone barbituric acid, semicarbazide, 5-pyrazolone type magenta couplers, acylacetanilide type yellow couplers, resorcinol, phloroglucinol, 2, 3 dihydroxynaphthalene, and sodium sulfite. The present invention will be explained in greater detail with reference to the following examples.

Example 1

On a triacetyl cellulose support having a subbing layer, the emulsion layers and assistant layers described below were coated in this order to prepare a sample.

First layer: Low sensitivity red-sensitive emulsion layer

100 g of 2-(heptafluorobutyramido) - 5 - {2' - (2",4" - di - t - acylphenoxy)butyramido} - phenol, which functions as a cyan couplers, was dissolved in a mixture consisting of 100 ml of tricresyl phosphate and 100 ml of ethyl acetate, and the resulting solution was mixed with 1 kg of a 10% gelatin aqueous solution with stirring at a high speed to make an emulsion. A 500 g portion of the resulting emulsion was mixed with 1 kg of a red-sensitive, low sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 3 mole %), and coated in a layer having a dry thickness of 2 um (corresponding to a dry coverage of 0.5 g silver per square meter).

Second layer: High sensitivity red-sensitive emulsion layer

100 g of 2 - (heptafluorobutyramido) - 5 - {2' - (2",4" - di - t - acylphenoxy)butyramido} - phenol, which functions as a cyan coupler, was dissolved in a mixture consisting of 100 ml of tricresyl phosphate and 100 ml of ethyl acetate, and the resulting solution was mixed with 1 kg of 10% gelatin aqueous solution with stirring at a high speed to make an emulsion. A 1 kg portion of the resulting emulsion was mixed with 1 kg of a red-sensitive, high sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 3 mole %), and coated in a layer having a dry thickness of 2 um (which corresponds to a dry coverage of 0.8 g silver per square meter).

Third layer: Interlayer

2,5 - Di - t - octylhydroquinone was dissolved in a mixture consisting of 100 ml of dibutyl phthalate and 100 ml of ethyl acetate, and the resulting solution was mixed with 1 kg of a 10% gelatin aqueous solution with stirring at a high speed to make an emulsion. A 1 kg portion of the thus made emulsion was mixed with 1 kg of a 10% gelatin aqueous solution, and coated in a layer having a dry thickness of 1 µm.

Fourth layer: Low sensitivity green-sensitive emulsion layer

A 500 g portion of an emulsion prepared in the same manner as the emulsion in the first layer except that 1 - (2,4,6 - trichlorophenyl) - 3 - {3 - (2,4 - di - t - amylphenoxyacetamido)benzamido} - 5 - pyrazolone was employed as a magenta coupler in place of the cyan coupler was mixed with 1 kg of a green sensitive, low sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 2.5 mole %), and coated in a layer having a dry thickness of 2.0 um (which corresponds to a dry coverage of 0.7 g silver per square meter).

Fifth layer: High sensitivity green-sensitive emulsion layer

A 1 kg portion of an emulsion prepared in the same manner as the emulsion in the first layer except that 1 - (2,4,6 - trichlorophenyl) - 3 - {3 - (2,4 - di - t - amylphenoxyacetamido)benzamido} - 5 - pyrazolone was employed as a magenta coupler in place of the cyan coupler was mixed with 1 kg of a green-sensitive, high sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 2.5 mole %), and coated in a layer having a dry thickness of 2.0 µm (which corresponds to a dry coverage of 0.7 g silver per square meter).

Sixth layer: Interlayer

A 1 kg portion of the emulsion used in the third layer was mixed with 1 kg of a 10% gelatin aqueous solution, and coated in a layer having a dry thickness of 1 pm.

Seventh layer: Yellow filter layer

An emulsion containing yellow colloidal silver was coated in a layer having a dry thickness of 1 um.

Eighth layer: Low sensitivity blue-sensitive emulsion layer

A 1 kg portion of an emulsion prepared in the same manner as the emulsion in the first layer except that a - (pivaloyl) - a - (1 - benzyl - 5 - ethoxy - 3 - hydantoinyl) - 2 - chloro - 5 - dodecyloxycarbonyl- acetanilide was employed as a yellow coupler in place of the cyan coupler was mixed with 1 kg of a blue-sensitive low sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 2.5 mole %), and coated in a layer having a dry thickness of 2.0 µm (which corresponds to a dry coverage of 0.6 g silver per square meter).

Ninth layer: High sensitivity blue-sensitive emulsion layer

A 1 kg portion of an emulsion prepared in the same manner as the emulsion in the first layer except that a - (pivaloyl) - a - (1 - benzyl - 5 - ethoxy - 3 - hydantoinyl) - 2 - chloro - 5 - dodecyloxycarbonyl- acetanilide was employed as a yellow coupler in place of the cyan coupler was mixed with 1 kg of a blue-sensitive, high sensitivity silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 2.5 mole %), and coated in a layer having a dry thickness of 2.0 µm (which corresponds to a dry coverage of 1.0 g silver per square meter).

Tenth layer: Second protective layer

1 kg of the emulsion employed in the third layer was mixed with 1 kg of a 10% gelatin aqueous solution, and coated in a layer having a dry thickness of 2 um.

Eleventh layer: First protective layer

A 10% gelatin aqueous solution containing a chemically unsensitized fine grain emulsion (grain size: 0.15 pm, 1 mole % silver iodobromide emulsion) was coated in a layer having a dry thickness of 1 um at a dry coverage of 0.3 g/m2.
The thus obtained multilayer coated film was named Sample A.
Sample B was produced in the same manner as Sample A except that the iodine content in the emulsion employed in the first layer was changed to 4.0 mole % and further, the iodine content in the emulsion employed in the second layer was changed to 2.5 mole %. Similarly, Sample C, Sample D and Sample E were produced in the same manner as Sample A except that the iodine content in the emulsion employed in the first layer was changed to 3.5 mole %, 4.5 mole % and 4.0 mole % respectively and further, the iodine content in the emulsion employed in the second layer was changed to 1.5 mole %, 2.5 mole % and 3.5 mole % respectively.
Each of these films was exposed to green tight through a wedge for sensitometry, and subjected to the reversal processings described below.
Cyan densities of each sample at the points where magenta densities (D_M) were 2.00 and 1.00 respectively were measured. Under the condition employed for such measurements, the maximum of magenta densities
was 3.20, and that of cyan densities
was 3.14. Results obtained are shown in Table 1.
Next, each of the above-described films was exposed to red light through a wedge for sensitometry and then subjected to the above-described reversal processings. Magenta densities of each of the resulting films were measured at the points of cyan densities (D_c) 2.00 and 1.00, respectively. Results obtained are shown in Table 2.
Therein, D^Max _C was 3.11, and D^Max _M was 3.18.
With respect to color reproducibility and color saturation of green color, it can be said that the greater the difference between magenta density and cyan density under the condition of exposure to green light, the better the saturation of green color. As for the saturation of red color, it can be evaluated by the difference between magenta density and cyan density under the condition of exposure to red light. Also, in this case the greater the difference, the better the saturation is. Therefore, the data in Table 1 and Table 2 are re-edited as follows.
It can be seen from the above table that in the samples of this invention the difference between cyan density and magenta density under green light exposure was greater, and a decrease in the difference between cyan density and magenta density under red light exposure was hardly observed. Therefore, an increase in color saturation was attained.

Example 2

Sample F was prepared in the same manner as Sample B in Example 1 except that the iodine content in the emulsion of the third layer was changed to 4.0 mole % and the iodine content in the emulsion of the fourth layer was changed to 2.5 mole %, and exposed to red light or green light through a wedge for sensitometry, followed by the above-described reversal processings.
Color saturation of this sample was measured and thereby, this sample has proved to be excellent in both red color saturation and green color saturation.

Claims

1. A silver halide multilayer reversal color photographic material, comprising a support having coated thereon a blue sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein at least one or these emulsion layers is comprised of a plurality of sublayers of differeing photographic sensitivity, characterized in that

a) when an emulsion layer is comprised of two sublayers the sublayer of a high sensitivity contains 40 to 80% by weight of the Ag-ions in the emulsion layer and the iodine content of the sublayer of the high sensitivity is lower than that of the sublayer of a low sensitivity by at least 0.3 mole%, and

b) when an emulsion layer is comprised of three sublayers, the sublayer of a high sensitivity and the sublayer of a medium sensitivity contain 40 to 80% by weight of the Ag-ions in the emulsion layer and the iodine content of the sublayer of the high sensitivity and the sublayer of the medium sensitivity is lower than that of the sublayer of the low sensitivity by at least 0.3 mole%.

2. The photographic material according to claim 1, characterised in that

a) the sublayer of the high sensitivity or

b) the sublayer of the high sensitivity and the sublayer of the medium sensitivity contain 45 to 70% by weight of the Ag-ions in the emulsion layer.

3. The photographic material according to claim 1, characterised in that the iodine content of

a) the sublayer of the high sensitivity or

b) the sublayer of the high sensitivity and the sublayer of the medium sensitivity is lower than that of the sublayer of the low sensitivity by 0.5 to 3.0 mole %.

4. The photographic material according to claim 1, characterised in that the sublayer of the high sensitivity or the sublayer of the high sensitivity and the sublayer of the medium sensitivity comprise(s) silver halide having a halide composition containing 0.5 to 5.7 mole % iodide.

5. The photographic material according to claim 4, characterised in that the sublayer of the high sensitivity comprises silver halide having a halide composition containing 1.5 to 4.5 mole % iodide.

6. The photographic material according to claim 4, characterised in that the sublayer of the low sensitivity comprises silver halide having a halide composition containing 0.8 to 6 mole % iodide.

7. The photographic material according to claim 6, characterised in that the sublayer of the low sensitivity comprises silver halide having a halide composition containing 2.0 to 5.0 mole % iodide.