JPH0473572B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material suitable for photographing. Conventional technology and its problems Silver halide photographic materials are made of paper, glass plates,
At least one photosensitive layer is carried on a support such as a resin film, and the surface layer or outermost layer may be a photosensitive layer, but usually a non-photosensitive protective layer is provided on the photosensitive layer. The surface layer or outermost layer consisting of a photosensitive layer or a non-photosensitive layer generally uses a hydrophilic colloid such as gelatin as a binder. Silver halide photographic materials using this gelatin as a binder in the surface layer have a high coefficient of friction against metal surfaces or other gelatin surfaces, and the surface is very easily damaged by contact or friction. In particular, since the silver halide contained in silver halide photographic light-sensitive materials as a photosensitive substance has the property of being sensitive to pressure, scratches on the surface layer can cause pressure fog and pressure desensitization. This causes defects such as, and has a fatal adverse effect on photographic images. In recent years, the manufacturing process of silver halide photographic materials,
i.e. faster processes such as coating, drying and processing or more complex packaging opportunities during processing;
Diversification of product formats and cameras,
As products have become more compact and have diversified usage conditions such as automatic winding and rewinding, they tend to be manufactured and used under harsh conditions.
The prevention of abrasion or abrasion-induced pressure fog is becoming an increasingly important issue. The protective layer of silver halide photographic materials usually includes:
The surface is roughened by containing fine particles of inorganic substances such as silica, titanium dioxide, and magnesium oxide, and organic substances such as polymethyl methacrylate, cellulose acetate propionate, and polystyrene, so that it becomes similar to other metal surfaces, gelatin surfaces, etc. Measures are being taken to prevent pressure fog by reducing the contact area and controlling the coefficient of friction. However, according to this method, the transparency of the silver halide photographic light-sensitive material may be impaired, and the sharpness of the formed image may be impaired.
Since this tends to cause problems such as deterioration of image quality such as graininess, the amount of fine particles used is naturally limited, and the effect of preventing pressure fog is not sufficiently exerted. U.S. Pat. No. 3,042,522 describes a silver halide photographic material in which the surface layer contains a combination of dimethyl silicone and a specific surfactant to impart slipperiness to the surface layer. , U.S. Patent No. 312,060 describes a silver halide photographic material in which a high boiling point organic solvent and solid paraffin are added to the surface layer by dispersing them in an aqueous gelatin solution; Under high humidity conditions, the film may stick together, resulting in a deterioration in so-called adhesion resistance. Furthermore, it may cause coating troubles during the manufacturing process, deterioration of photographic properties, or the additives in the surface layer may be present in the processing solution. This is accompanied by undesirable side effects such as leaching out and forming precipitates. JP-A-53-13923 and JP-A-53-85421 disclose measures to deal with pressure fog caused by physical pressure from the outside, such as when a silver halide photographic light-sensitive material is bent or tightly hugged. , describes a method of incorporating a high boiling point organic solvent or the like into a silver halide emulsion layer. However, in this method, since the high boiling point organic solvent is not miscible with the hydrophilic binder, when stored under high temperature and high humidity conditions,
There are disadvantages in that the high boiling point organic solvent migrates to the surface layer and adversely affects the inherent photographic properties of the silver halide emulsion. In this way, conventional pressure fog prevention methods produce new defects one after another due to the complex latent factors, and a vicious cycle of improving pressure fog and deteriorating other properties ends in a vicious cycle. You can think of it as if you don't know. 2. Description of the Related Art Silver halide photographic materials, particularly silver halide color photographic sightseeing materials, have been desired to have high sensitivity and excellent image quality. In general, in silver halide photographic materials, there is a proportional relationship between sensitivity and the occurrence of pressure fog, so it is extremely difficult to obtain a material with high sensitivity and little occurrence of pressure fog. In addition, in order to obtain a light-sensitive material that generally has high sensitivity and image quality, especially the sharpness of the dye image formed, it is necessary to consider the light scattering caused by the size of silver halide grains. It is preferable to use monodisperse silver halide grains that can be easily dispersed. However, when these monodisperse silver halide grains were used in a high-sensitivity silver halide emulsion layer, an unexpected deterioration in pressure fog resistance appeared. At present, photographic materials are becoming increasingly difficult to obtain. OBJECTS OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material which prevents the occurrence of pressure fog due to scratches, etc., without impairing photographic properties, transparency, adhesion resistance, etc. A second object of the present invention is to provide a silver halide photograph that can exhibit excellent pressure fog resistance even in a high-sensitivity silver halide emulsion layer containing monodisperse silver halide grains to improve image quality. Our purpose is to provide photosensitive materials. The above object of the present invention is to provide on a support at least one photosensitive layer comprising a plurality of silver halide emulsion layers having different photosensitivity but substantially the same color sensitivity. In the silver halide photographic light-sensitive material, the silver halide emulsion layer having the highest sensitivity among the plurality of silver halide emulsion layers constituting the photosensitive layer has a substantially rounded monodisperse emulsion layer. This is achieved by using a silver halide photographic material containing silver halide grains. DETAILED DESCRIPTION OF THE INVENTION As described above, the silver halide photographic light-sensitive material of the present invention has a plurality of silver halide emulsion layers having different photosensitivity but substantially the same color sensitivity on a support. Any material may be used as long as it is provided with at least one photosensitive layer composed of: A light-sensitive layer composed of a plurality of silver halide emulsion layers having different light sensitivities but substantially the same color sensitivity is a light-sensitive layer that is used for blue light, green light, or red light in ordinary color photography. It refers to a photosensitive layer that is sensitive to any type of light. Therefore, the silver halide photographic material of the present invention having at least one of the above photosensitive layers on a support does not have general color reproduction. A sticky multilayer silver halide color photographic material is included, in which case,
The photosensitive layers may be arranged in the order of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer from the support side, or may be in any other arrangement, but the former arrangement is preferred. Moreover, various non-photosensitive layers such as an intermediate layer may be provided between these photosensitive layers as necessary. Furthermore, the plurality of silver halide emulsion layers constituting each of these photosensitive layers are preferably arranged so that the silver halide emulsion layer furthest from the support is the layer with the highest photosensitivity, and the silver halide emulsion layers are arranged in order toward the support. The layers are arranged so as to lower the photosensitivity, and if necessary, a non-photosensitive layer may be provided between the silver halide emulsion layers. Therefore, the silver halide photographic material of the present invention having at least one such photosensitive layer can have various configurations as known in the art. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, which are constructed by directly stacking high-speed and low-speed silver halide emulsion layers with the same color sensitivity as upper and lower layers, are arranged in this order from the support side. A non-photosensitive layer is provided between each of these photosensitive layers and between each high-sensitivity layer and low-sensitivity layer,
As described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity,
The lower layer is a silver halide emulsion layer with even lower photosensitivity than the middle layer, and the farthest side from the support is the layer with the highest photosensitivity, and the halogenated layer has three layers whose photosensitivity gradually decreases toward the support. Those having a photosensitive layer composed of overlapping silver emulsion layers, or as described in Japanese Patent Publication No. 55-34932, a blue-sensitive layer, a high-sensitivity green-sensitive layer, a high-sensitivity green-sensitive layer, and a high-sensitivity Examples include a structure in which a high-speed red-sensitive layer, a low-speed green-sensitive layer, and a low-speed red-sensitive layer are arranged in this order. In the present invention, the monodisperse silver halide grains contained in the silver halide emulsion layer having the highest photosensitivity are, for example, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, etc. and the crystalline form of the particles is
Any crystal having a hexahedral, octahedral, dodecahedral or other crystal habit may be used as long as it is monodisperse,
Particularly preferred are octahedrons and dodecahedrons. Further, the monodisperse silver halide grains used in the present invention may have a uniform silver halide composition, but may also be core-shell type grains. In the present invention,
These monodisperse core shell type silver halide grains are
It consists of a core made of silver halide containing substantially silver iodide, and a shell made of silver bromide, silver chloride or silver chlorobromide covering this core, and the thickness of the shell is 0.01 to 0.1μ. Certain silver halide grains are preferred. Furthermore, the silver halide composition of the core contains 2 to 15 mol% of silver iodide, and the shell consists essentially of silver bromide, such that the silver iodide content is lower than that near the surface. Preferably, the grains are monodisperse core-shell type silver halide grains consisting essentially of silver iodobromide, which is different from the inside. Furthermore, the monodispersed silver halide grains used in the present invention can best exhibit the effects of the present invention if they have an average grain size of 0.65 μm or more. In the photosensitive layer according to the present invention, the sensitivity difference between the silver halide emulsion layer with the highest photosensitivity and the silver halide emulsion layer with the lowest photosensitivity is 0.1 to △logE.
1.0, more preferably 0.2 to 0.6, and the average grain size of the silver halide grains contained in the silver halide emulsion layer with the highest photosensitivity is 0.5 to 0.5μ, and the silver halide with the lowest photosensitivity The average grain size of the silver halide grains contained in the emulsion layer is preferably 0.1 to 0.8 microns. In this case, the silver halide grains contained in the low-sensitivity layer may be monodisperse or polydisperse, but monodisperse silver halide grains are preferred. In the present invention, the term "monodisperse silver halide grains having substantially roundness" means that, for example, in the case of an octahedral crystal, the radius of curvature of the roundness of the apex of any one triangle on the outer surface is , assuming a triangle with extended sides, r/10 to r/2, where r is the length of one side of the triangle.
In the case of hexahedral and tetradecahedral crystals, when focusing on the polygon with the largest area among the triangles, quadrilaterals, and hexagons that make up the outer surface, the roundness of the vertices of that polygon is The radius of curvature of is r/10 to r/2, assuming the length of the longest side is r, when the sides are extended to form a polygon.
say that it is. In the silver halide photographic material of the present invention,
In the silver halide emulsion layer having the highest photosensitivity, it is preferable that 60% by weight or more of the silver halide contained therein is substantially rounded monodisperse silver halide grains according to the present invention; It is preferable that most of the silver halide grains to be used are such monodisperse silver halide grains. The monodisperse core-shell type silver halide grains are obtained by using a monodisperse silver halide grain as a core and coating the core with a shell. In order to produce the above-mentioned monodisperse silver halide grains, a double-jet method is usually used to obtain monodisperse grains of a desired size while keeping the pAg constant. To obtain silver oxide particles, for example,
The method described in Publication No. 54-48521 etc. can be applied. That is, for example, it is produced by a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. In this case, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the addition rate as a function of time, pH, pAg, temperature, and other conditions. Here, since the particle size distribution of the monodisperse silver halide grains forms a substantially normal distribution, the standard deviation can be easily determined. If the width of the distribution is defined by the relational expression: standard deviation/average grain size x 100 = width of distribution (%), then the width of the distribution of the monodisperse silver halide grains according to the present invention is:
It is preferably 20% or less. In order to produce the silver halide emulsion constituting the silver halide emulsion layer with the highest photosensitivity according to the present invention, cubic grains formed from (100) planes and cubic grains formed from (111) planes are prepared by known methods. A monodisperse silver halide emulsion containing regular octahedral grains, tetradecahedral grains formed from (100) and (111) faces, or a mixture of these three is prepared, and in this emulsion, At any point from the time silver halide grains are formed to the start of chemical ripening, an appropriate amount of silver halide solvent is added to the emulsion at an appropriate time and mixed uniformly, and the solvent is applied to the surface of the silver halide grains. All you have to do is make it work. Note that after the silver halide grains are formed, the silver halide emulsion before being subjected to solvent treatment may be subjected to a desalting treatment (including washing with water). As the silver halide solvent used in the present invention,
Any material may be used as long as it can act on the surface of hexahedral, octahedral, or dodecahedral silver halide grains so that the apexes of the silver halide grains are substantially rounded as defined above, Further, the solvent is preferably a compound that does not react with silver halide to produce silver sulfide. For example, US Pat. No. 3,271,157,
No. 3531289, No. 3574628, each specification, JP-A-1987
-1019 and 54-158917, etc. (a) Organic thioethers, JP-A-53-82408,
(b) Thiourea derivatives described in JP-A-55-77737 and JP-A-55-2982, etc.; (c) Thiourea derivatives described in JP-A-53-144319; AgX with a thiocarbonyl group
Examples of solvents include (d) imidazoles, (e) sulfites, and (f) thiocyanates described in JP-A-54-100717, and further specific compounds include those listed below. . HO−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −S−(CH ₂ ) ₂
-OH (e) K ₂ SO ₃ (f) NH ₄ SCN KSCN The monodisperse silver halide grains according to the present invention contain cadmium salt, zinc salt, lead salt, thallium salt during grain formation, solvent treatment, etc. , iridium salt or its complex salt, rhodium salt or its complex salt,
Alternatively, an iron complex salt or the like may be coexisting. The silver halide emulsion used in the most photosensitive silver halide emulsion layer according to the present invention is doped with various metal salts or metal complex salts at the time of silver halide precipitate formation, grain growth, or completion of growth. It may be applied. For example, gold, platinum,
palladium, iridium, rhodium, bismuth,
Metal salts or complex salts such as cadmium, steel, etc. and combinations thereof can be applied. In the above production method, the Nudel water washing method, dialysis method, or coagulation precipitation method, which is commonly used in general emulsions, can be appropriately used as a means for desalting. The monodisperse silver halide emulsion used in the present invention may be used as is with its grain size distribution, but two or more monodisperse emulsions with different average grain sizes may be mixed at any time after grain formation. They may be mixed and used to obtain a predetermined gradation. Furthermore, the above-mentioned silver halide emulsions may contain sulfur sensitizers such as allythiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts, polyamine salts, etc. , noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or sensitization of water-soluble salts such as ruthenium, rhodium, iridium, etc. agents, specifically ammonium chloroparadate,
Chemical sensitization can be carried out using potassium chloroplatinate, sodium chloroparadide, etc. alone or in combination as appropriate. Further, the above-mentioned silver halide emulsion can contain various known photographic additives. for example
Photographic additives such as those described in Research Disclosure December 1978 Item 17643. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular limitations on the optical sensitization method for the emulsion used in the present invention, and examples include zeromethine dyes, monomethine dyes, dimethine dyes,
Optical sensitization can be carried out using an optical sensitizer such as a cyanine dye such as a trimethine dye or a merocyanine dye alone or in combination (for example, supercolor sensitization). These techniques are described in U.S. Patent Nos.
No. 2688545, No. 291329, No. 3397060, No. 3397060, No.
No. 3615635, No. 3628964, British Patent No. 1195302
No. 1242588, No. 1293862, West German Patent (OLS) No. 2030326, OLS No. 2121780, Special Publication No. 1973-
It is also described in No. 4936, No. 44-14030, etc.
The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material. The emulsion described above can contain various commonly used additives depending on the purpose. Examples of these additives include stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, and polyhydroxy compounds; aldehyde-based, aziridine-based,
Hardeners such as inoxazole type, vinyl sulfone type, acryloyl type, alposimide type, maleimide type, methanesulfonic acid ester type, triazine type, etc.; Development accelerators such as benzyl alcohol, polyoxyethylene type compounds; Chroman type, Claman type , bisphenol-based, and phosphite-based image stabilizers; lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers.
It is also possible to use colloidal silicon oxide. Examples of latics added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like. Hydrophilic colloids used in the emulsion according to the present invention include not only gelatin but also U.S. Pat.
No. 3312553, British Patent No. 1033189, Special Publication No. 39 Sho.
Gelatin derivatives, gelatin polymer grafts, synthetic hydrophilic polymer substances, natural hydrophilic polymer substances other than gelatin, etc. described in Nos. 5514 and 42-26845 can also be used alone or in combination. can. Examples of the support according to the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene tephthalate, polystyrene, and the like. These supports are appropriately selected depending on the intended use of each silver halide photographic material. These supports are subjected to undercoat processing if necessary. In addition, in the multilayer silver halide color photographic light-sensitive material according to the present invention, the photosensitive layer according to the present invention adjusted to have red sensitivity, green sensitivity, and blue sensitivity has cyan,
Techniques and materials used for color photosensitive materials may be used, such as incorporating a combination of magenta and yellow couplers, and known open-chain ketomethylene couplers can be used as the yellow coupler. Among these, benzoylacetanilide and piparoylacetanilide compounds are useful. As magenta couplers, pyrazolone compounds, pyrazolotriazole compounds, indazolone compounds, and cyanoacetyl compounds can be used, and as cyan couplers, phenol compounds, naphthol compounds, etc. can be used. When incorporating these couplers into the photosensitive layer according to the present invention, the couplers contained in the silver halide emulsion layer with the highest photosensitivity and the couplers contained in the silver halide emulsion layer with the lowest photosensitivity are selected. The coupler amount ratio is 1 for low-sensitivity layer to 1 for high-sensitivity layer by weight.
0.15-0.5 is preferred. Furthermore, the ratio of coupler to silver halide in these layers is 0.016 to 0.03 mole of coupler per mole of silver halide in the silver halide and emulsion layer with the highest sensitivity;
Photographic coupler 0.06 to 1 mole of silver halide in the silver halide emulsion layer with the lowest photosensitivity
Preferably it is 0.10 mol. In addition to couplers, these silver halide emulsion layers contain, for example, colored couplers, development inhibitor-releasing substances (DIR substances), timing DIRs, and other substances to prevent unnecessary fogging and contamination due to air oxidation of the developing agent. It may also contain a hydroquinone derivative. Specific Uses of the Invention After exposure, the silver halide photographic material of the invention can be developed by a commonly used known method. The color developing solution that can be used in the present invention preferably has an aromatic primary amine color developing agent as a main component. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Diamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-
dodecylamino)-toluene, 2-amino-5-
(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)
Aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-5-
(N-ethyl-N-β-methoxyethyl)aminotoluene and the like. Development is followed by the usual steps of bleaching, fixing or bleach-fixing, washing and drying to remove silver and silver halides. Specific effects of the invention According to the silver halide photographic material of the invention,
It is possible to satisfactorily prevent the occurrence of pressure fog due to scratches and the like during manufacturing or use without impairing photographic properties such as sensitometric properties. In particular, even in high-sensitivity silver halide emulsion layers containing monodisperse silver halide grains to improve image quality, good pressure fog resistance can be achieved without causing disadvantages such as desensitization. As described above, the silver halide photographic material of the present invention provides a highly sensitive and high image quality photographic material, especially as a silver halide color photographic material for photographing. Specific Examples of the Invention The present invention will be explained in more detail with reference to specific examples below, but the embodiments of the present invention are not limited thereto. Example 1 [Preparation of monodispersed emulsion] Into a reaction vessel, silver halide seed particles and gelatin aqueous solution were charged in advance, and pAg and
While controlling the pH, add an ammoniacal silver nitrate aqueous solution and potassium iodide and potassium bromide aqueous solutions in proportion to the increase in surface area during grain growth.
By changing the alkali halide composition, the silver iodide content was adjusted to 7 mol%, and by changing the amounts of ammoniacal silver nitrate and potassium halide, the particle size and pAg during the reaction were adjusted.
The crystal habit was changed by changing the value. The core/shell emulsion was produced by the method described in Japanese Patent Application Laid-open No. 54-48521. Thereafter, each emulsion was divided into two parts, and one part was subjected to a desalting operation to remove excess salt and used as a comparison emulsion. To the octahedral emulsion, 40 mg/Ag x 1 mol per 1 mol of tetramethylthiourea silver halide was added and treated by stirring at 60°C for 30 minutes, followed by desalting treatment in the same manner as the comparative emulsion. pAg was adjusted to 8.2 at 40°C. Furthermore, each emulsion was subjected to optimal gold sensitization and sulfur sensitization, and after ripening, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 6-
Nitrobenzimidazole was added and gelatin was further added to obtain a monodisperse silver iodobromide emulsion. Table 1 shows the monodispersed silver iodobromide emulsion (14
Species).

[Table] [Preparation of photosensitive material] Sample 1 was prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film. (In all examples below, the amount added to the silver halide color photographic light-sensitive material is shown per 1 m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver.) (Preparation of Sample-1 ) Layer 1: 0.4g black colloidal silver and 3g gelatin
An antihalation layer containing g. Layer 2: A layer containing 1.2 g of a low-speed green-sensitive silver iodobromide emulsion (an emulsion obtained by color-sensitizing emulsion sample K listed in Table 1 above to green-sensitivity). 2.2 g gelatin and 0.8 g 1-(2,4,
6-trichlorophenyl)-3-[3-(2,4-
di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.016 g of 4-octadecylsuccinimide-2-(1-phenyl-5-
Tetrazolylthio)-1-indanone DIR compound (hereinafter referred to as D-1) and 0.15 g of 1-(2,
4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) A low-speed green-sensitive emulsion layer containing 0.95 g of tricresyl phosphate dissolved therein. Layer 3: A layer containing 1.8 g of a highly sensitive green-sensitive silver iodobromide emulsion (an emulsion obtained by color-sensitizing emulsion sample A listed in Table 1 above). High speed green sensitive emulsion layer containing 1.9 g of gelatin and 0.25 g of tricresyl phosphate in which 0.2 g of magenta coupler (M-1) and 0.049 g of colored magenta coupler (CM-1) were dissolved. Layer 4: Protective layer containing 2.3g gelatin. Subsequently, in exactly the same manner as the samples obtained above, a total of 10 types of samples were prepared by changing the combinations of the emulsions used in layer 2 and layer 3, respectively, according to Table 2 below. Samples 1 to 10 respectively
And so.

【table】

[Table] [Measurement of pressure fog] After applying a load to the photosensitive surface of these 10 types of unexposed samples using a scratch hardness tester with a needle head of 0.3 mm, they were processed according to the following processing steps to eliminate pressure fog. The generated load was measured. The results are shown in Table 3. Development process (38°C) Processing time Color development...3 minutes 15 seconds Bleaching...6 minutes 30 seconds washing...3 minutes 15 seconds fixation...6 minutes 30 seconds water washing...3 minutes 15 seconds stability Bath: 1 minute 30 seconds In each treatment step, the composition of the treatment liquid used was as follows. Color developer composition: 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 , adjust to PH10.0. Bleach composition: Ethylenediaminetetraacetate iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
1.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1 and adjust the pH to 6.0. Fixer composition: Ammonium thiosulfate 50% aqueous solution 162ml Anhydrous sodium sulfite 12.4ml Add water to bring the solution to 1 and adjust the pH to 6.5. Stable solution composition: Forman phosphorus 37% aqueous solution 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1.

[Table] As is clear from the above results, it is clear that Samples 4 to 10 according to the present invention have significantly better resistance to pressure fog due to scratches than the comparative samples. Example 2 Sample 11 was prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film. Layer 1: Layer 1 described in Example 1 Layer 2: Layer containing 1.4 g of a low-sensitivity green-sensitive silver iodobromide emulsion (an emulsion color-sensitized to green-sensitivity from emulsion sample L listed in Table 1 above) . 1.2 g gelatin and 0.8 magenta coupler (M-1) and 0.016 g DIR compound (D-
1), plus 0.15g colored coupler (CM-1)
A low-speed green-sensitive emulsion layer containing 0.95 g of tricresyl phosphate dissolved therein. Layer 3: A layer containing 0.9 g of a medium-sensitivity green-sensitive silver iodobromide emulsion (an emulsion obtained by color-sensitizing emulsion sample K listed in Table 1 above to green sensitivity). Medium green sensitive emulsion layer containing 0.9 g gelatin and 0.25 g tricresyl phosphate in which 0.24 g magenta coupler (M-1) and 0.015 g colored magenta coupler (CM-1) were dissolved. Layer 4: A layer containing 1.3 g of a highly sensitive green-sensitive silver iodobromide emulsion (an emulsion obtained by color-sensitizing emulsion sample A listed in Table 1 above). High speed green sensitive emulsion layer containing 1.2 g of gelatin and 0.22 g of tricresyl phosphate in which 0.20 g of magenta coupler (M-1) and 0.02 g of colored magenta coupler (CM-1) were dissolved. Layer 5: Protective layer containing 2.3g gelatin. Further Samples 12 to 20 were prepared in exactly the same manner as Sample 11 obtained above by changing the emulsions contained in Layer 2, Layer 3, and Layer 4 to the emulsion samples listed in Table 4 below. .

[Table] The obtained 10 types of samples were treated in the same manner as in Example 1, and the load at which pressure fog occurred was measured. The obtained results are shown in Table 5 below.

[Table] As is clear from the above results, sample 17 of the present invention
It is clear that samples 20 to 20 have significantly better resistance to pressure fog due to scratches than other samples 11 to 16. Samples 19 and 20 using core/shell emulsions also have excellent pressure fog resistance. Example 3 Sample 21 was prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film. Layer 1: Layer 1 as described in Example 1 Layer 2: Layer containing 1.4 g of a low-speed red-sensitive silver iodobromide emulsion (an emulsion color-sensitized to red sensitivity from emulsion sample K listed in Table 1 above) . 1.2 g of gelatin and 0.8 g of 1-hydroxy-2-[δ(2,4-di-t-amylphenoxy)-n-butyl]naphthamide, hereinafter referred to as cyan coupler (C-1) (and 0.065 g of 1
-Hydroxy-4-[4-(1-hydroxy-8-
Acetamide-3,6-disulfo-2-naphthylazo(phenoxy)-N-[δ-(2,4-di-t
Contains 0.65 g of tricresyl phosphate in which -amylphenoxy)butyl-2-naphthamide, disodium (hereinafter referred to as colored cyan coupler (CC-1)) and 0.015 g of DIR compound (D-1) are dissolved. Low sensitivity red-sensitive emulsion layer. Layer 3: A layer containing 1.3 g of a highly sensitive red-sensitive silver iodobromide emulsion (an emulsion obtained by color-image-sensing emulsion sample A listed in Table 1 above). High-speed red-sensitive emulsion layer containing 1.2 g of gelatin and 0.23 g of tricresyl phosphate in which 0.21 g of cyan coupler (C-1) and 0.02 g of carado cyan coupler (CC-1) were dissolved. Layer 4: 0.04 g of di-n-butyl phthalate (hereinafter referred to as DBP) in which 0.07 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)) was dissolved and Intermediate layer containing 0.8g gelatin. Layer 5: Layer 2 as described in Example 2 Layer 6: Layer 3 as described in Example 2 Layer 7: 0.15 g yellow colloidal silver, 0.2 g antifouling agent (HQ-1) dissolved Yellow filter layer containing 0.11g DBP and 1.5g gelatin. Layer 8: Layer containing 0.5 g of a low-speed blue-sensitive silver iodobromide emulsion (emulsion of emulsion sample K listed in Table 1 above). 1.9 g gelatin and 1.5 g α-pivaloyl-α-(1-benzyl-2-phenyl-3,5
-Dioxoimidazolidin-4-yl)-2'-chloro-5'-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (hereinafter referred to as yellow coupler (Y-1)) was dissolved in 0.6
A low-speed blue-sensitive emulsion layer containing g DBP. Layer 9: Layer containing 1.0 g of a highly sensitive blue-sensitive silver iodobromide emulsion (emulsion of emulsion sample A listed in Table 1 above). High-speed blue-sensitive emulsion layer containing 0.65 g of tricresyl phosphate in which 1.5 g of gelatin and 1.3 g of yellow coupler (Y-1) were dissolved. Layer 10: Protective layer containing 2.3g gelatin. Similar to sample 21 obtained above, the layer 2,
Samples 22 and 23 were prepared by changing the emulsions contained in layer 3, layer 5, layer 6, layer 8, and layer 9 to other emulsion samples as shown in Table 6 below.

[Table] The three types of samples obtained were treated in the same manner as in the examples, and the load at which pressure fog occurred in each photosensitive layer was measured. The obtained results are shown in Table 7 below.

[Table] As is clear from the above results, it is clear that Samples 22 and 23 according to the present invention have significantly better resistance to pressure fog due to scratches than the other Sample 21. (3) Further, an unexposed sample identical to Samples 21 to 23 was placed in close contact with a transparent wedge, exposed to white light, and developed in the same process as in Example 2 to obtain a sample with a dye image. Ta. The sensitivity and fog of the obtained color images were measured and the obtained results are shown in Table 8. The fog in the table is the value obtained by subtracting the mask density from the minimum density value. The sensitivity represents a relative value, with the sensitivity value of the magenta image forming unit layer of Sample 21 exposed to white light being 100.

[Table] As is clear from the above results, the samples of the present invention
Samples 22 and 23 are not inferior in photographic performance compared to the other sample 21, and in fact have improved sensitivity.

Claims (1)

[Claims] 1. A silver halide photograph in which at least one photosensitive layer comprising a plurality of silver halide emulsion layers having different light sensitivities but substantially the same color sensitivities is provided on a support. In the photosensitive material, the silver halide emulsion layer with the highest sensitivity among the plurality of silver halide emulsion layers constituting the photosensitive layer includes:
A silver halide photographic light-sensitive material characterized by containing monodisperse silver halide grains having substantially round shapes.