JP2516740B2 - Silver halide photographic material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has high sensitivity, is excellent in graininess in a low density portion of an image, and has a wide exposure latitude. , A silver halide photographic light-sensitive material having improved photographic characteristics.

[Prior art and its problems]

Conventionally, silver halide photographic light-sensitive materials (hereinafter referred to as photographic light-sensitive materials) have been required to have various improvements in performance, but in recent years, they have high sensitivity, and in particular, photographic light-sensitive materials have been developed with the downsizing of cameras. Since the screen size of the material is required to be small, there is an extremely strong demand for technological development concerning high image quality (particularly graininess) in the photographic light-sensitive material. As a technique for improving the graininess, a method using a monodisperse silver halide emulsion is most effective, as disclosed in JP-A-58-28743, 58-14829, 58-100847 and the like. However, these methods have a drawback that the exposure latitude is not widened.

On the other hand, in order to improve this exposure latitude,
(1) A silver halide emulsion layer having the same color sensitivity in each of the blue, green, and red color sensitivity of the light-sensitive material is formed into a plurality of layers having different sensitivities, for example, two to three layers. (2) At least two monodisperse silver halide grains having different average grain sizes are contained in a silver halide emulsion layer, (3) Also, JP-B-58-4
As shown in No. 332, a method of using several kinds of monodisperse silver halide grains having different surface iodide compositions depending on the average grain size in a silver halide emulsion layer is known, but the exposure latitude is improved. However, the exposure latitude and the graininess have reciprocity, and the graininess cannot be said to be sufficiently improved. Particularly in the case of a photographic print image, the improvement in graininess in the low-density region (fog + 0.4 to fog + 0.7) of the photographic light-sensitive material, in which the graininess is most conspicuous and determines image quality, is not satisfactory.

OBJECT OF THE INVENTION The object of the present invention is to have high sensitivity and to be excellent in graininess in a low density region of an image, that is, in a region of a leg (fog + 0.4 to fog + 0.7) in a photographic characteristic curve. An object is to provide a photographic light-sensitive material having an improved exposure latitude.

Specific Structure of the Invention As a result of intensive studies by the present inventor, the above-mentioned object is to provide a photographic light-sensitive material having a plurality of light-sensitive silver halide emulsion layers on a support. It has been found to be achieved by a silver halide photographic light-sensitive material characterized in that at least one of the emulsions represented by the following A and the emulsion represented by the following B is contained as a main component.

A: A substantially monodisperse silver halide emulsion having a silver iodide content of 5 mol% or more B: A silver iodide content of less than 5 mol% and an average grain size of the silver halide emulsion Y is the average grain size X of the silver halide emulsion used in A above, The present invention will be described in detail below.

The photographic light-sensitive material of the present invention, on the support as described above,
It has a plurality of photosensitive silver halide emulsion layers.

In the present invention, the plurality of light-sensitive silver halide emulsion layers are preferably layers having substantially the same color sensitivity but different sensitivities.

Here, "substantially the same color sensitivity" means that each of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer having sensitivity to blue light, green light and red light respectively in a normal color photographic system. In the range of color sensitivity, it means that the color sensitive areas can be regarded as substantially the same even if there is a slight shift.

In the present invention, the photographic light-sensitive material has, on the support, a light-sensitive layer having a plurality of silver halide emulsion layers having substantially the same color sensitivity and different sensitivities as described above. However, it also includes commonly used photographic light-sensitive materials. In the photographic light-sensitive material of the present invention, the arrangement of the light-sensitive silver halide emulsion layers is not limited, but the red-sensitive layer, in order from the support side,
A green-sensitive layer and a blue-sensitive layer are preferred. If necessary, various intermediate layers may be provided between the above layers and / or between the plurality of silver halide emulsion layers in the photosensitive layer.
Alternatively, two or more may be provided.

When the photosensitive layer is composed of a plurality of layers having different sensitivities as described above, the layer farthest from the support side among the plurality of silver halide emulsion layers is set as the most sensitive layer and is directed toward the support. It is preferable that they are arranged so that the photosensitivity becomes lower.

In the photographic light-sensitive material of the present invention, the emulsion represented by A (hereinafter referred to as emulsion A) and the emulsion represented by B (hereinafter referred to as emulsion) in one or more arbitrary layers of the plurality of silver halide emulsion layers described above. (Referred to as B) can be contained in combination. The effect of the present invention is remarkable when it is applied to a layer other than the highest sensitivity layer.

Emulsion A used in the present invention has a silver iodide content of 5 mol%.
As described above, the emulsion is preferably 7 to 15 mol% (preferably a silver iodobromide emulsion), and is a substantially monodisperse emulsion. The substantially monodisperse silver halide grain may be a normal crystal such as a cube, a tetradecahedron or an octahedron, may be composed of twins, or may be a mixture thereof. It is preferably a crystal.

The silver halide grains of Emulsion A used in the present invention preferably have a grain structure composed of two or more layers having different silver iodide contents (core / shell type emulsion). The silver iodide content in the outermost surface layer (shell portion) of the two or more layers is preferably lower than that in the inner layer (core portion). The silver iodide content of the core portion is preferably 6 mol% or more, more preferably 8 to 35 mol%, and further preferably 10 to 25 mol%. The silver iodide content of the shell portion is preferably less than 5 mol%, more preferably 0.5 to 4.0 mol%.

Further, the proportion of the shell portion of the core / shell type silver halide grains is preferably 10 to 80%, more preferably 15 to 80%.
70%, more preferably 20-60%.

When Emulsion A used in the present invention is a core / shell type emulsion, the content difference between the core portion having a high silver iodide content and the shell portion having a low content of silver halide grains has a sharp boundary. It may be one, and the boundary is not always clear. It may be continuously changing. As a method of continuously changing the halogen composition at the boundary between the core and the shell, a method of gradually changing the added halide liquid composition in the double jet method can be used. The silver iodide composition in the core part and the shell part may be unevenly distributed.

As a method for obtaining an emulsion composed of core / shell type normal crystals, a water-soluble silver salt solution and a water-soluble halide solution are added to a gelatin solution containing seed particles which are normal crystals, and a double jet method under control of pAg and pH. Can be obtained by adding. To determine the addition rate, refer to JP-A-54-4
You can refer to No. 8521 and No. 58-49938.

Regarding the method for producing an emulsion comprising twin crystals of core / shell type, reference can be made to JP-A-54-118823, for example. These methods are characterized by forming a silver iodide nucleus in the initial stage and then adding a water-soluble silver salt and a water-soluble halide solution to cause a conversion reaction to form a core made of silver iodobromide.

The core / shell type twin crystal emulsion is produced by ripening a multiple twin nucleus emulsion in the presence of a silver halide solvent to obtain a monodisperse spherical seed emulsion, which is then grown by the double jet method. You can also get it.

In the present invention, the monodispersed silver halide grains are those in which the weight of silver halide contained within a grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains. Preferably 70% or more, particularly preferably 80%
% Or more.

Here, the average particle size is the product n _i × r _i ³ of the frequency n _i and r _i ³ of particles having a particle size gamma _i means the particle diameter r _i at which the maximum (significant figure 3 Digits and minimum digits are rounded off.)

The term "particle size" used herein means the diameter of spherical silver halide grains, and the diameter of grains having a shape other than spherical when the projected image is converted into a circular image having the same area.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is not measured). There shall be more than 1000 discriminants.)

In this specification, the term “average particle size” is used in the meaning defined above.

In the present invention, a highly monodisperse emulsion can be obtained by allowing a hydroxytetrazaindene compound to be present during grain growth of the monodisperse emulsion A.

Emulsion B used in the present invention has a silver iodide content of 5 mol%.
It is an emulsion (preferably silver iodobromide emulsion) of less than 1, preferably 1 to 4 mol%.

The silver halide grains in Emulsion B may be a regular crystal such as a cube, a tetradecahedron and an octahedron, may be composed of twins, or may be a mixture thereof.

The size distribution of silver halide grains in Emulsion B may be monodisperse or polydisperse, but monodisperse is preferable.

Further, the silver halide grains in Emulsion B may be of a core / shell type or of a uniform composition, but the internal silver iodide content is higher than that of the surface thereof. Is preferred.

The average grain size Y of Emulsion B is Y / X with respect to the average grain size X of Emulsion A.
<0.7, preferably 0.3 <Y / X <0.6.

The average particle size of Emulsion A is preferably 0.2 to 5 μm, more preferably 0.3 to 2 μm, and particularly preferably 0.4 to 1.5 μm.

The mixing ratio of emulsion B to emulsion A is preferably low. The mixing ratio of Emulsion B is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and further preferably 15 to 30 mol%.

Emulsion A and Emulsion B in the present invention are preferably chemically sensitized and spectrally sensitized to substantially the same color sensitivity. Therefore, in the present invention, a light-insensitive fine grain silver halide emulsion is mixed. It is fundamentally different from the sensitization technology.

Emulsion A and Emulsion B used in the present invention are contained in combination in the light-sensitive layer as described above, but the light-sensitive layer is a low-sensitivity silver halide emulsion layer (hereinafter simply referred to as "low-sensitivity emulsion layer") When it is composed of two layers having different sensitivities, that is, a sensitivity silver halide emulsion layer (hereinafter referred to as a high sensitivity emulsion layer), both emulsion A and emulsion B are contained in combination with a layer other than the highest sensitivity emulsion layer. It is preferable.

In addition, a non-photosensitive intermediate layer may be provided between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer, and the intermediate layer may be a photographic coupler substantially contained in the high-sensitivity emulsion layer or the low-sensitivity emulsion layer. A photographic coupler that develops in the same hue may be incorporated.

When the photosensitive layer is composed of three layers of a low-sensitivity emulsion layer, a medium-sensitivity emulsion layer and a high-sensitivity emulsion layer, emulsion B is added to the low-sensitivity emulsion layer and high-sensitivity emulsion layer and / or medium-sensitivity emulsion layer. It is preferred to include a combination of emulsion A in the layers.

Furthermore, the above-mentioned non-photosensitive intermediate layer may be provided between the medium-speed emulsion layer and the low-speed emulsion layer, and the above-mentioned photographic coupler may be contained in the non-photosensitive intermediate layer.

With the above-described aspect, the present invention can exert the effect more effectively.

In the present invention, the above-mentioned photosensitive layer can be used as a layer having any color sensitivity, but it is preferable that at least the green-sensitive layer is a photosensitive layer containing the emulsion A and the emulsion B of the present invention. It is preferable that the green-sensitive layer and the red-sensitive layer are more preferable, and the green-sensitive layer, the red-sensitive layer and the blue-sensitive layer are photosensitive layers containing the emulsion A and the emulsion B of the present invention.

As described above, the photosensitive layer in the invention contains Emulsion A and Emulsion B in combination, but may contain other polydisperse emulsion and / or monodisperse emulsion, and further, In addition to Emulsion A and Emulsion B, an emulsion having an arbitrary average grain size, halogen composition and distribution can also be included, but the amount of the silver halide emulsion used is such that it does not impair the characteristics of the present invention. It is preferably 50% or less, more preferably 30% or less of the total number of moles of silver halide emulsion in the photosensitive layer.

Further, as a method of mixing and using the emulsion A and the emulsion B used in the present invention, the grains obtained after the completion of the first ripening (physical ripening) step may be mixed, but preferably the respective grains are mixed. It is preferable that the particles are sensitized and mixed after the completion of 2 aging (chemical aging). Specifically, they may be mixed immediately after the completion of the second ripening, or they may be mixed after setting the emulsion after the ripening.

Next, the method for preparing the silver halide emulsion used in the present invention will be described.

The silver halide grains of the silver halide emulsion used in the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. Alternatively, for example, a method in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size may be used. When growing silver halide grains, the pH in the reaction vessel, pAg, etc. are controlled, and as described in, for example, JP-A-54-48521, an amount of silver that matches the growth rate of silver halide grains is used. It is desirable that the ions and halide ions be sequentially injected and mixed at the same time.

For example, "Basics of Photographic Engineering" (Corona Publishing Co., Ltd., 1979) No. 158
Although there is a general description regarding the above on the page, more specifically, as a method for obtaining a mixed silver halide grain having an extremely narrow grain size distribution in Belgian Patent No. 636,801,
In order to prevent an increase or decrease in the number of particles when adding the residual reaction component to the seed particles that have been formed so as to increase in number in advance, the remaining reaction components soluble silver salt and soluble halogen salt There is disclosed a method for preparing a so-called layered emulsion in which is added to the seed grains at the same time in an addition amount suitable for the growth rate of grains and at the same time, the silver ion concentration of the emulsion is always constant. In addition, Japanese Patent Publication No.
54-158220, 55-124139, 55-142329, 56-30
The seed particles with a narrow distribution similar to the above in No. 122 etc.,
The simultaneous mixing method describes a method of obtaining a desired emulsion by adding a reaction component in an amount corresponding to the growth rate of grains while keeping the silver ion concentration constant, and the present invention can employ any of these techniques. .

Further, excess halogen compounds generated during the preparation of the emulsion used in the present invention or salts and compounds such as nitrates and ammonia, which are by-produced or become unnecessary, may be removed. As a removing method, a Nudel washing method, a dialysis method, a coagulation precipitation method, or the like commonly used in general emulsions can be appropriately used.

In the present invention, in the process of producing a silver halide emulsion,
For example, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof may coexist.

In the present invention, the silver halide emulsion can be spectrally sensitized with various dyes. Dyes used include cyanines, merocyanines, complex cyanines and complex merocyanines (ie tri-, tetra- and polynuclear myanines and merocyanines), oxonol, hemioxonol,
Included are polymethine dyes including styryl, merostyryl and streptocyanin.

Cyanine is a spectral sensitizing dye, quinolium, pyridinium, isoquinolinium, 3H-indolium, benz [e] indolium, oxazolium, oxazolinium, thiazolium, thiazolinium, selenazolium,
Selenazolinium, imidazolium, imidazolinium, benzoxazolinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthothia It contains two basic heterocyclic nuclei linked by a methine bond, such as those derived from zolium, sodium and imidazopyrazinium quaternary salts.

Merocyanine spectral sensitizing dyes include barbituric acid, 2
-Thiobarbituric acid, rhodanine, hydantoin, 2
-Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1,3-dione,
Derived from 1,3-dioxane-4,6-dione, pyrazoline-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-dione. Such an acid nucleus and a cyanine dye-type basic heterocyclic nucleus are bound by a methine bond.

Spectral sensitizing dyes useful for sensitizing silver halide emulsions in the present invention are described in British Patent No. 742,112 and U.S. Pat.
1,846,300, 1,846,301, 1,846,302, 1,84
6,303, 1,846,304, 2,078,233, 2,089,729
No., No. 2,165,338, No. 2,213,238, No. 2,231,658,
2,493,747, 2,493748, 2,526,632, 2,73
No. 9,964 (Reissue Patent No. 24,292), No. 2,778,823, No.
2,917,516, 3,352,857, 3,411,916, 3,43
1,111, 2,295,276, 2,481,698, 2,503,776
No., No. 2,688,545, No. 2,704,714, No. 2,921,067,
2,945,763, 3,282,933, 3,397,060, 3,6
60,102, 3,660,103, 3,335,010, 3,352,68
0, 3,384,486, 3,397,981, 3,482,978,
No. 3,623,881, No. 3,718,470 and No. 4,025,349. Examples of useful dye combinations, including supersensitizing dye combinations, are described in U.S. Patents 3,506,443 and 3,672,8.
No. 98. As an example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-light-absorbing additive, U.S. Pat.
221,805 using thiocyanate in the process of spectral sensitization, bis-triazinylaminostilbene as shown in U.S. Pat.No. 2,933,390, and U.S. Pat.No. 2,937,089 Using sulfonated aromatic compounds, using mercapto-substituted heterocyclic compounds as shown in U.S. Pat.No. 3,457,078, and using iodide as shown in British Patent No. 1,413,826, cited above. Other compounds can be used, including those as described in Gllman "Review of the Mechanism of Supersensitization".

The sensitizing dye may be added at any time such as the start of chemical ripening (also called second ripening) of the silver halide emulsion, the progress of ripening, the end of ripening, or an appropriate timing prior to emulsion coating. .

As a method of adding a sensitizing dye to the above photographic emulsion, various conventionally proposed methods can be applied.
For example, as described in US Pat. No. 3,469,987, the sensitizing dye may be dissolved in a volatile organic solvent, the solution may be dispersed in a hydrophilic colloid, and the dispersion may be added to an emulsion. Still further, the sensitizing dyes of the present invention individually dissolve the same or different solvents, and before adding to the emulsion,
These solutions can be mixed or added separately.

In the present invention, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol or acetone is preferably used as a dye solvent when the sensitizing dye is added to the silver halide emulsion.

In the present invention, when the sensitizing dye is added to the silver halide emulsion, the amount of the sensitizing dye added is 1 × 10 5 per mol of silver halide.
^-5 mol ~ 2.5 × 10 ^-2 mol is preferable, more preferably 1.0
X 10 ^-4 mol to 1.0 x 10 ^-3 mol.

The sensitizing dye can also be used in combination with other sensitizing dyes or supersensitizers.

For the silver halide emulsion according to the present invention, various chemical sensitization methods generally applied can be used. That is, active gelatin; water-soluble gold salt, water-soluble platinum salt, water-soluble halodium salt, water-soluble rhodium salt, water-soluble iridium salt and other noble metal sensitizers; sulfur sensitizers; selenium sensitizers; polyamines, first chloride The chemical sensitization may be performed alone or in combination with a chemical sensitizer such as a reduction sensitizer such as tin.

In the present invention, known sulfur sensitizers can be used. Examples thereof include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents 1,574,944 and 2,4
No. 10,689, No. 2,278,947, No. 2,728,668, No. 3,501,31
3, 3,656,955 each specification, German Patent No. 1,422,86
9, the sulfur sensitizers described in JP-B-56-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is about 10 ^-7 mol to 1 mol of silver halide.
About 10 ^-1 mol is preferable.

In the present invention, selenium sensitization can be used instead of or in combination with sulfur sensitization, and selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, and selenoketones. , Selenoamides, selenocarboxylic acids and esters, selenophosphates, diethyl selenide, and selenides such as diethyl diselenide can be used, and specific examples thereof are U.S. Pat.Nos. 1,574,944 and 1,602,592,
No. 1,623,499.

The addition amount varies over a wide range similarly to the sulfur sensitizer, but as a guide, it is preferably about 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide.

In the present invention, gold iron oxide is +1 as the gold sensitizer.
Valence or +3 may be used, and various gold compounds are used.
Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably in the range of about 10 ^-7 to 10 ^-1 mol per mol of silver halide.

The sensitization method of the silver halide grains in the present invention may be combined with a sensitization method using another noble metal, for example, a metal such as platinum, palladium, iridium or rhodium, or a salt thereof.

In the present invention, reduction sensitization can also be used in combination. The reducing agent is not particularly limited, but examples thereof include known stannous chloride, thiourea dioxide, hydrazine derivatives, silane compounds and the like.

The reduction sensitization is preferably performed during the growth of silver halide grains or after the completion of sulfur sensitization and gold sensitization.

The silver halide emulsion of the present invention can coexist with a known silver halide solvent at any point in the production process. As a silver halide solvent, (a) US Pat. No. 3,271,
No. 157, No. 3,531,289, No. 3,574,628, JP-A-54-1019
No. 54-158917 and Japanese Patent Publication No. 58-30571, and (b) JP-A Nos. 53-82408 and 55.
-77737 and 55-29829 and the like, (c) having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319 Silver halide solvent, (d) imidazoles described in JP-A-54-100717, (e) sulfite, (f) thiocyanate, (g) ammonia, (h) JP-A-57-19622.
No. 8 hydroxyalkyl-substituted ethylenediamines, (i) substituted mercaptotetrazoles described in JP-A-57-202531, (j) substituted benzimidazoles described in JP-A-58-54333. Etc.

The silver halide grains of the present invention, during the production process thereof, at the end of chemical ripening for the purpose of preventing the occurrence of fog during storage or development processing, or for the purpose of stabilizing photographic performance,
Various compounds may be included.

For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles. , Mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole) and the like, mercaptopyrimidines, mercaptotriazines, thioketone compounds such as oxazoline thione, and further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid Known as antifoggants or stabilizers such as amides, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. It can be added a number of compounds. These chemicals are preferably added during chemical ripening or before coating.

As the binder of the silver halide emulsion of the present invention, various hydrophilic colloids including gelatin are used. Gelatin includes not only gelatin but also derivative gelatin. Derivative gelatin includes a reaction product of gelatin acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. The thing etc. are included. Examples of the acid anhydride used for the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, and the like, and the isocyanate compound includes, for example, phenyl. Isocyanate, p-bromophenyl isocyanate, p-chlorophenyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthyl isocyanate and the like can be mentioned.

Furthermore, examples of the compound having an active halogen atom include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m-sulfone. Benzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminobenzenesulfonyl chloride, 2-
Carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2
-Amino-5-methylbenzenesulfonyl chloride,
It includes phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride and the like.

Further, as a hydrophilic colloid for preparing a silver halide emulsion, in addition to the above derivative gelatin and ordinary photographic gelatin, colloidal albumin, if necessary,
Agar, gum arabic, textran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, polyacrylamides, imidized polyacrylamides, caseins such as vinyl alcohol-vinyl cyanoacetate copolymers. Vinyl alcohol polymer containing urethane carboxylic acid group or cyanoacetyl group, polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymer obtained by polymerization of protein or saturated acylated protein and monomer having vinyl group, polyvinyl pyridine, polyvinyl amine , Polyaminoethylmethacrylate, polyethyleneimine, etc. can also be used.

The silver halide emulsion of the present invention contains various surface active agents for various purposes such as coating aids, antistatic properties, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (eg development acceleration, contrast enhancement, sensitization). An agent may be included.

That is, U.S. Patent Nos. 2,240,472 and 2,831,766,
3,158,484, 3,210,191, 3,294,540, 3,5
07,660, British Patents 1,012,495, 1,022,878, and
1,179,290, 1,198,450, U.S. Pat.No. 2,739,891
No., No. 2,823,123, No. 1,179,290, No. 1,198,450,
No. 2,739, 891, No. 2,823, 123, No. 3,068,101, No.
3,415,649, 3,666,478, 3,756,828, British Patents 1,397,218, 3,113,816, 3,411,413, and
3,473,174, 3,345,974, 3,726,683, 3,84
3,368, Belgian Patent 731,126, British Patent 1,138,
514, 1,159,825, 1,374,780, U.S. Pat.No. 2,2
71,623, 2,288,226, 2,944,900, 3,235,91
No. 9, No. 3,671,247, No. 3,772,021, No. 3,589,906,
No. 3,666,478, No. 3,754,924, West German patent application (OLS)
1,961,683 and JP-A-50-117414, 50-59025,
For example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, described in JP-B-40-378, 40-379, 43-13822, etc.)
Polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl or alkyl aryl ether polyethylene glycol esters,
Polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, sugar alkyls Esters, also nonionic surfactants such as urethanes or ethers, triterbenoid saponins, alkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N -Acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene acetate Carboxy such as Kirurin acid esters, sulfo group, phospho group, an anionic surfactant containing a sulfuric acid ester group, phosphoric ester group sugar acidic group,
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl petanes,
Amphoteric surfactants such as amine imides and amine oxides, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and sulfonium containing aliphatic or heterocyclic rings. Alternatively, a cationic surfactant such as a sulfonium salt can be used.

In the silver halide emulsion of the present invention, as a development accelerator,
West German patent application (OLS) 2,002,871 in addition to the above surfactants
No. 2,445,611, No. 2,360,878, British Patent No. 1,352,
It may contain imidazoles, thioethers, selenoethers, etc. described in No. 196 and the like.

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, magenta, cyan and yellow couplers may be contained in combination in the light-sensitive layers adjusted for green sensitivity, red sensitivity and blue sensitivity, respectively. Generally used techniques and materials may be applied. The coupler may be either 4 equivalents or 2 equivalents with respect to silver ions. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be included. Further, the coupler may be such that the product of the coupling reaction is colorless or light-colored.

As the yellow color-forming coupler, various open-chain ketomethylene type couplers can be used. Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color couplers that can be used include U.S. Pat.Nos. 2,875,057, 3,265,506, and 3,40.
No. 8,194, No. 3,551,155, No. 3,582,322, No. 3,725,072
No. 3,891,445, West German patent 1,547,868, West German patent application (OLS) 2,213,461, 2,219,917, 2,261,361.
Nos. 2,414,006 and 2,263,875 can be mentioned.

As a magenta color coupler, a pyrazolone compound,
A pyrazolotriazole compound, an indazolone compound, a cyanoacetyl compound or the like can be used, and a pyrazolone compound is particularly advantageous. Specific examples of magenta color forming couplers that can be used include U.S. Pat.
2,983,608, 3,062,653, 3,127,269, 3,31
1,476, 3,419,391, 3,519,429, 3,558,319
Nos. 3,582,322, 3,615,506, 3,834,908,
3,891,445, West German patents 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,418,959
No. 2,424,467, and Japanese Examined Patent Publication No. 40-6031.

As the cyan color coupler, a phenol compound, a naphthol compound or the like can be used. Specific examples thereof are U.S. Pat.Nos. 2,369,929, 2,434,272, and 2,474,
293, 2,521,908, 2,895,826, 3,034,892
No., No. 3,311,476, No. 3,458,315, No. 3,476,563,
3,583,971, 3,591,383, 3,767,411, West German patent application (OLS) 2,414,830, 2,454,329, JP-A-4
Examples include those described in 8-59838.

Examples of colored couplers include U.S. Pat.
6,560, 2,521,908, 3,034,892, Japanese Patent Sho 44-20
No. 16, No. 3822335, No. 42-11304, No. 44-32461, Japanese Patent Application No. 49-98469, No. 50-118029, West German patent application (OLS)
Those described in 2,418,959 can be used.

Examples of the DIR coupler include U.S. Pat.
Issue, Issue 3,617,291, Issue 3,701,783, Issue 3,790,384,
No. 3,632,345, West German patent application (OLS) No. 2,414,006,
2,454,301, 2,454,329, British Patent No. 953,454,
Those described in Japanese Patent Application No. 50-146570 can be used.

In addition to the DIR coupler, a compound releasing a development inhibitor with development may be contained in the photographic light-sensitive material. For example, those described in U.S. Pat.Nos. 3,297,445, 3,379,529 and West German Patent Application (OLS) 2,417,914 are used. it can. Other JP-A-55-85549, 57-94752, 56-65134, 56
-135841, 54-130716, 56-133734, 56-1358
41, U.S. Patent No. 4,310,618, British Patent No. 2,083,640
Issue, Research Disclosure, No.18360 (1979
Year), No.14850 (1980), No.19033 (1980), No.1
9146 (1980), No.20525 (1981), No.21728 (1982
The couplers described in (Year) can also be used.

Two or more kinds of the above couplers can be contained in the same layer. Also, the same compound may be contained in two or more different layers.

Various methods can be used to introduce the coupler into the photosensitive layer, for example, the method described in US Pat. No. 2,322,027. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), Benzoic acid esters (eg, octyl benzoate), alkylamides (eg, diethyllaurylamide), etc., or organic solvents having a boiling point of about 30 ° C. to 150 ° C., eg, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary It is dissolved in butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

In general, these couplers are preferably added in an amount of 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ mol, per 1 mol of silver in the photosensitive layer. .

The photographic light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color antifoggant, and specific examples thereof are U.S. Patent Nos. 2,360,290, 2,336,327, and the same.
2,403,721, 2,418,613, 2,675,314, 2,70
1,197, 2,704,713, 2,728,659, 2,732,300
No. 2,735,765, JP-A-50-92988, 50-92989
No. 50-93928, No. 50-110337, No. 50-23813 and the like.

As the antistatic agent, diacetyl cellulose, a styrene perfluoroalkylridium maleate copolymer, an alkali salt of a reaction product of a styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, and the like are effective. Examples of matting agents include polymethylmethacrylate, polystyrene and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. In addition, as a latex added for improving the physical properties of the film, a copolymer of an acrylate ester, a vinyl ester, or the like and another monomer having an ethylene group can be exemplified. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.

Examples of the support of the photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
There are glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene and the like, and these supports are appropriately selected according to the intended use of each photographic light-sensitive material.

These supports are subjected to an undercoating process if necessary.

After exposure, the photographic light-sensitive material of the present invention can be developed by a method generally used.

The black-and-white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols and aminobenzenes, and further contains alkali metal salts such as sulfites, carbonates, bisulfites, bromides and iodides. be able to. Color development can be performed by a commonly used color development method. In the reversal method, first develop with a black negative developer,
Then, it is exposed to white light or processed in a bath containing a fogging agent, and color development is carried out with an alkali developing solution containing a color developing agent. The processing method is not particularly limited, and any processing method can be applied. For example, as a typical one, a method of performing bleach-fixing processing after color development, and further performing washing with water and stabilizing processing, or After color development, bleaching and fixing may be separately performed, and if necessary, a method of washing with water and stabilizing treatment may be applied. The photographic light-sensitive material of the present invention is disclosed in JP-A-58-14834,
You may perform water washing alternative stabilization treatment as shown in 58-105145, 58-134634 and 58-18631, and Japanese Patent Application Nos. 58-2709 and 59-89288.

The photographic light-sensitive material of the present invention can be used for black and white in general, and also has various uses such as X-ray, infrared, micro, silver dye bleaching, reversal and diffusion transfer. It can be effectively applied to materials.

Specific Example of the Invention (1) Preparation of Monodisperse Emulsion A silver halide seed emulsion was mixed with an aqueous silver nitrate solution while controlling the pAg and pH in the reaction kettle into a reaction kettle into which an aqueous gelatin solution had been charged. After adding potassium bromide aqueous solution at the same time while controlling the addition time, Kao Atlas Demol N aqueous solution and magnesium sulfate aqueous solution were added, precipitation desalting was performed, gelatin was added, and pAg
= 7.8, pH = 6.0, and the seed particles and gelatin aqueous solution were added to the reaction kettle, and pAg and p
While controlling H, an ammoniacal silver nitrate aqueous solution and a potassium iodobromide aqueous solution were added in proportion to the increase in surface area during grain growth, the composition of the potassium iodobromide aqueous solution was changed at an appropriate particle size, and the addition was continued. . Precipitation desalting is performed in the same manner as the seed emulsion, and gelatin is added to pAg8.3, pH6.0.
Emulsion was obtained. Further, sodium thiosulfate, chloroauric acid and ammonium rhodanate are added, and chemical aging is performed.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added, and gelatin was added to obtain a monodisperse core / shell silver iodobromide emulsion. Here, by changing the ratio of potassium iodide and potassium bromine, the mol% of silver iodide is changed as shown in Table 1, and by changing the addition amounts of ammoniacal silver nitrate and potassium halide, the grain size is changed. Furthermore,
By changing the grain system when changing the composition of the potassium iodobromide aqueous solution during the growth of silver halide grains,
As shown in Table 1, the monodisperse emulsion samples Em-1, 2, 4, 5, 6, 7, 9, 10,
11, 14 and 15 were prepared.

(2) Preparation of polydisperse emulsion Aqueous silver nitrate solution and alkali halide solution were added to gelatin solution and excess halide in advance and allowed to fall naturally into a reaction kettle kept at 60 ° C., and then Kao Atlas Demol N aqueous solution and sulfuric acid were added. Precipitation and desalting were carried out by adding an aqueous magnesium solution, gelatin was added, and pAg7.8, pH6.0
Emulsion was obtained. Furthermore, chemical aging was performed using sodium thiosulfate, chloroauric acid and ammonium rhodanide.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added, and gelatin was added to obtain a polydisperse silver iodobromide emulsion.
The average grain size and grain size distribution were changed by changing the silver iodide mol% by changing the alkali halide composition, and by changing the addition time of the silver nitrate aqueous solution and the alkali halide aqueous solution. The polydisperse emulsions Em-3, 8, 12, 13, and 16 as shown in (4) were prepared.

Example 1 A sample was prepared by successively coating the following layers on a transparent support made of a cellulose triacetate film subjected to subbing processing.

In Example 1, the amount added to the photographic light-sensitive material is shown per 1 m ² , and the silver halide emulsion and colloidal silver are shown in values converted into silver.

Sample 1 Layer 1: Antihalation layer containing 0.3 g of black colloidal silver and 2 g of gelatin.

Layer 2: Intermediate layer containing 1.0 g of gelatin.

Layer 3: Low-sensitivity red-sensitive silver iodobromide emulsion layer containing 1.5 g of silver iodobromide [1.5 g of gelatin and 0.9 g of cyan coupler (C-1) and 0.07 g of colored cyan] Coupler (CC-1) further contains 0.02 g of DIR compound (D-1). Layer 4: 1.5 g of silver iodobromide emulsion layer shown in Table 2 [1.5 g of gelatin and 0.17 g of cyan coupler (C-1) and 0.0
3g color cyan coupler (CC-1) and 0.02g D
It contains an IR compound (D-1). Layer 5: Intermediate layer identical to Layer 2.

Layer 6: Low-sensitivity green-sensitive silver iodobromide emulsion layer containing 1.5 g of silver iodobromide (1.5 g of gelatin and 0.8 g of magenta coupler (M-1) and 0.12 g of colored magenta). Coupler (CM-1) 0.02 g DIR compound (D-
1) is contained. Layer 7: High-sensitivity green-sensitive silver iodobromide emulsion layer containing 1.5 g of silver iodobromide shown in Table 2 [1.5 g of gelatin and 0.17 g of magenta coupler (M-1) and 0.05 g of colored Magenta coupler (CM-1) 0.02g DIR compound (D-
1) is contained. Layer 8: 0.1 g yellow colloidal silver, 0.1 g antifouling agent (HQ-
A yellow filter layer containing 0.06 g of di-n-butyl phthalate in which 1) was dissolved and 1.5 g of gelatin.

Layer 9: Low-sensitivity blue-sensitive silver iodobromide emulsion layer containing 0.9 g of silver iodobromide [1.0 g of gelatin and 1.5 g of yellow coupler (Y-1) and 0.06 g of DIR compound] (D-
1) is contained. Layer 10: High-sensitivity blue-sensitive silver iodobromide emulsion layer containing 1.0 g of silver iodobromide [1.0 g of gelatin and 0.3 g of yellow coupler (Y-1) and 0.06 g of DIR] Compound (D
-1) is contained. Layer 11: Protective layer containing 1.5 g of gelatin.

These nine types of samples were exposed to green color through a wedge according to a conventional method and then subjected to the following processing.

The composition of the processing solution used in each processing step is as follows.

[Color developer composition] [Bleaching liquid composition] [Fixer composition] [Stabilizing liquid composition] The relative sensitivity, granularity, and exposure latitude of each of the color images obtained by the above processing were measured using green light. The width of the exposure latitude is the linear exposure range on the sensitometric curve.
e, hereinafter referred to as LES), the ratio of the exposure dose at both ends is expressed in logarithm. The relative sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives the density of fog +7, and the speed of the granularity is the cherry microdensity of RMS at the density of fog +0.4 and the density of fog +0.7. Tommeter, model P
25 μm using DM-5, type AR (manufactured by Konishi Rokusha Kogyo KK)
Of the standard deviation of the variation of the density value when scanned with the aperture of
It was performed by obtaining the value as 1000 times.

As can be seen from the results in Table 3, in the full-color photographic light-sensitive material according to the present invention, the low density region (fog + 0.4 to
It is clear that the exposure latitude is improved and high sensitivity is realized while maintaining the excellent graininess at (fog + 0.7).

This effect is particularly large when Emulsion A is a core / shell type emulsion. Further, it is understood that this effect is great when the emulsion B is a surface low iodine type core / shell emulsion.

Example 2 Samples Nos. 10 to 15 were prepared by sequentially coating the following layers on a support made of an undercoated cellulose triacetate film from the support side.

First layer: Antihalation layer containing black colloidal silver (dry film thickness 2.0 μm) Second layer: Intermediate layer made of gelatin (dry film thickness 0.8 μm) Third layer: Red-sensitive low-sensitivity silver halide emulsion layer Table- Emulsion shown in 4 (0.25 mol of silver halide per kg,
(Including 20 g of gelatin) was prepared in the usual manner, and this emulsion 1
kg was chemically sensitized with gold and sulfur sensitizers, and as a red-sensitizing sensitizing dye, anhydrous 9-ethyl-3,3'-di- (3-sulfopropyl) -4,5,4 ', 5- Dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-3 ', 9 -Diethyl-3- (4-sulfobutyl) oxythiacarbocyanine hydroxide was added for color sensitization and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.25
g, 0.01 g of 1-phenyl-5-mercaptotetrazole was added.

Next, 400 ml of the following dispersion (COP-1) was added to 1 kg of this emulsion to prepare an emulsion, which was coated so that the amount of silver would be 0.7 g / m ² .

Fourth layer; intermediate layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness: 0.5 μm) Fifth layer: red-sensitive medium-sensitive silver halide emulsion layer Emulsion shown in Table 4 (per 1 kg) 0.25 mol silver halide,
Gelatin (including 25 g) was chemically and color sensitized in the same manner as the above emulsion, and 100 ml of the following dispersion (COP-2) was added to 1 kg of this emulsion to prepare an emulsion. / m
² was applied.

Sixth layer: Red-sensitive high-sensitivity silver halide emulsion layer Emulsion shown in Table 4 (0.25 mol of silver halide per kg,
Gelatin (including 30 g) was chemically and color sensitized in the same manner as in the above emulsion, and 80 ml of the following dispersion (COP-3) was added to 1 kg of this emulsion to prepare an emulsion. / m ²
Was applied.

7th layer: an intermediate layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness: 0.8 μm) 8th layer: green sensitive low-sensitivity silver halide emulsion layer Emulsion shown in Table 4 (per 1 kg) 0.25 mol silver halide,
Gelatin (containing 20 g) was prepared by a conventional method.

1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-as a green sensitizing dye.
Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-
9-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine; anhydrous 9-ethyl-3,3'-di- (3
-Sulfopropyl) -5-6-5'-6'-di-benzooxacarbocyanine hydroxide was added for color sensitization,
Then 0.25 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 0.01 g of 1-phenyl-5-mercaptotetrazole were added.

Next, 350 ml of the following dispersion (COP-4) was added to 1 kg of this emulsion to prepare a green-sensitive low-sensitivity silver halide emulsion.
It was applied so as to be 0.6 g / m ² .

9th layer; same as 4th layer 10th layer; green-sensitive medium-sensitive silver halide emulsion layer Emulsion shown in Table 4 (0.25 mol of silver halide per kg,
Gelatin (including 20 g) was chemically and color sensitized in the same manner as the green-sensitive low-sensitivity silver halide emulsion, and 120 ml of the following dispersion (COP-5) was added to 1 kg of this emulsion to give a green-sensitive emulsion. Prepared a medium-speed silver halide emulsion with a silver content of 2.1 g
It was applied so as to be / m ² .

11th layer: Green-sensitive high-sensitivity silver halide emulsion layer Emulsion shown in Table 4 (0.25 mol of silver halide per kg,
Chemical sensitization and color sensitization of gelatin (containing 30 g) were carried out in the same manner as the above emulsion, and 60 ml of the following dispersion (COP-6) was added to 1 kg of this emulsion to prepare a green-sensitive high-sensitivity silver halide emulsion. Then, it was applied so that the amount of silver would be 1.8 g / m ² .

Twelfth layer: Intermediate layer made of gelatin (0.5 μm dry film thickness) Thirteenth layer: Gelatin layer containing yellow colloidal silver and 2,5-di-tert-octylhydroquinone (0.8 μm dry film thickness)
m) 14th layer: Blue-sensitive low-sensitivity silver halide emulsion layer Emulsion shown in Table 4 (0.25 mol of silver halide per kg,
Chemical sensitization (including 70 g of gelatin) was performed, and 1200 ml of the following dispersion (COP-7) was added to 1 kg of this emulsion to prepare an emulsion.
It was coated so that the amount of silver was 0.3 g / m ² .

Fifteenth layer: Blue-sensitive high-sensitivity silver halide emulsion layer Emulsion shown in Table 4 (0.25 mol of silver halide per kg,
Chemically sensitized (including 45 g of gelatin) and 1 kg of this emulsion
To 200 ml of the following dispersion (COP-7) was added to prepare an emulsion,
It was applied so that the amount of silver was 1.3 g / m ² .

16th layer: 1st protective layer Gelatin layer containing UV absorber and fine grain silver halide emulsion (coating amount 0.15 g / m ^{2 as in} Example 1) (dry film thickness 1.0
μm) Seventeenth layer; second protective layer Gelatin layer containing matting agent (dry film thickness 0.5 μm) In each layer, a gelatin hardening agent and a surfactant were added in addition to the above composition.

 The dispersion used in Example 2 is as follows.

Dispersion (COP-1) Coupler (C-2) 18g and Coupler (CC-1) 0.8g
Was dissolved in a mixture of 18.8 g of dioctyl phthalate and 62 ml of ethyl acetate, added to 310 ml of 5% gelatin aqueous solution containing 1.0 g of sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed by a colloid mill to prepare 400 ml.

Dispersion (COP-2) 2.5 g of coupler (C-2), 1.0 g of coupler (CC-1) and 0.3 g of DIR compound (D-2) were added to dioctyl phthalate 4.0
The mixture was dissolved in a mixture of 14 g of ethyl acetate and 14 ml of ethyl acetate, added to 70 ml of 5% gelatin aqueous solution containing 0.2 g of sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed by a colloid mill to prepare 100 ml.

Dispersion (COP-3) 1.5 g of coupler (C-3), 0.5 g of coupler (C-4) and 0.2 g of DIR compound (D-2) were dissolved in a mixture of 9.0 g of tricresyl phosphate and 8 ml of ethyl acetate. , 62 ml of 5% gelatin aqueous solution containing 0.2 g of sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed by a colloid mill to prepare 80 ml.

Dispersion (COP-4) 10 g of coupler (M-1), 5.5 g of coupler (M-2) and 0.2 g of DIR compound (D-2) were dissolved in a mixture of 15 g of tricresyl phosphate and 51 ml of ethyl acetate, It was added to 260 ml of a 5% gelatin aqueous solution containing 1.8 g of sodium isopropylnaphthalenesulfonate, and emulsified and dispersed by a colloid mill to prepare 350 ml.

Dispersion (COP-5) Coupler (M-1) 3.4g, Colored coupler (CM-
1) 1.3 g and DIR compound (D-2) 0.1 g were dissolved in a mixture of tricresyl phosphate 9.5 g and ethyl acetate 16 ml,
Sodium triisopropyl naphthalene sulfonate 1.1g
Was added to 95 ml of a 5% gelatin aqueous solution containing and was emulsified and dispersed by a colloid mill to prepare 120 ml.

Dispersion (COP-6) 1.0 g coupler (M-1), 0.8 g coupler (M-2),
0.3 g of colored coupler (CM-1) and DIR compound (D-
2) 0.1 g of tricresyl phosphate 5.0 g, ethyl acetate
It was dissolved in 6.5 ml of the mixture, added to 45 ml of a 5% gelatin aqueous solution containing 0.5 g of sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed in a colloid mill to prepare 60 ml.

Dispersion (COP-7) 60 g of coupler (Y-1) was added to tricresyl phosphate 2
5% dissolved in a mixture of 4 g and 20 ml of ethyl acetate and containing 3.0 g of sodium triisopropylnaphthalenesulfonate
The solution was added to 900 ml of an aqueous gelatin solution and emulsified and dispersed by a colloid mill to prepare 1200 ml.

The samples Nos. 10 to 15 thus obtained were evaluated by the same exposure and development as in Example 1.

 The results are shown in Table-5.

As can be seen from the results of Table-5, the full-color photographic light-sensitive material of the present invention has an improved exposure latitude while maintaining excellent graininess at low density (fog + 0.4, fog + 0.7), It is clear that the concentration is achieved.

This effect is particularly great when Emulsion A is a core / shell type emulsion.

Further, this effect is great when the emulsion B is a surface low iodine type core / shell emulsion.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inoue Sohei Goto 1 Sakura-cho, Hino City, Konishi Roku Photo Industry Co., Ltd. (72) Inventor Yoshiharu Mochizuki 1-hour Sakura-cho, Hino City, Konishi Roku Photo Industry Co., Ltd. (56) References JP-A-57-58137 (JP, A) JP-A-57-178235 (JP, A) JP-A-58-14829 (JP, A) JP-A-59-72440 (JP, A) JP-A-59 -74548 (JP, A) JP-A-56-78831 (JP, A) International Publication 83/00234 (WO, A)

Claims (7)

(57) [Claims] 1. A photographic light-sensitive material having a plurality of light-sensitive silver halide emulsion layers on a support, wherein at least one of the light-sensitive silver halide emulsion layers has the emulsion represented by the following A and the emulsion represented by the following B. A silver halide photographic light-sensitive material comprising an emulsion as a main component. A: A substantially monodisperse silver halide emulsion having a silver iodide content of 5 mol% or more B: A silver iodide content of less than 5 mol% and an average grain size of the silver halide emulsion Y is the average grain size X of the silver halide emulsion used in A above, Silver halide emulsion in the range having the relation 2. An emulsion represented by A is a core / shell type silver halide emulsion.
A silver halide photographic light-sensitive material as described in the above item. 3. The halogen according to claim 2, wherein the core in the core / shell type silver halide emulsion comprises a silver halide emulsion having a silver iodide content of 6 mol% or more. Silver photographic light-sensitive material. 4. The emulsion according to claim B is a core / shell type silver halide emulsion.
The silver halide photographic light-sensitive material as described in the item 2, item 2 or item 3. 5. An emulsion represented by B is a substantially monodisperse emulsion, and the emulsions of claims 1 and 2 are characterized in that:
The silver halide photographic light-sensitive material as described in the item 3, item 3 or item 4. 6. The photographic light-sensitive material is a color photographic light-sensitive material, and the first, second, and third claims.
Item 4. The silver halide photographic light-sensitive material according to Item 4 or 5. 7. An emulsion represented by A and an emulsion represented by B are both chemically sensitized and spectrally sensitized to have substantially the same color sensitivity. , Second
The silver halide photographic light-sensitive material as described in the item 3, item 3, item 4, item 5, or item 6.