JPS61243443A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material superior in color reproductivity and wide exposure latitude by incorporating an emulsion higher in silver iodide content and another emulsion lower in said content to a photosensitive silver halide emulsion layer. CONSTITUTION:At least one of photosensitive silver halide emulsion layers is composed essentially of the monodispersed emulsion A having a silver iodide content of >=6mol% and the emulsion B having an average grain diameter same as that of the silver iodide of the emulsion A and a compsn. near the surface same as that of the emulsion A but a silver iodide content lower than that of the emulsion A as the content of the total grains. The emulsion A has a silver iodide content in the shell part lower than that in the core part, thus permitting an interimage effect to be given by the presence of the emulsion contg. a specified amt. of silver iodide, and bidirectionality to be caused between different photosensitive layers to each other.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic material having excellent color reproducibility and sharpness, and improved exposure latitude and graininess. This invention relates to a silver halide photographic material suitable for color use.

[Prior art and its problems]

One of the properties required for color photographic materials is that when one color-sensitive layer forms a dye image, the oxidized product of the color developing agent generated therein causes the other color-sensitive layers to develop color. It should not be cloudy, that is, it should have high color purity. In addition, one of the important characteristics, especially for negative photographic materials, is that they can faithfully reproduce a wide exposure range, that is, have a wide exposure latitude. A further characteristic is that the image is smooth and free from roughness, ie, has good graininess.
Various attempts have been made to impart these properties to multilayer silver halide color photographic materials (hereinafter referred to as color photographic materials), but these have not yet been sufficient.

Conventionally, compounds that release development inhibitory substances during development, so-called D
It is known to include an IR compound in a color photosensitive material. Various types of these DIR compounds are used. For example, a so-called DIR coupler reacts with an oxidized form of a color developing agent during development to form a coloring dye and releases a development inhibitor; , so-called DIR substances that do not form coloring dyes, those that directly release development inhibitory substances (by reacting with oxidized products of color developing agents), and those that indirectly release development inhibitory substances, such as JP-A-54- No. 145135, No. 57-154234, No. 58-162949, No. 58-205150, No. 5
No. 9-195643, No. 59-206834, No. 59
-206836, 59-210440, 60-
7429 etc. (hereinafter referred to as timing D)
Examples include -, which is called an IR compound. In this specification, those exhibiting the above-mentioned DIR effect are collectively referred to as DIR compounds.

When these DIR compounds are used in color photosensitive materials: 1.
During development, a development inhibiting substance is released from the DIR compound and has the effect of inhibiting the development of other silver halide emulsion layers, the so-called interimage effect (interlayer effect).

1.1. E effect) can be obtained. Conventionally, attempts have been made to utilize this interimage effect to improve the color purity, especially the color purity of primary colors, when reproducing the colors of objects on color photosensitive materials for printing.

That is, a red-sensitive silver halide emulsion layer containing a diffusion-resistant cyan coupler, a green-sensitive silver halide emulsion layer containing a diffusion-resistant magenta coupler, and a diffusion-resistant yellow coupler are sequentially contained on a support. A DIR compound is incorporated into a 2-photosensitive material having a blue-sensitive silver halide emulsion layer to improve color purity. However, when this type of compound is used, it is possible to exhibit the inhibitory effect at a specific distance from the developed silver halide grains, resulting in a significant improvement in color purity based on the so-called interimage effect. . Also, the sharpness is improved based on the adjacent effect, but
It has the disadvantage that the graininess improvement effect is small.

No. 128,528/1983 has a silver halide emulsion layer containing a double-layered emulsion, and a different spectral sensitization from this emulsion layer to utilize the development effect between the other emulsion layers and 9. A color light-sensitive material for reversal is disclosed which has an improved intermediate image effect. Also U.S. Patent 3,404.00
No. 2 discloses a color light-sensitive material for the diffusion transfer method, which has emulsion layers having different silver iodide contents and has an improved interimage effect.

These technologies utilize iodide ions released during development.
Although it utilizes the interimage effect, it has the disadvantage that the interimage effect due to iodine ions is smaller than that of DIR compounds, and the effect cannot be controlled.

Generally speaking, as a characteristic of photography, when imagewise exposure is performed on a light-sensitive material, it is necessary that even if there is overexposure or underexposure, an imagewise image is formed with the brightness and darkness of the subject as appropriate on the negative of the light-sensitive material. A light-sensitive material with a wide latitude for overexposure and underexposure has been strongly desired.

However, in reality, it is a common problem with light-sensitive materials that graininess and sharpness deteriorate as exposure increases.

For example, to obtain a light-sensitive material with a wide exposure latitude,
Conventional techniques include a method of constructing a light-sensitive material using a silver halide emulsion with a wide grain size distribution, a method of constructing a light-sensitive material using a silver iodobromide emulsion having a high silver iodide content, or a light-sensitive material. Methods have been proposed to reduce the amount of silver halide in silver halide emulsions used in the production of silver halide emulsions, but all of these techniques have the problem of significant deterioration of graininess and reduction of the photosensitivity of the photosensitive material. Remaining.

In addition, technology has been provided that attempts to widen the exposure latitude of photosensitive materials without deteriorating graininess.
It's true. For example, in negative peripheral 2-photosensitive materials, DIR
A method of reducing the color density of an image using a compound,
Alternatively, methods have been disclosed in which the color density of the image is similarly lowered by using a coupler having a large amount of equivalents, but in these techniques, in order to compensate for the tonality of the light-sensitive material, a large amount of nitrogen is used. Silver oxide is required, which is a big disadvantage in terms of resource conservation and cost.

A method of forming a light-sensitive material by using a mixture of several types of emulsions containing silver halogenide grains having different average grain sizes is also known, but the effect of improving the exposure latitude was not sufficient.

Furthermore, a technique has been disclosed in which the silver halide emulsion is an emulsion consisting of monodisperse silver halide grains, and a photographic material is constructed by using a mixture of several types of these emulsions. For example, in Japanese Patent Publication No. 58-4332, several types of halides having the same grain size and different silver iodide contents in the surface layer (near the surface of the silver halide grains) of monodisperse silver halide grains are disclosed. By using a mixture of silver oxide emulsions, a wide range of exposure latitude is achieved. However, this method has the disadvantage that the effect of improving graininess is not so large as to be satisfactory, and that the emulsion does not have good storage stability over time.

[Purpose of the invention]

The purpose of the present invention is to have excellent hexagonal reproducibility and sharpness,
Another object of the present invention is to provide a color photosensitive material with improved exposure latitude and graininess.

Still another object of the present invention is to provide a light-sensitive material containing a silver halide emulsion that has excellent storage stability over time.

[Structure of the invention]

The inventors have conducted extensive studies to achieve the above-mentioned objective,
The present invention has been completed by finding that the object can be achieved by the photosensitive material shown below. In a photographic material having a plurality of photosensitive silver halide seed grains on a support, the photosensitive halogenated A silver halide photographic material characterized in that at least one of the silver emulsion layers contains an emulsion represented by A and an emulsion represented by B below as main components.

A: A substantially monodisperse emulsion having a silver iodide content of 6 mol % or more as a whole grain.

B: It has substantially the same average grain size as the silver iodide in the emulsion shown in the above entry, and the composition near the grain surface is substantially the same as that of the emulsion shown in A, but the grain as a whole An emulsion with a lower silver iodide content than the emulsion shown by A.

In the present invention, monodisperse silver halide grains are those in which the silver halide emulsion contained within a grain size range of ±20% around the average grain size A accounts for 60% or more of the total weight of the silver halide grains. It is preferably 70% or more, even more preferably 80% or more. The average particle size a is the frequency of particles having the particle size r. It is defined as the particle size γ1 (three significant figures) when the product n, xγi3 of degrees ni7r,3 is maximum.

The particle size here means, in the case of spherical halogenated particles,
In the case of particles having a shape other than spherical, this is the diameter when the projected image is converted into a circular image with the same area. The particle diameter can be obtained, for example, by photographing the particles with an electron microscope magnifying the particles 10,000 to 50,000 times, and actually measuring the particle diameter or the area of the projected image on the burrito. The number of particles to be measured is indiscriminately set to 1000 or more.

In the present invention, silver halide grains consisting of substantially monodisperse silver halide grains (hereinafter referred to as monodisperse silver halide grains of the present invention) may be normal crystals or twin crystals, and the shape may be, for example, It may be any of hexahedrons, octahedrons, dodecahedrons, plate-like bodies, and spherical bodies, or it may be a mixture of these various shapes.

You can.

Although the method for producing the monodisperse silver halide grains of the present invention is not limited, for example, grains of a desired size can be obtained by a double jet method while controlling pAg and... Further, highly monodisperse silver halide grains can be obtained by the method described in JP-A-54-48521 and the like. 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. At this time, silver halide grains having a higher degree of monodispersity than K can be obtained by appropriately selecting the addition rate of -1 pAg, temperature, etc.

The twinned monodisperse silver halide grains of the present invention are disclosed in JP-A-51
-39027, 51-88017, 52-15
No. 3428, No. 54-118823, No. 54-142
It can be made by the method described in No. 329, etc.

In addition, twinned emulsions containing highly monodisperse silver halide grains are produced by forming core grains consisting of silver iodobromide multiple twins with a silver iodide content of 5 mol % or less in the presence of a silver halide composition. It can be obtained by physically ripening to produce a mass of monodisperse spheres, and then growing the grain by adding a water-soluble silver salt and a water-soluble halide. Furthermore, monodispersity can be improved by making a tetrazaindene compound present during the growth of the emulsion.

The silver iodide content in the whole grains of the emulsion A (hereinafter referred to as emulsion A) according to the present invention is 6 mol% or more, preferably 7 to 30 mol%, more preferably 9
It is a silver iodobromide emulsion having a silver iodide content of ~15 mol%.

If the silver iodide content of emulsion A is less than 67 lXK, the desired effects of the present invention cannot be obtained.

In the present invention, the emulsion A preferably used has a grain structure composed of two or more layers having different silver iodide contents, and the outermost layer of the two or more layers is preferably used as the emulsion A. The silver iodide content in the layer (felt part) K is preferably lower than the silver iodide content in the inner layer (core part). The silver iodide content in the core is preferably 7 to 40 mol%, more preferably 8 to 3 mol%.
It is 0 mol%, more preferably 9 to 20 mol%.

The silver iodide content in the shell portion is preferably less than 6 mol%, more preferably 1 to 5 mol%.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide composition may have a sharp boundary, or may have a continuous boundary that is not necessarily clear. It may be something that changes. As a method of continuously changing the halogen composition at the boundary between the core and the shell, a method of gradually changing the composition of the added halide liquid in the double jet method can be used. The silver iodide composition in the core part and the shell part may be unevenly distributed.

Furthermore, the core/
The proportion occupied by the shell portion of Fell-type silver halide grains is 5
It is preferably ~80% (mol % based on the total number of moles of halogenation), more preferably 10-70%, and furthermore, KtEtL< is 20-60S.

The method for producing a core/shell emulsion consisting of normal crystals is as follows:
For example, in a gelatin solution containing normal crystalline seed particles,
A water-soluble silver salt solution and a water-soluble halide solution were mixed with PAg and -
can be obtained by adding by double jet method under the control of In determining the addition rate, reference may be made to JP-A-54-48521, JP-A-58-49938, and the like.

The method for producing a core/shell type emulsion consisting of twin crystals is as follows:
For example, Japanese Patent Application Laid-open No. 118823/1983 can be referred to. These methods are characterized by initially forming silver iodide nuclei, 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.

Core/shell type twin emulsions are produced by ripening a multiple twin core emulsion in the presence of a silver halide composition to form a monodisperse spherical seed emulsion, which is then processed using the double jet method in which the halogen composition is controlled. It can be obtained even if it is grown well.

The distribution state of silver iodide in the silver halide grains can be detected by various physical measurement methods. It can be investigated by measuring the luminescence at

In the present invention, the silver halide composition near the grain surface of the emulsion B (hereinafter referred to as emulsion B) is substantially the same as the halogen composition near the grain surface of emulsion A. Substantially the same means that the molar difference in silver iodide content is 1
It means less than %.

Emulsion B according to the present invention is characterized in that the average silver iodide content of the silver halide grains as a whole is lower than that of emulsion A. The average silver iodide content is lower than that of emulsion A when the average silver iodide content of emulsion B is 1 mol% compared to the silver iodide content of emulsion A.
or more, more preferably 2 mol% or more 1O
The effect is particularly great when the content is low, in the range of less than mol%.

Emulsion B related to #iK of the present invention may be monodisperse or polydisperse, but a monodisperse emulsion is preferred. The preferred range of monodispersity in this case follows the definition of emulsion A above.

Further, the grain shape of the silver emulsion B according to the present invention may be normal crystal or twin crystal, for example, hexahedral, octahedral, dodecahedral, plate-like, or spherical. It may also be a mixture of these various shapes.

Furthermore, the intragrain no-gen composition of emulsion B according to the present invention may be uniform, or it may be of the so-called core/shell type in which the internal and surface compositions are different, but it is preferable that it be of the core/shell type. preferable.

Emulsion A and Emulsion B according to the present invention are preferably substantially composed of silver iodobromide, and may contain silver chloride as long as the effects of the present invention are not impaired.

The present invention is characterized in that the grain sizes of emulsion A and emulsion B are substantially the same, and "substantially the same" means the ratio of the average grain size 7A of emulsion A to the average grain size 7B of emulsion B. is FB/
A A (Say that it is 0, 7 (A is determined by the method described above.)

Emulsion A and emulsion B according to the present invention are preferably color sensitized to have substantially the same color sensitivity.

Further, emulsion A and emulsion B according to the present invention are preferably chemically sensitized so that their relative photographic sensitivities are within 50 to 200%.

Furthermore, the molar mixing ratio of emulsion A and emulsion B in the present invention is preferably in the range of 0.1 to 0.9 when expressed as the ratio of emulsion A (EmA/(翫A+EmB)). And more preferably 0.3 to 0.8.
・→ Ru.

Furthermore, the I-silver halide emulsion layer of the present invention can be applied to any photosensitive layer, such as a blue-sensitive layer, a green-sensitive layer, or a red-sensitive layer.
When each photosensitive layer is composed of two or more layers having different sensitivities, it can be applied to any layer such as a high-sensitivity layer, a medium-sensitivity layer, a low-sensitivity layer, etc.

The emulsion layer consisting of the silver halide emulsion of the present invention can further contain other emulsions as long as the effect of mixing emulsions A and B is not impaired, but the amount of the other emulsions to be mixed is It is preferable to keep it within 30 mol%.

In the present invention, for example, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, etc. may be present in the process of producing the silver halide emulsion according to the present invention.

Further, the silver halide emulsion according to the present invention can be spectrally sensitized using a silver dye. The dye used ((
Includes polymethine dyes, including cyanine, merocyanine, complex cyanine and complex merocyanine (i.e. tri-, tetra- and polynuclear cyanine and merocyanine), oxonol, hemioquinol, styryl, merostyryl and streptocyanine.

Cyanine spectral sensitizing dyes include gynolinium, pyridinium, inquinolinium, 3H-indolium, oxacillium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacylinium, imidazolium, imidazolinium, benzoxacillinium, benzothiazo Lium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium,
Included are two basic heterocyclic nuclei linked by a methine linkage, such as derived from naphthoselenazolium, thiazolinium, dihydronaphthothiazolium, pyrylium and imidazopyrazinium quaternary salts.

Merocyanine spectral sensitizing dyes include barbituric acid, 2-
Thiobarbir II, 0-danine, hydantoin, 2
-Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-inxacillin-5-one, indan-1,3-dione, cyclohexane-1,3-dione, 1,3-dioxane-4,6 cyanines with acidic nuclei such as those derived from diones, pyrazoline-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, mapnonitrile, isoquinolin-4-one and chroman-2,4-dione. The basic heterocyclic nucleus of the pigment type forms a methine bond (including those that are bonded together).

Spectral sensitizing dyes useful for sensitizing silver halide emulsions are described in British Patent No. 742.112 and US Pat.

No. 846.300, No. 1,846,301, No. 1,8
46.302, 1,846.303, 1,84
No. 6,304, No. 2,078,233, No. 2,089
, No. 729, No. 2.165.338, No. 2,213.
No. 238, No. 2,231.658, No. 2,493.7
No. 47, No. 2 493.748, No. 2,526.63
No. 2, No. 2,739.964 (Reissue Patent No. 24,29
2), 2,778.823, 2,917,51
No. 6, No. 3.352゜857, No. 3.411,916
No. 3.431.111, No. 2,295.276, No. 2,481,698, No. 2.503.776,
2,688.545, 2゜704.714, 2,921,067, 2.945.763, 3
．． No. 282,933, No. 3,397.060, No. 3.
660.102, 3.660.103, 3.3
No. 35.010, No. 3.352,680, No. 3.38
No. 4,486, No. 3.397,981, No. 3.482
．． No. 978, No. 3.623.881, No. 3,718.
No. 470 and No. 4,025,349. Examples of useful dye combinations, including supersensitized color combinations, are given in U.S. Pat.
No. 2,898. An example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-light absorbing additive is the use of thiocyanate in the process of spectral sensitization as disclosed in U.S. Pat. No. 2,221,805; 2,933
．． using bis-triazinylaminostilbenes as disclosed in U.S. Pat. No. 390, sulfonated aromatic compounds as disclosed in U.S. Pat.
Using mercapto-substituted heterosalt compounds as taught in U.S. Pat. No. 3,457,078, British Patent No. 1,413
Using iodide as disclosed in No. 826, Gilman et al.
Other compounds can be used, including those described in "The Mechanism on the Super Sensitizer".

The above-mentioned sensitizing dye may be added at the beginning of chemical ripening (also called second ripening) of the silver halide emulsion, during ripening, after ripening, or at an appropriate time prior to emulsion coating, even in a later process. No problem.

Various methods can be used to add the sensitizing dye to the emulsion. For example, US Patent 3°469.9
87, by dissolving the sensitizing dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to the emulsion. Still further, the sensitizing dyes of the invention can be dissolved individually in the same or different solvents and the solutions can be mixed together or added separately before being added to the emulsion.

In the present invention, when adding the sensitizing dye to the silver halide emulsion, examples of the dye solvent include methyl alcohol,
Ethyl alcohol, acetone, water-miscible organic solvents are preferably used.

In the present invention, when a sensitizing dye is added to a silver halide emulsion, the amount added is IX per mole of silver halide.
10-' mole to 2.5 X 10-" mole is preferred, more preferably 1.OX 10-' mole to 1.OX 10-" mole.
0X1O mole.

Various commonly used chemical sensitization methods can be applied to the silver halide grains related to the present invention. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water-soluble iridium salts; sulfur sensitizer; selenium sensitizer; polyamine, primary chloride; Chemical sensitization can also be carried out using a chemical sensitizer such as a reduction sensitizer such as tin, alone or in combination.

In the present invention, various kinds of sulfur sensitizers can be used as the above-mentioned sulfur sensitizer. Examples include thiosulfate, allylthiocarbamide thiourea, allyl isotheacyanate, cystine, p-toluenethiosulfonate, and -monodanine. Other U.S. Patent No. 1,574.944,
2,410,689, 2.278.947, 2.728.668, 3.501.313, 3
, No. 656.955, German Patent No. 1.422,869, Japanese Patent Publication No. 56-24937, Japanese Patent Publication No. 55-45016
Sulfur sensitizers described in No. 1, etc. can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as voice, temperature, and silver halide grain size, but as a guide, halide #! It is preferably about 10 moles to about 10 moles per mole.

In the present invention, selenium sensitization can be used instead of sulfur sensitization or in combination with sulfur sensitization. Selenium sensitizers include aliphatic isoselenocyanates such as allylinselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethylselenide, dietherdiselenide, etc. Noselenides etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 1.574,944 and 1,602.
No. 592 and No. 1,623.499.

The amount of the selenium sensitizer added varies over a wide range like the sulfur sensitizer, but as a guideline it is preferably about 10 mol to lθ mol per 1 mol of hydride #1.

In the present invention, the oxidation number of gold is used as the gold sensitizer.
.

may have a valence of +1 or +3, and various types of gold compounds are used. Typical examples include chloroaurate, potassium chloroaurate, auric tricturide, potassium auric thio7anate, potassium iodoaurate, tetracyano auric a7ad, ammonium aurothiocyanate, pyridyl trichlorogold, etc. .

The amount of the gold sensitizer added varies depending on the conditions of S, but as a rough guide, it is preferably in the range of about 10 moles to 10 moles of halogenated #1.

The method of sensitizing silver halide grains in the present invention can also be carried out in combination with a method of sensitizing silver halide grains using other noble metals, such as metals such as platinum, palladium, iridium, and rhodium, or their salts.

In the present invention, reduction sensitization may also be used in combination.Reducing agents are not particularly limited, but include known stannous chloride, thiourea dioxide, hydrazine derivatives, silane compounds, and the like.

It is preferable to perform reduction sensitization during the growth of silver halide grains or after completion of sulfur sensitization and gold sensitization.

The silver halide emulsion according to the present invention can contain various silver halide solvents at any point in its manufacturing process. As the helff silvergenide solvent, (a) U.S. Patent 3.
271.157, 3.531,289, 3.5
74.628, JP-A-54-1019, JP-A No. 54-1
Organic thioethers described in No. 58917 and Japanese Patent Publication No. 58-30571, etc., (b) JP-A-53-8240
No. 8, No. 55-77737, No. 55-29829, etc., and is a thiourea visiting conductor, (C) JP-A No. 53-1
Silver halide solvents having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in No. 44319, etc.; , (e) sulfite, (f) thiocyanate, (g) ammonia, (h) JP-A-57-
Hydroxyalkyl-substituted ethylenediamines described in No. 196228 etc., (i)! ＃Opening opening 7-202
Examples include mercaptotetrazole derivatives described in JP-A-58-54333, etc., and (j) benzimidazole derivatives described in JP-A No. 58-54333.

The silver halide emulsion according to the present invention includes a manufacturing process thereof,
Various compounds may be added at the end of chemical ripening to prevent capri formation during storage or development or to stabilize photographic performance.

For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles,
lobenzimidazoles, promobenzimitazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles*<special Kl-phenyl-5-mercaptotetrazole), etc. Mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, as well as benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hyde-quinone alligator conductors, aminophenol derivatives, gallic acid derivatives,
A number of compounds known as anti-capri agents or stabilizers can be added, such as ascorbic acid derivatives and the like. These chemicals are preferably added during chemical ripening or before coating.

Various hydrophilic colloids including gelatin are used as binders for the silver halide emulsion of the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes reaction products with gelatin acid anhydride, reaction products between gelatin and incyanate,
Alternatively, reaction products of gelatin and a compound having an active halogen atom are included. Examples of acid anhydrides used in the reaction with gelatin include maleic anhydride,
Includes heptalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, etc., and incyanate compounds include, for example, phenyl incyanate, p-bromophenyl incyanate, p-chlorophenylisocyanate, p- Examples include tolylisocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like.

Examples of compounds having active halogen atoms include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, P-7znoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, P-)luenesulfonyl chloride, and m-nitrobenzene. Sulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-2) I'-4-aminobenzenesulfonyl chloride, 2
-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2
-amino-5-methylbenzenesulfonyl chloride,
7thalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate,
Included are fluoride chloride and the like.

In order to prepare a silver halide emulsion, KR aqueous colloids are used, in addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as required, colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl content of 19 to Cellulose derivatives such as cellulose acetate hydrolyzed to 26% K, polyacrylamides, imidized polyacrylamides, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymers, Polyvinyl alcohol--polyvinylpyrrolitone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with vinyl group-containing heptamers, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. You can also use

The ζ-ge/fertilized steel emulsion according to the present invention can be used for various purposes such as coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and zero-intrinsic improvement (e.g., development acceleration, high contrast, sensitization). It may also contain various surfactants.

That is, U.S. Patent No. 2,240.472, U.S. Patent No. 2.83
No. 1.766, No. 3.158,484, No. 3.210
゜No. 191, No. 3.294,540, No. 3.507.
660, British Patent No. 1,012.495, British Patent No. 1,02.
No. 2,878, No. 1.179:290, No. 1.198
．． No. 450, U.S. Pat. No. 2,739,891, U.S. Pat.
23.123, 1.179.290, 1.19
No. 8,450, No. 2,739,891, No. 2,823
．． No. 123, No. 3°068, No. 101, No. 3,415.
No. 649, No. 3,666.478, No. 3.756.8
No. 28, British Patent No. 1,397.218, British Patent No. 3.113
．． No. 816, No. 3.411, No. 413, No. 3.473.
No. 174, No. 3,345.974, No. 3.726.6
No. 83, No. 3.843.368, Belly Patent 1, 1
No. 38,514, No. 1,159,825, No. 1,37
No. 4.780, U.S. Pat. No. 2,271.623, U.S. Pat.
No. 288.226, No. 2,944,900, No. 3.2
No. 35,919, No. 3,671,247, No. 3,77
No. 2,021, No. 3.589.906, No. 3.666
．． No. 478, No. 3,754,924, West German patent application (
OLS) No. 1,961,683 and Japanese Patent Application Publication No. 1973-
No. 117414, No. 50-59025, Special Publication No. 117414-
378, 40-379 and 43-13822, such as saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers). Polyethylene glycol esters, polyethylene glycol sorbitan esters,
polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Glycidol visiting conductors (e.g. alkenylsuccinic polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoid saponins, Alkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates,
Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups such as alkyl phosphates, N-synalkyl phosphates, amino acids, aminoalkyl Sulfonic acids, aminoalkyl sulfates or phosphates, alkyl, betaines, amine imides, amine oxides, amphoteric surfactants, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridium, imidazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonium salts and sulfonium or sulfonium salts containing aliphatic or heterocycles can be used.

In addition to the above-mentioned surfactants, the silver halide emulsion according to the present invention contains, as a development accelerator, West German patent application (OLS) 2
, 002,871, 2,445.611, 2,
It may also contain imidazoles, thioethers, selenoethers, etc., which are described in No. 360,878, British Patent No. 1,352,196, and the like.

In addition, in order to apply the silver halide emulsion of the present invention to a color photosensitive material, magenta, cyan, and yellow couplers are added to the silver halide emulsion adjusted to be green-sensitive, red-sensitive, and/or blue-sensitive, respectively. The method and material used for light-sensitive materials for photosensitive materials may be used, and the coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule. The coupler may be either 4-equivalent or Fi2-equivalent to silver ion. It may also contain a colored turnip 2-1 having a color correction effect or a coupler (so-called DIR coupler) that releases a development inhibitor upon development. Additionally, the coupler may be such that the product of the coupling reaction is colorless.

As the yellow color-forming coupler, various open-chain ketomethylene type Kab 2- can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat. Nos. 2,875.057 and 3.265.5.
No. 06, No. 3.408.194, No. 3.551.15
No. 5, No. 3.582.322, No. 3.725.072
No. 3,891,445, West German Patent No. 1,547.8
No. 68, West German Patent i [(OLS) 2,213.461
No. 2,219,917, No. 2,261,361, No. 2,414,006, No. 2,263.875, etc.

As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
, No. 600.788, No. 2.983.608, No. 3.
No. 062,653, No. 3,127, No. 269, No. 3.3
No. 11.476, No. 3.419゜391, No. 3.51
No. 9,429, No. 3.558.319, No. 3.582
, No. 322, No. 3.615.506, No. 3.834,
No. 908, No. 3.891,445, West German Patent No. 1,8
No. 10.464, West German Patent Application (OLS) 2.408
, No. 665, No. 2,417.945, No. 2,418.
No. 959, No. 2,424,467, Special Publication No. 1977-1960
This is what is described in No. 31, etc.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples are U.S. Pat. Nos. 2,369,929 and 2.434,27.
No. 2, No. 2.474,293, No. 2,521.908
No. 2,895.826, No. 3.034゜892, No. 3.311,476, No. 3,458,315,
3.476.563, 3.583.971, 3.591.383, 3,767.4114! , German patent publication H (OLS) No. 2,414,830, same 2
, 454, 329, and JP-A-48-59838.

As a colored coupler, for example, U.S. Patent No. 3.47
No. 6,560, No. 2,521,908, No. 3.034
．． No. 892, Special Publication No. 44-2016, No. 38-223
No. 35, No. 42-11304, No. 44-32461, and OLS No. 2,418.959 can be used.

In the photosensitive layer according to the present invention, the above-mentioned DIR compounds can be further advantageously used, and examples of the DIR compound include, for example, U.S. Pat. No. 3,227.554, U.S. Pat. No. 3.701.783,
3.790.384, 3.632゜345, 3.933.500, 4,095,984, 4
, No. 149,886, No. 4,286.054, No. 4,
No. 359,521, West German patent application (OL8) 2°414
．． No. 006, No. 2,454,301, No. 2,454.
No. 329, British Patent No. 953.454, Japanese Unexamined Patent Publication No. 57-1
No. 54234, Special Publication No. 48-28690.

JP 54-145135, JP 57-151944, JP 52-82424, U.S. Patent No. 2,327, 554
No. 3,958,993, Japanese Unexamined Patent Publication No. 14513/1983
No. 5, No. 58-162949, No. 58-205150
No. 59-195643, No. 59-206834, No. 59-206836, No. 59-210440,
Those described in No. 60-7429 and the like can be used.

Typical specific examples of the DIR compound of the present invention are described below in the margins, but the present invention is not limited thereto.

[Exemplary compounds]

NO□ (D-5) OH (D-6) (D-7) (D-8) (D-9) (D-10) (D-11) OH NO□ (D-12) OH COOC1□H25 (D-13) (D-17) (D-18) (D-19) (D-20) (D-21) (D-22) (D-23) n (D-30) H (D- 32) H (D-33) H H (D-34) H (D-36) (D-37) 2Hs (D-38) OH (D-39) (D-40) (D-41) OH ( D-42) (D-43) OH (D-45) OH (D746) H (D-,47) (D-48) (D-49')
,.

(D-50) In addition to the DIR coupler, the light-sensitive material of the present invention may contain a compound that releases a current inhibitor along with 3JI, for example, U.S. Pat.
No. 29, West German patent application (OLS) No. 2,417.914 can be used, and other JP-A No. 55-855
No. 49, No. 57-94752, No. 56-65134, No. 56-135841, No. 54-130716,
No. 56-133734, No. 56-135841, U.S. Patent No. 4.310゜618, British Patent No. 2,083.6
No. 40, Research Fist Disclosure, Oni 18360
(1979), 14850 (1980), Arashi 19
033 (1980), Arashi 19146 (1980),
11JL120525 (4981), Na21.72
The couplers described by K. B. (1982) can also be used.

Two or more of the above couplers may be included in the same layer. Furthermore, the same compound may be contained in two or more different layers.

A variety of methods can be used to introduce couplers into the silver halide emulsion layer, such as those described in US Pat. No. 2,322,027. For example, 7 tar acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphoric acid esters (diphenyl phosphate, triphenyl heptophosphate, tricresyl phosphate,
Dioctyl butyl 7-mole 7-ate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (
such as diethyl laurylamide), or with a boiling point of about 3
After dissolving in an organic solvent at 0°C to tSO°C, for example, lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-nitoxyethyl acetate, methyl cellosolve acetate, etc. Dispersed in hydrophilic colloids.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

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

These couplers generally contain between 2×10 moles and 5×10 moles of silver per mole of silver in the silver halide emulsion layer.
-' mol, preferably 1×10 mol to 5×10 mol.

The photosensitive material of the present invention uses hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives,
It may also contain ascorbic acid derivatives, specific examples of which are disclosed in U.S. Pat. Nos. 2,360,290 and 2.336.3.
No. 27, No. 2,403.721, No. 2,418,61
No. 3, No. 2,675.314, No. 2゜701, 197
No. 2,704,713, No. 2.728, '659
No. 2,732.300, No. 2,735.765, JP-A No. 50-92988, No. 50-92989,
It is described in No. 50-93928, No. 5O-IIO337, Japanese Patent Publication No. 50-23813, etc.

As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-7 minobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. Examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, and other monomers having ethylene groups. Gelatin plasticizers include glycerin and glycol compounds, and thickeners include styrene-sodium maleate copolymer and alkyl vinyl ether! Supports for photosensitive materials made using the silver halide emulsion prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypyrene synthetic paper, and glass. paper, cellulose acetate, cellulose nitrate,
Supports such as polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc. are appropriately selected depending on the intended use of each photosensitive material.

These supports are subjected to surface treatment or undercoat treatment (undercoat layer) as necessary.

After exposure, the photosensitive material of the present invention can be developed by a commonly used known method.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, amine phenols, and amine benzenes, as well as sulfites, carbonates, and other alkali metal salts.
May include bisulfites, bromides, iodides, and the like. Further, when the light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal method, the image is first developed with a black negative developer, then exposed to white light or treated with a bath containing a capri agent, and then color developed with an alkaline developer containing a color developing agent.

There are no particular restrictions on the processing method, and any processing method can be applied, but typical examples include a method in which after color development, a bleach-fixing process is performed, and if necessary, further washing with water and a stabilizing process are performed; After development, bleaching and fixing may be carried out separately, and if necessary, washing and stabilization may be carried out. The photosensitive material of the present invention is disclosed in JP-A-58-14834 and JP-A-58-10.
No. 5145, No. 5g-134634 and No. 58-18
No. 631 and Japanese Patent Application No. 58-2709 and No. 59-8
A stabilization treatment as an alternative to water washing as shown in No. 9288 or the like may be performed.

The photosensitive material of the present invention can be used not only for color use but also for various uses such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching method, reversal use, and diffusion transfer method. It can be effectively applied to photosensitive materials.

〔Effect of the invention〕

Compared to the case where the average grain size ratio of emulsion A and emulsion B defined in the present invention is outside the above range, or the case where monodisperse emulsions with different surface silver iodide contents are used, the present invention In this case, an excellent interimage effect can be obtained, and
It is completely unexpected that improved graininess, exposure latitude and good color reproduction are obtained, especially that the interimage effect is bidirectional between different photosensitive layers relative to each other. This is a feature of the present invention. Furthermore, compared to the case where emulsions having different surface silver iodide contents are mixed, the variation in performance over time after mixing is small.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[Preparation of polydisperse emulsion]

A silver nitrate aqueous solution and an alkali halide aqueous solution were allowed to fall naturally into a reaction vessel maintained at 60°C to which an aqueous gelatin solution and an excess halide had been added in advance, and then an aqueous Demol N solution manufactured by Kao Atlas Co., Ltd. and an aqueous magnesium sulfate solution were added for precipitation and desorption. Salt, add gelatin, pAg 7.8
, p) 16.0 emulsion was obtained.

Furthermore, chemical ripening was performed using sodium thiosulfate, chloroauric acid, and rhodan ammonium, and 4-hydroxy-6
-Methyl-1,3,3a, 7-chitrazaindene and 1
-Phenyl-5-mercaptotetrazole was added, and gelatin was further added to obtain a polydisperse silver iodobromide emulsion. This was done by changing the alkali halide composition (by changing the molar percentage of silver iodide and by changing the addition time of the silver nitrate aqueous solution and the alkali halide aqueous solution), thereby changing the average particle size and particle size distribution.

[Preparation of monodisperse emulsion]

Seed particles of silver iodobromide with a silver iodide content of 2 mol % of silver halide and an aqueous gelatin solution were introduced into a reaction vessel K, and the pAg and grains in the reaction vessel were heated while stirring. , an ammoniacal silver nitrate aqueous solution, and potassium iodide and potassium bromide aqueous solutions were added in proportion to the increase in surface area during grain pregrowth. Next, Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and sulfuric acid! Add aqueous magnesium solution for precipitation and desalting, add gelatin, and prepare pAg7.
An emulsion of 8.-6.0 was obtained.

Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, chemical ripening was performed, and 4-hydrochloric acid-6
-Methyl-1,3,3a, ? -tetrazaindene and 6
- Nidrobenzimidazole was added, and gelatin was further added to obtain a monodisperse silver iodobromide emulsion.

Here, the grain size can be adjusted by changing the ratio of potassium iodide and potassium bromide, by changing the silver iodide mole, and by changing the amounts of ammoniacal silver nitrate and potassium rhodanide. , and the crystal habit was changed by changing the pAg value during the reaction.

Table - Physical properties of each silver iodobromide emulsion prepared by IK are shown.

As a measure of the width of the exposure latitude, the linear exposure range (1inear exposure 5cale,
Below.

Sensitivity is expressed as a relative value of the reciprocal of the exposure that gives a Capri density of +0.3.

Granularity is defined as the value 1000 times the standard deviation of the variation in density value that occurs when a dye image with a dye image density of 10 is scanned by a microdensitometer with a circular scanning aperture of 25 μm (
It, M, S, ) are expressed as relative values, with the control sample being 100.

Example 1 Sample 1 was prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film.

[Sample l]

Layer 1: black colloidal silver 0.411 and gelatin 3g
Antihalation layer layer 2 containing 1.52 and 2.2 g of gelatin, a mixture of emulsions E and E of Table 1, each sensitized to red sensitivity, and 1.
OJ9 cyan coupler (c-i) 0.075. j9 colored cyan coupler (CC-1) and 0.01! j
1-hydroxy-2-[δ-(2,4-di-t-amylphenoxy)-n-butyl]naphthamide, 0.03
A low-speed red-sensitive emulsion layer containing 0.82 tricresyl 7-m-7-A (hereinafter referred to as TCP) in which a DI compound (D-1) of 1 is dissolved.

Layer 3...High-sensitivity red-sensitive silver iodobromide emulsion of 1,5I (Table-
9 emulsion prepared by color-sensitizing the emulsion layer described in 1 to red sensitivity), 1.2 g
gelatin and 0.26F cyan coupler (0-1
) and 0.0:J colored cyan coupler (Co-1
) dissolved 0, 30! High-speed red-sensitive emulsion layer containing 9 'I' CPs.

Layer 4: 0.04 Jil of n-dibutyl phthalate [hereinafter referred to as DBP] in which 0.07/l of 2.5-di-t-octylhydride-quinone [hereinafter referred to as antifouling agent (HQ-1)] was dissolved. ] and an intermediate layer containing 0.8 g of gelatin.

Layer 5: 1.4 g of a mixture of the emulsions in Table 1 and E, each color sensitized to green sensitivity, and 2.2 I of gelatin and 0.0 g of a mixture of emulsion E and 2.2 I of gelatin.
89 magenta coupler (M-1), 0.15. P colored magenta coupler (CM-1), 0.025. p
0,95. ! i'
A low-speed green-sensitive emulsion layer containing TCP.

Layer 6: 1.6 g of emulsion A color sensitized to green sensitivity,
Dissolve 1.9I of gelatin, 0.20.9 of magenta coupler (M-1), and 0.049.9 of colored magenta coupler (CM-1) to give 90.2511 of T.
Highly sensitive green-sensitive emulsion layer containing CP.

Layer 7: 0.15F yellow colloidal silver, 0.11.9 DBP dissolved with 0.21 antifouling agent (HQ-1)
and a layer of yellow filter containing 1.5I gelatin.

Layer 8: Emulsion D of Table 1, each color sensitized to blue sensitivity,
Mixture o of C and E, emulsion of sII, and gelatin of 1,99 and yellow coupler (Y-1) of 1.51i
A low-speed blue-sensitive emulsion layer containing TCP of 0.67 in solution.

Layer 9...color sensitized to blue sensitivity 0, 8. Emulsion A of ii, 1.5I gelatin and 1.30p of yellow coupler (Y-1) were dissolved in 0.65. iil TCP
A highly sensitive blue-sensitive emulsion layer containing

Layer lO...Protective layer with 2.3I gelatin.

Samples 2 to 7 were prepared in the same manner as Sample 1 above.

The emulsions used for each, the mixing ratio, the amount of (D-1) added, etc. are listed in Table-2.

(CC-t) (D-1) (M-1) Each of these samples was exposed to white light through an optical wedge and then processed through the following processing steps to obtain a dye image. Table 2 shows the characteristic values obtained by changing the time and matching the same gradation.

Treatment Step [Treatment Temperature 38° C.] Treatment Time The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

[Bleaching solution] [Fixing solution] [Stabilizing solution] On the other hand, in order to evaluate color reproducibility, each sample was exposed to green light through a wedge. The above-mentioned development process was performed after uniformly exposing red light at an exposure amount such that

The color density of the red-sensitive layer should originally be 1.5 because it was exposed without using a wedge, but there is an interlayer effect during development, the so-called interimage effect (IIE).
Therefore, the development of the red-sensitive layer is suppressed depending on the density developed in the green-sensitive layer, and the red density decreases. If the red density when the green density is maximum is Dl, the strength of IIE is ΔD
It was expressed as cR=(1,5-Dl)/1.5. That is, Δ
The larger the DGR value, the stronger the IIE, and the higher the green color purity.

In the same way, each sample was exposed to red light through a wedge, then uniformly exposed to green light at an exposure amount such that the green density would be 1.5 when exposed only to green light, and then the same development process was performed. I asked for The results are shown in Table-2.

The results in Table 2 show that the light-sensitive materials Na2-5 containing a mixture of emulsions A and B of the present invention had a comparative sample size of 1.6.
Compared to No. 7, sensitivity, graininess, color reproducibility, and exposure latitude are improved.

Moreover, sample winds 2 to 5 of the present invention are sample N1 of the prior art.
Comparing to 11K, the desensitization in forced deterioration test (3 times) under high temperature (50℃, 80% R, H) is less than 1/2, and it has excellent stability over time. understood.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Agent: Nobuaki Sakaguchi (and one other person)

Claims (1)

[Scope of Claims] In a photographic light-sensitive material having a plurality of light-sensitive silver halide emulsion layers on a support, at least one of the light-sensitive silver halide emulsion layers contains an emulsion represented by the following A and an emulsion represented by B. A silver halide photographic material characterized by containing an emulsion as a main component. A: A substantially monodisperse emulsion having a silver iodide content of 6 mol % or more as a whole grain. B: It has substantially the same average grain size as the silver iodide in the emulsion represented by A, and the composition near the grain surface is substantially the same as that of the emulsion represented by A, but the grains as a whole An emulsion with a lower silver iodide content than the emulsion represented by A.