JPS584332B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved exposure latitude.

In general photographic materials, it is required to obtain favorable images in a wide exposure range.

That is, a photographic material having a wide exposure latitude is desired.

Conventionally known wide latitude techniques mainly include the following methods.

One method is to widen the particle size distribution of silver halide grains according to a desired latitude.

However, it is known that silver halide photosensitive materials produced using this method have a number of problems, including deterioration in storage stability, graininess, processing stability, and desilvering properties.

Compounds that imagewise release a development inhibitor during development, such as inhibitor-releasing developers and inhibitor-releasing couplers (D
IR couplers) and inhibitor-releasing compounds (DIR substances)
It is known that the latitude can be widened by applying this to photosensitive materials.

However, these compounds not only widen the latitude but also cause desensitization during storage, and there is a limit to the extent to which they can widen the latitude.

Furthermore, latitude can be controlled by increasing the iodine content of the silver halide emulsion, but this has the disadvantage that increasing the iodine content of the silver halide emulsion lowers the emulsion sensitivity.

None of the above methods is sufficient to provide the desired wide latitude and satisfactory sensitivity.

Accordingly, an object of the present invention is to provide a silver halide photographic material having high sensitivity, excellent storage stability, graininess, processing stability and desilvering properties, and a wide exposure latitude.

Another object of the present invention is to provide a silver halide photographic material having excellent sharpness and wide exposure latitude.

An object of the present invention is to provide a monodisperse silver halide emulsion layer in which the silver halide grains in the emulsion layer are comprised of at least two types of silver iodobromide or silver halide grains having different silver iodide contents in the surface layer. This is achieved by a photographic light-sensitive material having on a support at least one silver halide emulsion layer consisting essentially of grains of silver bromide.

In the present invention, a silver halide emulsion consisting essentially of grains consisting essentially of silver iodobromide refers to a silver halide emulsion in which the composition of silver halide contained in the silver halide emulsion consists of silver iodobromide and other halides. It refers to silver halide grains or silver halide emulsions containing components other than silver iodobromide, such as silver chloride, to the extent that the photographic performance of the silver halide emulsion is not impaired.

When the component other than silver iodobromide is silver chloride, for example, if its content is up to about 5 mol % of the total silver halide, it can be considered to be substantially the same as a silver iodobromide emulsion.

The silver halide grains contained in the silver halide emulsion layer of the present invention are preferably made of silver halide with a silver iodide content of 0 to 12 mol % and the remaining silver halide being silver bromide. The silver halide composition of the silver halide grain whose surface layer has a lower silver iodide content may be silver bromide.

A monodisperse silver halide emulsion layer refers to an emulsion layer in which the silver halide grains are composed of monodisperse silver halide grains, and monodisperse silver halide grains mean a grain size between each grain. It means a group of silver halide grains with small differences.

In the present invention, the silver halide grains in the monodisperse silver halide emulsion layer account for at least 95% of the silver halide grains.
A group of silver halide grains having a grain size (in number) within ±50% of the average grain size.

Furthermore, at least 95% (by number) of the silver halide grains
A group of silver halide grains having a grain size within ±40% of the average grain size has a higher degree of monodispersity and further enhances the effects of the present invention, which will be described later.

The surface layer of silver halide grains in the present invention refers to a layer having a thickness of 0.05 μm on the surface of silver halide grains.

In reality, the surface layer of a silver halide grain does not have an interface with the inside of the grain, but the concept of a surface layer has an important meaning in the structure of the present invention.

In the monodisperse silver halide emulsion layer of the present invention, it is sufficient that the silver halide grains in the emulsion layer include grains having different silver iodide contents in the grain surface layer.

The monodisperse silver halide emulsion layer of the present invention has a surface layer with a relatively high silver iodide content corresponding to 10% of the total number of silver halide grains contained in the layer. The difference between the silver iodide content and the average silver iodide content of grains having a surface layer with a relatively low silver iodide content, which also corresponds to io% of the total number of grains, is the difference between the individual grains of the two types. It is preferable that the photographic sensitivity is distinguishable.

In the present invention, the effect of the present invention is further enhanced if the difference in silver iodide content between the surface and surface layers is 1.0 mol% or more.

More preferably, this difference in silver iodide content is in the range of 2.0 mol% to 80 mol%.

Although the silver iodide content inside the silver halide grains (other than the surface layer) in the silver halide emulsion layer according to the present invention is arbitrary,
When applied to ordinary photographic materials, 0 to 12 mol% is appropriate.

The silver halide emulsion used in the monodisperse silver halide emulsion layer of the present invention includes at least two types of monodisperse halide emulsions having approximately the same average grain size and having different silver iodide contents in the surface layer of the silver halide grains. It can be manufactured by mixing a silver emulsion.

Such a silver halide emulsion before mixing can be prepared by a known and commonly used force method.

That is, silver halide particles may be generated and dispersed by adding an aqueous solution of a water-soluble silver salt, such as silver nitrate, and an alkali halide aqueous solution to a dispersion medium such as an aqueous gelatin solution. A method of adding an aqueous solution of a water-soluble silver salt to a mixture of a dispersion medium such as an aqueous gelatin solution and an aqueous solution of an alkali halide; Various methods can be applied, such as a method of adding an aqueous solution, a method of simultaneously adding an aqueous silver salt solution and an aqueous alkali halide solution to a dispersion medium such as an aqueous gelatin solution, and the like.

In addition, highly monodisperse silver halide emulsions were developed in JP-A-54
The method described in Publication No.-48521, that is,
It can be produced by a method in which an aqueous solution of (io)potassium bromide-gelatin and an aqueous ammoniacal silver nitrate solution are added to a gelatin solution containing silver halide seed particles while changing the addition rate as a function of time.

At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate.

Also useful in this invention are core/shell emulsions made by the method disclosed in GB 1,027,146.

Also useful are silver halide emulsions obtained by the conversion methods disclosed in US Pat. No. 2,592,250 and British Patent No. 635,841.

In producing the various silver halide emulsions described above, it is possible to produce a variety of silver halide grains having different silver iodide contents in their surface layers.

In this way, a silver halide emulsion containing at least two types of monodisperse silver halide grains having almost the same grain size but different silver iodide contents in the surface layer is produced, and these are mixed in an appropriate ratio. By doing so, the monodisperse silver halide emulsion of the present invention can be produced.

The silver halide grains can be mixed at an appropriate time during the process of producing the photographic material according to the present invention.

That is, it may be carried out at any time during the production of silver halide grains, before chemical ripening, during chemical ripening, or before coating.

The silver halide photographic material according to the present invention only needs to have at least one monodisperse silver halide emulsion layer according to the present invention, and may have two or more layers.

For example, in color silver halide photographic materials,
All or some of the silver halide emulsion layers can be monodisperse silver halide emulsion layers of the present invention.

When the present invention is applied to a multilayer color silver halide photographic light-sensitive material, it can be applied to all or part of the emulsion layers of the red-sensitive, green-sensitive and blue-sensitive light-sensitive layers constituting the material.

The photosensitive layer herein refers to a layer or layer group consisting of at least one emulsion layer that is sensitive to light in the same wavelength range.

For example, a green-sensitive photosensitive layer may be composed of a low-speed red-sensitive emulsion layer and a high-speed red-sensitive emulsion layer, and the present invention can be applied to both or either of these two emulsion layers.

Further, since the silver halide photographic light-sensitive material according to the present invention can achieve a wide latitude with the monodisperse silver halide emulsion layer, it is possible to adopt a structure in which there are fewer silver halide grains in a certain grain size range. .

The Theory of the Photographic Process by T. H. James, 4th edition, 580-585
0.35μ to 0.55μ as stated on page
Since silver halide grains having a grain size in the range of /'% are most likely to cause light scattering, such silver halide grains are a major factor in deteriorating sharpness.

By applying the present invention, from 0.35μ to 0.55μ
A photographic light-sensitive material can be produced in which the amount of μ silver halide grains is minimized.

That is, the monodisperse silver halide grains included in the present invention include a monodisperse silver halide emulsion layer with an average grain size of 0.35μ or less and a monodisperse silver halide emulsion layer with an average grain size of 0.55μ or more. Due to the structure of two or more layers including the silver emulsion layer, 0
．． It is possible to produce a photographic light-sensitive material containing fewer silver halide grains of 35μ to 0.55μ.

As shown in Example 3, such a photographic material has excellent sharpness and also has good linearity in its characteristic curve.

The silver halide photographic material according to the present invention can be effectively used in various uses such as general black and white, X-ray, color, infrared, micro, silver dye bleaching, reversal, and diffusion transfer. Can be applied.

The silver halide photographic material according to the present invention can have a non-photosensitive layer on the support.

Conventionally known techniques can be applied as is to the non-photosensitive layer.

Further, the silver halide photographic emulsion layer may also contain an emulsion layer other than the monodisperse silver halide photographic emulsion layer according to the present invention.

For the photographic emulsions of these emulsion layers, the same techniques as described below for the silver halide photographic emulsions according to the present invention can be applied.

The silver halide emulsions according to the invention can be chemically sensitized.

They can be done by any conventional method.

Namely, active 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 sensitizers; selenium sensitizers; polyamines, primary chloride Chemical sensitization can be carried out using a substitute sensitizer such as a reduction sensitizer such as tin alone or in combination.

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using an optical sensitizer such as a cyanine dye such as a cellomethine dye, a monomethine dye, a dimethine dye, a trimethine dye, or a merocyanine dye alone or in combination. (e.g., superchromatic sensitization).

Furthermore, the silver halide photographic light-sensitive material according to the present invention can be used for various photographic purposes depending on the purpose of the photosensitive layer and/or other constituent layers (for example, an intermediate layer, a subbing layer, a filter layer, a protective layer, an image-receiving layer, etc.). Additives may be included.

For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salt polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, acryloyl-based, alpodiimide-based, maleimide-based, methane Hardeners such as sulfonic acid esters and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Image stabilizers such as Chroman, Claman, bisphenol and phosphite esters; Wax, higher fatty acids There are lubricants such as glycerides and higher alcohol esters of higher fatty acids.

In addition, anionic, cationic, and nonionic surfactants can be used as coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used.

Mordants include N-guanylhydrazotu compounds,
Quaternary onium salt compounds and the like are effective.

Effective antistatic agents include diacetyl cellulose, styrene perfluoroalkylridium 8 maleate copolymer, and alkali salts of the reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid. be.

Examples of the color turbidity inhibitor include polymers containing vinylpyrrolidone monomers, polymers containing vinylimidazole monomers, and the like.

Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers.

Furthermore, it is also possible to use colloidal silicon oxide.

Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups.

Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

Furthermore, in the case of a color silver halide emulsion, a coupler for forming a color image is contained.

Useful couplers include open-chain methylene yellow couplers, pyrazolone magenta couplers, and phenolic or naphthol cyan couplers, which can be combined with colored couplers for automasking (e.g., by binding to the active sites of the coupler). (couplers with a split-off group having an azo group as a group), osazone-type compounds, development-diffusive dye-releasing couplers, development inhibitor-releasing compounds (developing by reacting with an oxidized form of an aromatic primary amine developing agent) It is a compound that releases an inhibitory compound,
It is also possible to use a so-called DIR coupler that reacts with an oxidized product of an aromatic primary amine developing agent to form a colored dye and a so-called DIR substance that forms a colorless compound.

In order to incorporate these couplers into a silver halide color photographic light-sensitive material, various known techniques conventionally used for couplers can be applied.

For example, Hayabusa can be dissolved and contained in a high boiling point solvent.
Further, the coupler and the high-boiling point solvent can be separately dispersed into fine particles and then mixed for use, and in the method of dispersing these, it is also preferable to use a low-boiling point solvent.

A low boiling point solvent can be used in place of a high boiling point solvent, and can also be used in combination with a high boiling point solvent, and each of these solvents can be used alone or in combination of two or more.

Alternatively, part or all of the high-boiling solvent that is immiscible with water may be replaced with a polymer that is insoluble in water and soluble in organic solvents.

In the case of a coupler having a water-soluble group, it can also be used as a Fischer type coupler, ie, dissolved in an alkaline solution.

The silver halide photographic material according to the present invention is produced by coating a support with a silver halide emulsion layer and other constituent layers containing the above-mentioned divine photographic additives as necessary. Advantageously used supports include, for example, balik paper, polyethylene-coated paper,
Polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acecool,
Supports include polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the purpose of use of each silver halide photographic light-sensitive material.

These supports are subjected to undercoat processing if necessary.

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

The enemies of black and white development are alkaline solutions containing developing agents such as hydroxybenzenes, amine phenols, and amine benzenes, and other alkali metal salts such as sulfites, carbonates,
May include bisulfites, bromides, iodides, and the like.

Further, in the case of a silver halide color photographic light-sensitive material, 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-and-white negative developer, then exposed to white light or treated with a bath containing a fogging 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, bleach-fixing is performed, and if necessary, further washing with water and stabilization treatment are performed, or after color development. , a method in which bleaching and fixing are carried out separately, and further water washing and stabilization treatment are carried out as necessary.

It is also known to process low silver halide light-sensitive materials using an amplifier agent such as a hydrogen peroxide cobalt complex salt, and these methods can also be used for processing.

In addition, these treatments may be carried out at high temperatures in order to perform them quickly, or may be carried out at room temperature or lower in special cases.

Pre-hardening treatment can also be performed when performing high temperature rapid treatment.

Furthermore, depending on the type of processing agent used, auxiliary baths such as various types of neutralization baths may be required, and these auxiliary baths can be used as necessary.

When the silver halide photographic light-sensitive material according to the present invention is used for color purposes, particularly useful color developing agents used for color development include primary phenylenediamines and derivatives thereof, such as the following: This can be cited as a representative example.

4-amino-N,N-diethylaniline, 3-methyl-
4-amine-N,N~diethylaniline, 4-amine-
N-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethynole-N-β-j nidroxyethynoleaniline, 3-methyl-4-ami7-
N-ethyl-N-. -β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-N,N-diethylaniline, 3-methoxy~4-amino-N-ethyl-N-β
~Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3
-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,N-dimethylaniline,
N-ethyl-N-β- [β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β(β-methoxyethoxy)ethyl-3-methyl-4~ These include aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate.

The photographic light-sensitive material having a monodisperse silver halide emulsion layer according to the present invention has a wide latitude despite the narrow particle size distribution (that is, monodisperse) of silver halide grains in the emulsion layer, and Has high sensitivity.

In addition to the advantages of wide latitude and high sensitivity,
It also has the advantages of a medium-dispersion emulsion in that it has excellent graininess, processing stability, and desilvering properties.

Therefore, the present invention has a superior latitude width compared to the conventional wide latitude technology using a silver halide emulsion with a wide grain size distribution, and also improves storage stability, graininess, processing stability, desilvering property, and Desensitization is significantly improved.

Next, the present invention will be illustrated by examples, but the present invention is not limited thereto.

Example 1 The divine silver halide emulsion shown in Table 1 was prepared by the following manufacturing method.

Emulsions N, 0 and P were produced by the conventional double jet method.

Emulsions A, B, C, D and K are disclosed in JP-A-54-48521.
A monodisperse emulsion was produced by the method described in the publication (hereinafter this emulsion will be referred to as a functional addition method emulsion).

Emulsions T] and F were prepared from emulsions A and B, respectively, by a conventional iodine conversion method.

Emulsions G, H, I, J, L and M are British Patent No. 1,02
This is a core/shell emulsion produced by the method described in No. 7,146.

However, emulsions produced by the functional addition method with silver iodide contents of 1 mol % and 8 mol %, respectively, were used for the cores.

After each of these emulsions was gold-sulfur sensitized and further color-sensitized using a green-sensitive sensitizing dye, these emulsions were mixed in the ratios shown in Table 1, and magenta coupler-1-(2
,4,6-trichlorophenyl)-3-(3-(
2. 4-di-t~amylphenoxyacetamide)
Penzamide]-5-pyrazolone and the development inhibitor-releasing compound 2-(1-phenyl-5-tetrazolylthio)-6-[α-(2,4-di-t-amylphenoxy]acetamido]indanone (1) together. A dispersion of tricresyl phosphate dissolved in tricresyl phosphate and protected by a conventional method was prepared at a concentration of 0.1 coupler per mole of silver halide.
0 mol, and the development inhibitor releasing compound was added in an amount of 7.5×10 −3 mol, and coated on a cellulose acetate film base.

Table 1 shows the mixing ratio of the emulsion (single emulsion or mixed emulsion) used in these samples, the average grain size, the fluctuation rate (percentage of the standard deviation of grain size to the average grain size), and the zero percentage of silver halide grains.
．． The silver iodide content of the surface layer with a thickness of 0.05 μm was shown.

These coated samples were exposed to green light through a wedge and subjected to Konishi Roku CNK-4B color negative development.

Sensitometric results of these developed samples are shown in Table 2.

As a measure of the width of exposure latitude, the linear exposure range described in The Theory of the Photographic Process, 4th edition, pages 501-502 by T.H.
scale, hereinafter referred to as L. E. S. ) was used.

The sensitivity was expressed as a relative value of exposure amount of fog density + 0.1.

As is clear from the results in Table 2, the samples of the present invention have higher sensitivity than the comparative samples. E. S. The value is large.

As mentioned above, L. E. S. The value is a measure of the breadth of exposure latitude; L. E. S. A large value means a wide exposure latitude.

Moreover, the sample of the present invention has excellent graininess even though it has higher sensitivity than the comparative sample.

In addition, each of the above coating samples was divided, and one part was heated to 20°C.
In an atmosphere of relative humidity 60%, and one part at 50℃ relative humidity 8
It was stored for 3 days in a 0% atmosphere.

These samples were then exposed to light in the manner described above, and then subjected to the same NECA color development process.

Next, the fog of the magenta colored image formed on the sample,
Relative sensitivity (sensitivity at 20° C. and 60% relative humidity of sample No. 13 in Table 3 is taken as 100) and maximum concentration were measured.

The results are shown in Table 3. As is clear from Table 3, in an atmosphere of high vortex and high humidity, the sample of the present invention had a lower
Example 7 It can be seen that fogging, desensitization, and decrease in maximum density are significantly reduced, and the test sticks of the present invention exhibit excellent photographic performance even when stored under high temperature and high humidity conditions.
2 The monodispersed emulsions of comparative emulsions N, 0, P and B, C, D used in Example 1 were gold-sulfur sensitized, and mixed emulsions as shown in Table 4 were prepared. 2071 Bore-edged silver plated film by conventional method
l! ? /1 0 0CiL, Se-f)chi7 4 0”
! Each coating was applied at a ratio of //100CrI (trial t1 numbers 14 to 20).

These samples were subjected to a white stepwise exposure followed by a D-76 black and white negative development process.

Table 4 shows the results of Sensitome l-IJ-. This result shows that the test needle of the present invention has a wide latitude and high sensitivity.

In addition, the results showed that the test sticks of the present invention were superior to the comparative samples in terms of graininess.

Further, each of the above coated samples was divided and one part was stored at 20°C in an atmosphere of 60% relative humidity, and the other part was stored at 50°C in an atmosphere of 80% relative humidity for 3 days.

These samples were then subjected to white step exposure, followed by D-76 black and white negative development.

Next, the fog of the silver image formed on the sample and the relative sensitivity (
The sensitivity of test t1 of sample number 20 in Table 5 at 20°C and 60% relative humidity was set as 100) and the maximum concentration were measured.

Table 5 shows that the samples of the present invention have improved storage stability under high temperature and high humidity conditions compared to the comparative samples.

Tables 4 and 5 show that the samples according to the present invention (sample numbers 17 and 18) have excellent exposure latitude, high sensitivity, and improved storage stability.

Example 3 Two types of negative color photosensitive materials were prepared by sequentially coating each of the constituent layers from the first layer to the tenth layer described below on a cellulose triacetate film base.

All the emulsions used in the sample No. 21 were produced by the usual double jet method, and the emulsion used in the sample No. 22 was the monodisperse silver halide emulsion of the present invention.
These were obtained by mixing emulsions with different silver iodide contents produced by the functional addition method described in JP-A-54-48521.

Table 6 shows the emulsions used in Samples 21 and 22.

In Samples 21 and 22, these emulsions and other photographic constituent layers were coated in multiple layers in the following order.

The mixed emulsions shown in Table 6 were mixed after chemical sensitization and color sensitization.

In addition, all of the following constituent layers contain 1,3 as a hardening agent.
．． Appropriate amounts of 5-triacryloylhexahydro-S-triazine and 1,2-bis(vinylsulfonyl)ethane, zaponin as a coating aid, and dextran sulfate as a viscosity modifier were added.

1st layer Gelatin solution containing antihalation black colloidal silver at 3mg/100% silver
It was coated so that the amount of geladin was 30mg/cm2/100cm2.

2nd Layer: Low-speed red-sensitive photographic emulsion layer In sample 2l, a mixed emulsion of emulsion number 3 was optically sensitized, and in sample sample 22, a mixed emulsion of emulsion number 8 was optically sensitized using a red-sensitive sensitizing dye.

These photographic emulsions were each coated with a strong cyan coupler, 1-hydroxy-4-(2-ethoxycarbonylphenylazo)-N-(α-(2,4-di-t-amylphenoxy;butyl)-2- 5 parts by weight of naphthamide and cyan coupler l-hydroxy-N-(
20 parts by weight of δ-(2,4-c-t-amylphenoxy)butyl:-2-naphthamide was dissolved in tricresyl phosphate, and a dispersion obtained by protecting and dispersing it by a conventional method was prepared using cyan coupler per mole of AgXl. 0.0
Added to make 94 mol, silver 14mg/100cm
2 gelatin was coated at a ratio of 270 mg/100 cm2.

Third layer: High-speed red-sensitive photographic emulsion layer Sample 21 uses emulsion No. 4 and sample 22 uses emulsion No. 11, which is optically sensitized using a red-sensitive sensitizing dye. The dispersion used was added so that the amount of coupler was 0.035 mol per 1 mol of silver halide, silver 19 mg/100 cm2, gelatin 25 mg/100 cm2.
It was coated at a ratio of m2.

4th layer Intermediate layer gelatin solution gelatin 1 37/2? / 1 0 0
It was painted so that it became crft.

5th Layer Low-Sensitivity Green-Sensitive Photographic Emulsion Layer In sample 21, emulsion number 3 was used, and in sample 22, a mixed emulsion number 8 was optically sensitized using a green-sensitive sensitizing dye.

A colored magenta coupler, l-
(2,4.6-1-lichlorophenyl)-313-[α
1(2,4-di-t-amylphenoxy)-ace1.amide]anilino}-4-(meth1hexyphenylazo)-
5- 5 parts by weight of pyrazolone and Mazenk Kabler 1-(2,4,6-trichlorophenyl)-3-(
26 parts by weight of 3-(2,4.--di-t-amylphenoxyacetamido)benzamide]-5-pyrazolone;
2-(]--phenyl-5, a development inhibitor releasing compound
-tetrazolylthio)-6-[α-(2,4-di-1
-amylnoenoxy)acetamide]indanone (])
2 parts by weight were dissolved together in tricresyl phosphate,
A dispersion protected by a conventional method was mixed with 0.0 mol of coupler per 1 mol of AgX, and 7.5 mol of development inhibitor-releasing compound.
X10-3 mol, silver 14m! ? '
/ 100 d gelatin 29"!? / 100 d.

6th layer High-speed green-sensitive photographic emulsion layer Sample 21 uses emulsion number 4, sample 22 emulsion number 11 mixed emulsion is optically sensitized using a green-sensitive sensitizing dye, and this is used in the fifth layer. The dispersion was mixed with 0.035 moles of coupler and 2.6× development inhibitor releasing compound per mole of AgX.
Added to make 10-4 mol, silver 17mg/100
The gelatin was coated at a ratio of 25 mg/100 cm2.

7th Layer An intermediate layer gelatin solution was applied so that the gelatin content was 13 mg/100 cm2.

8th layer yellow filter, gelatin bath solution containing yellow colloidal silver 1mg/100% silver
It was coated so that the gelatin amount was 13 mg/100 cm2.

9th layer Blue-sensitive photographic emulsion layer Sample 21 is a mixed emulsion of emulsion number 5, sample 22 is a mixed emulsion of emulsion number 14, and yellow coupler -α-(4-(1-benzyl-2- phenyl-3,5-dioxo-l,2,4-toIJazolidinyl)]-α-pivalyl-2-chloro-5-[γ-(2,
A dispersion of 4-di-t-amylphenoxy)butylamido]acetanilide was mixed with 0.2 coupler per mole of AgX.
Added to make 1 mol, silver 10mg/100cm2
The gelatin was coated at 40 mg/100 cm2.

10th Layer A protective layer gelatin solution was coated on each layer so that the gelatin concentration was 13 mg/100 cm 2 .

The two multilayered samples thus obtained were subjected to white stepwise exposure and then subjected to Konishiroku CNK-4B color negative development.

The sensitometric results of these developed samples are shown in Table 7.

The sensitivity value is 100 the red light measurement sensitivity of sample 21 (comparison).
It is a relative value.

L., which was used in Example 1 as a measure of latitude width.
E. S. (Linear exposure range) values are shown.

As is clear from the above results, sample (22) of the present invention
It can be seen that the lens has excellent photographic performance and a very wide exposure latitude can be obtained.

In addition, each of the above coating samples was divided, and one part was heated to 20°C.
In an atmosphere of relative humidity 60%, and one part at 50℃ relative humidity 8
It was stored for 3 days in a 0% atmosphere.

These samples were then exposed to light using the method described above, and then subjected to the same negative color development process.

As the sensitometric results of these developed samples, Table 8 shows the minimum density (Dmin) and relative sensitivity (the sensitivity of sample number 21 in Table 8 at 20°C and relative humidity 60% is 1).
00) and the maximum concentration (Dmax).

As is clear from Table 8, under a high temperature and high humidity atmosphere, the samples of the present invention exhibit less fogging, less desensitization, and less decrease in maximum density than the comparative samples, and have excellent storage stability. I understand that.

Also, surprisingly, the sharpness of the sample of the present invention (sample number 22) was significantly improved.

As described in the detailed description of the invention, in the sample of the present invention (sample number 22), there are few silver halide grains having a grain size in the range of 0.35μ to 0.55μ, so the sharpness due to light scattering is It is thought that the deterioration is small.

From the above results, the sample to which the present invention was applied (sample number 22
) has a wide latitude, high sensitivity, and improved storage stability and sharpness.

Claims (1)

[Claims] 1 A monodisperse silver halide emulsion layer in which the silver halide grains in the emulsion layer are substantially composed of at least two types of grains consisting essentially of silver iodobromide having different silver iodide contents in the surface layer. 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer.