JPS61172143A - Photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to elevate graininess remarkably without impairing sharpness by combining the first coupler with the second coupler different from each other in the dispersion process and reactivity at the early stage of development. CONSTITUTION:The first coupler dispersed in oil droplets has an oleophilic group and soluboe in a high-b.p. solvent. The second coupler dispersed into an aq. alkaline soln., preferably, has at least one acidic group, such as sulfonic or carboxylic group, and the coupler itself and a coloring dye are not diffused into a hydrophilic colloid. In an emulsion layer contg. both couplers the second coupler is soluble in alkali, and in a dispersed state, and since it is rapid in the early stage development reaction, graininess is remarkably enhanced. Not only graininess but also sharpness can be kept good by regulating the second coupler to <=50mol% or the total amt.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to photographic materials, particularly silver halide color photographic materials.

BACKGROUND OF THE INVENTION In recent years, improvements in the sensitivity, graininess, and sharpness of silver halide color photographic materials (hereinafter sometimes referred to as color light-sensitive materials) have been particularly desired in order to improve image quality.

However, when silver halide grains are made larger to increase sensitivity, graininess deteriorates.

Furthermore, increasing the amount of coupler and silver halide in order to increase sensitivity results in an increase in the thickness of the emulsion layer, which reduces sharpness.

Therefore, it is generally difficult to achieve both high sensitivity and graininess and sharpness, and with conventional technology,
It has not been possible to sufficiently improve image quality by using couplers and silver halide, which are the basic constituent materials of color photosensitive materials.

OBJECTS OF THE INVENTION An object of the present invention is to provide a photographic material that can achieve high sensitivity and significantly improve graininess without impairing sharpness.

20 Structure of the invention and its effects, that is, the present invention has a silver halide emulsion layer containing a first coupler dispersed in oil droplets and a second coupler dispersed in an aqueous alkali solution, and this silver halide emulsion layer The ratio of the second coupler to the total amount of couplers is 50 mol%
and the first coupler is a coupler with a slow initial development reaction, and the second coupler is a coupler with a fast initial development reaction.

According to the present invention, it has been found that the objects of the present invention can be fully realized by combining the above-mentioned first and second couplers having different dispersion methods and different initial development reactivities. In this case, the first coupler dispersed in oil droplets has a lipophilic group and is soluble in a high-boiling organic solvent (however, an alkali-soluble group is not required).

Further, the second coupler dispersed in an aqueous alkaline solution preferably has at least one acidic group, such as a sulfonic acid group or a carboxyl group, and the coupler itself and the coloring dye preferably do not diffuse into the hydrophilic colloid (in this case, ,
As a group for preventing diffusion, at least one organic group having 8 or more carbon atoms is made to exist at a non-active site, that is, at a position from which it is not separated by the campling reaction). In the emulsion layer containing the first coupler and the second coupler, the second coupler is in an alkali-soluble form and is in a dispersed state, and the initial reaction during development is fast, resulting in a marked improvement in graininess. Since the second coupler is contained in an amount of 50 mol % or less of the total amount of couplers, not only graininess but also sharpness can be maintained well.

The ratio of the second coupler is preferably 30 mol% or less, and 10
More preferably, it is less than mol%. The first coupler may be added in the form of conventional high-boiling organic solvent droplets, but an alkaline solution of the second coupler may be added before or after forming the droplets.

In the present invention, a method for measuring the above-mentioned "initial development reaction" will be explained below.

First, high-sensitivity silver iodobromide (silver iodide 4 mol%, average grain size 0.
9μ) An emulsion containing 0.01 mol of coupler (0.02 mol in the case of 2-equivalent coupler) per 1 mol has a silver coverage of 1.6 g/m'' and a gelatin amount of 1.6 g/ll1z. After coating on a cellulose triacetate base and drying, the resulting photographic film piece was exposed to 1.6 CMS, and then subjected to the following treatments (1) to (6) (processing temperature: 38°C).

During color development, the film piece is left standing and immersed.

(1) Color development 10 seconds (2) Bleaching 6 minutes (3) Washing with water 3 minutes (4) Fixation 6 minutes (5) Washing with water 3 minutes (6) Stabilization 3 minutes The composition of the treatment liquid used in each step is as follows.

Color developer: 4-(N-ethyl-N-β-hydroxyethylamino)
-2-Methyl-aniline sulfate 4.5 g Anhydrous sodium sulfite 4.0 g Sodium nitrilotriacetate 1.0 g Sodium carbonate 30.0 g Potassium bromide
1.4 g Hydroxylamine sulfate 2.4 g Add water 1.01 Bleach solution: Ammonium bromide 160.0 g Ethylenediaminetetraacetic acid iron ammonium salt 110.0 g Glacial acetic acid 10.0 ml Add water to 11. Ammonia (28%) pH 6 with water
．． Adjust to 0.

Fixer: Ammonium thiosulfate (70%) solution 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 1N
and adjust the pH to 6.0 using acetic acid.

Stabilizer: Formalin (37% aqueous solution) 1.5mJ
Konidax (manufactured by Konishiroku Photo Industry ■) 7.5m! Add water to make 1N.

The density of the obtained piece is measured, and those with a color density of 0.03 or more are defined as "couplers with a fast reaction in the initial stage of development" in the present invention, and those with a color density of 0.01 or less are defined as "couplers with a fast reaction in the early stage of development" in the present invention. A slow-reacting coupler.

Among the couplers used in the present invention, the first coupler is called a protected type coupler that has a slow initial development reaction. However, it is preferable to use a four-equivalent coupler that is highly compatible with high-boiling point solvents, and has a color density of 0.01 or less when measured by the method described above, and preferably one that does not develop any color when developed at 10". Specific structures include the following, but are not limited to these.

C-2 C-3 C-5 C-6 On the other hand, it is preferable that the second coupler is a so-called Fischer type coupler, which has a fast reaction in the initial stage of development. An active site that reacts with an oxide to produce the desired dye (Y, MSC), a ballast group (preferably an organic group having 8 or more carbon atoms) that does not migrate in the gelatin film, and a water-soluble group that dissolves in an alkaline aqueous solution (preferably is a sulfonic acid or carboxylic acid group)
A compound having at least one of each in its molecule, which has a color density of 0 when measured by the method described above.
．． 0.03 or more, preferably 0.07 or more. Specifically, the following compounds are applicable, but are not limited thereto.

C-1 H C-2 OOH C-5 FC-6 FC-7 C-8 Cr z Hz s OCHzCHtCOOH As a method for dispersing the first coupler and the second coupler, known methods can be employed. In order to disperse oil droplets of the first coupler, JP-A-59-102234, JP-A-59-105
The methods described in No. 645, No. 59-109055, etc. may be applied.

For example, phthalate esters (e.g. dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricrendyl phosphate, trioctyl phosphate, etc.), N-substituted acid amides (N,N-diethyllaurinamide, etc.) Boiling point organic solvents alone or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol monoacetate, After dissolving the coupler in a mixture with a low-boiling point organic solvent such as acetylacetone, nitromethane, carbon tetrachloride, chloroform, etc., it is mixed with an aqueous gelatin solution containing a surfactant, and after stirring, it is processed using a homogenizer, colloid mill, etc. The silver halide emulsion used in the present invention can be prepared in addition to the silver halide emulsion after emulsification and dispersion using a dispersion means such as a flow jet mixer or an ultrasonic dispersion device. At the same time, a step of removing the low boiling point organic solvent may be included. Here, the ratio of high boiling point organic solvent to low boiling point organic solvent is 1:
The ratio is preferably 0.1 to 1:50, more preferably 1:1 to 1:20.

In this case, as an oil droplet dispersion aid, JP-A-59-1056
The surfactants described in No. 45 can be used.

Examples of the surfactant include alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates, alkylsulfates, alkylphosphates, sulfonesuccinates, and sulfoalkylpolyoxyethylene alkylphenyl ethers. anionic surfactants such as steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids and alkyl betaines, etc. Cationic surfactants such as quaternary ammonium salts and the like can be used. Specific examples of these surfactants can be found in "Surfactant Handbook" (Sangyo Tosho, 1966) and "Emulsifier/Emulsification Equipment Research/Technical Data Collection" (Science Panronsha, 1966)
1978).

On the other hand, for dispersing the second coupler in an alkaline aqueous solution, the method described in JP-A-59-60437 and the like may be employed. In this case, since 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. The amount of coupler added is preferably such that the total amount of coupler is 0.017 mol or more per mol of silver halide.

The photographic material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., and may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, magenta, magenta,
It has a structure in which a silver halide emulsion layer containing yellow and cyan couplers and a non-photosensitive layer are laminated on a support in an appropriate number and order of layers, but the number and order of layers are It may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in silver emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to P in the mixing pot.
It may also be produced by controlling and sequentially adding H and PAg simultaneously. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention may be formed by cadmium salt, zinc salt, zinc, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, It is possible to add metal ions using iron salts or complex salts and embed them inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitization can be achieved inside the particles and/or on the particle surfaces. Liquid can be applied.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (1,0,0) plane to the (1,1,1) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by conventional methods. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Even if the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect along with the sensitizing dye, or a compound that does not substantially absorb visible light, but which strengthens the sensitizing effect of the sensitizing dye. good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Silver halide is used during chemical ripening, and/or at the end of chemical ripening, and/or after chemical ripening, for the purpose of preventing fog during storage or photographic processing, and/or keeping photographic performance stable. Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the emulsion.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming coupler is selected for the blue light-sensitive emulsion layer. , a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color anti-capri agent may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention is added to reduce the gloss of the photosensitive material and improve the addability.
A matting agent can be added to prevent the sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, worsening, etc.).

The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be prepared directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
The coating may be applied via one or more subbing layers (to improve wear resistance, hardness, antihalation properties, frictional properties, and/or other properties).

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, T-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can be image-formed by color development known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.1 to about 30 g per color developer 11, preferably from about 1 g to about 1.5 g per color developer 11.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers include N,
It is an N'-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N
, N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N,N'-diethylaniline,
Examples include 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, Alkaline agents such as potassium carbonate, alkaline earth sulfites, alkali metal bisulfites 1
．． Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or higher, most commonly about io to
It is about 13.

In the present invention, after color development processing, processing is performed with a processing solution having fixing ability (for example, a fixing solution, a bleach-fixing solution).
When the processing liquid having the fixing ability is a fixing liquid, a bleaching process is performed beforehand. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its structure is aminopolycarboxylic acid or oxalic acid,
Metal ions such as iron, cobalt, and copper are coordinated with organic acids such as citric acid. The most preferred organic acids used to form such organic metal complexes include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching solution and bleach-fixing solution used in the sodium acetate salt contain the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. In addition, pH buffering agents such as borates, oxalates, acetates, carbonic acid supports, phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added can be appropriately added.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid It may contain one or more pH buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When carrying out the process of the present invention while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleaching fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. , the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

E. EXAMPLES The present invention will be described in detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

In order to evaluate the effectiveness of the present invention, coupler emulsions of each type were first prepared. Fisher type couplers are dissolved in IN caustic potassium aqueous solution, then gelatin 1
0% aqueous solution and adjust the pn to 7.0% with IN citric acid aqueous solution.
Adjusted to 0. The protected type coupler is dissolved in a mixed solvent of tricrenyl phosphate and ethyl acetate, then mixed with a 10% gelatin aqueous solution containing Alkanol XC (manufactured by DuPont) as a surfactant, and emulsified and dispersed using a colloid mill. ,Ta. The Fischer type coupler dispersion can also be added to a mixture of protected type couplers and emulsified and dispersed in a colloid mill, but at this time it is not necessary to add a surfactant.

After the coupler emulsion obtained as described above was added to a silver halide gelatin emulsion, a photosensitive layer consisting of each layer having the composition shown below was coated on a triacetate cellulose film support, which was provided with an undercoat layer. Sample (I) was prepared.

1. Emulsion layer negative recording sensitized silver iodobromide (1 mol% 7.0) Coating amount of silver
1.6g/s” Coupler S C-3-----0 for 1 mole of single eye
．． 018 Molar Coupler F C-4-------Single Silver 1
0.001 mole gelatin per mole
1.6g/w” tricrenyl phosphate 0.5g/m”2, protective layer gelatin 1.3g/m”2
．． 4-dichloro-6-hydroxy-5-1-riazine sodium salt 0.05 g/m"For comparison, a photosensitive sample (I
I) was prepared. That is, the couplers in the emulsion layer were as follows.

Coupler 5C-3-.-1111 per mole of silver 0.
The light-sensitive sample obtained in the above manner was subjected to wedge exposure at 1.6 CMS, and then subjected to the following treatment using the processing solution described above (processing temperature: 38°C).

(1) Color development 3 minutes 15 seconds (2) Bleaching 6 minutes 30 seconds (3) Washing 3 minutes 15 seconds (4) Fixing 6 minutes 30 seconds (5) Washing 3 minutes 15 seconds (6) Stabilization 3 minutes 15 seconds processing The table below shows the results of measuring the concentration of the sample using green light.
Shown in 1.

Table 1 From this, it is clear that the graininess has improved, and the sensitivity has also increased by 10%. Incidentally, the gamma of the straight line portion at this time was 1.35 in both cases. Also, relative sensitivity is the reciprocal of the exposure amount that gives a color density of fog + 0.2, and the value of sample ■ is 100
It was calculated as

A multilayer photosensitive sample (2) consisting of each layer having the composition shown below was prepared on a large flame-treated cellulose triacetate base.

1. 1st layer: gelatin layer containing black colloidal silver 2. 2nd layer
Layer = gelatin layer 3 containing an emulsified dispersion of 2,5-di(1)-octylhydroquinone, 3rd layer: low-sensitivity red-sensitive emulsion layer silver iodobromide (red sensitized with a photosensitive dye) (iodide Silver 5 mol%) ------- Coated silver amount 1.85 g/+
w” Coupler S C-5 ------- 1 to 0.04 moles per mole of silver Coupler F C-8 ------- 1 silver
0.002 mol 1-hydroxy-4-(2-
carboethoxyphenylazo)-N-(α-(2,4-
di-t-amylphenoxy)butyl]-2-naphthamide (S C-7) --------- per mole of silver
0.004 mol 2-(1-phenyl-5-tetrazolylthio)-6-[α-(2,4-di-t-amylphenoxy)acetamide]indanone (SC-8)-.-Silver 1
0.003 mol per mole (compounds other than FC-8 are emulsified and dispersed with tricrenyl phosphate.FC
-8 is alkali dispersion, and the following layers use the same addition method) [. 4th layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide (red sensitized with a photosensitive dye) (Silver iodide 8
Moa L/%),------Amount of silver per coating 2
．． 01 g/m+" coupler sc -5----0.02 mol coupler sc-7 for 1 mol of single eye
-------0.001 mol coupler 5 per mol of eye
C-8・----0.002 mol i per mol of silver, 5th layer: same as 2nd layer of intermediate layer, 6th layer: low-sensitivity green-sensitive emulsion layer silver iodobromide ( green sensitized with photosensitive dye) (silver iodide 4 mol%) ---1 ---Amount of coated silver 1.6 g/m"
Coupler 5C-3---0.05 per mole of silver
Molar coupler F C-6------0.0015 mol per mol of silver 1-(2,4,6-dolichlorophenyl)-3-(3-(α-(2,4-di- t-amylphenoxy)acetamido)penzamide]-4-(4-
Methoxyphenylazo)-5-pyrazolone (SC-9)
-・-0.01 mol coupler S C- per 1 mol of silver
8-------0.003 mol gelatin per 1 mol of single eye 1.2 g/m"7, 7th
Layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide (green sensitized with photosensitive dye) (silver iodide 7 mol%)---Amount of silver per coating 1.8 g/n+
"Coupler S C-3--1~--1! 0.01 mol per 1 mole Coupler SC-8---0.001 mol per 1 silver 8, 8th layer: Yellow filter Gelatin layer 9 containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-octylhydroquinone, 9th layer: low-sensitivity blue-sensitive emulsion layer silver iodobromide (silver iodide 6 mol %) --- Coated silver amount: 1.6g
/m'' Coupler S C-2--1--0.
25 mol coupler F C-2------0.015 mol 10 per mol of silver, 10th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide (silver iodide 8 mol%)--- 11--Amount of coated silver 1.1 g/+a2 Coupler 5C-2---0.0 per mole of silver
6 mol 11, 11th layer: gelatin protective layer In addition, as comparative sample
-2 were respectively removed, and instead 5C-5, 5C-3 and 5C-2 were each increased by the number of moles corresponding to the Fischer type coupler. The thus obtained photosensitive material was subjected to wedge exposure and wedge exposure for FTM measurement, and was then developed in the same manner as in Example 1.

The measured values of the obtained pieces are shown in Table 2.

Table 2 As a result, the samples based on the present invention had less fog and
Graininess is greatly improved while maintaining good sharpness.

Agent: Hiroshi Aisaka, Patent Attorney (Spontaneous) Procedural Amendment 1985 Patent Application No. 12295 2 Name of invention Photographic light-sensitive material 3 Relationship to the case of the person making the amendment Patent applicant address Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-26-2 Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Number of inventions increased by amendment 7, Subject of amendment (1), between lines 10 and 111 on page 34 of the specification,
“I will add gelatin 2.0g/n?J.

(2) Between the second line from the bottom of No. 34 and Suesha, "Gelatin 1.8 g/n?J is added.

(3), between the third and second lines from the bottom of page 35, “
Add gelatin 1.7 g/m.

(4) On page 36, between lines 6 and 7, there is a message that says ``Gelatin 2.5g/n?J''.

(5) On page 36, between lines 10 and 111, there is a message that says ``Add 1.4 g/ml of gelatin.

- Above -

Claims (1)

[Claims] 1. A silver halide emulsion layer containing a first coupler dispersed in oil droplets and a second coupler dispersed in an aqueous alkali solution, and in this silver halide emulsion layer, the ratio of the second coupler to the total amount of couplers is 50 mol. % or less,
and a photographic light-sensitive material, wherein the first coupler is a coupler with a slow initial development reaction, and the second coupler is a coupler with a fast initial development reaction.