JP2849868B2 - Method for producing silver halide photographic emulsion and silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for producing a silver halide photographic emulsion useful in the field of photography, and a silver halide color photographic material using the emulsion. More specifically, fog is low,
The present invention relates to a method for producing a silver halide photographic emulsion having high sensitivity and a silver halide color photographic light-sensitive material using the emulsion.

[Conventional technology]

In recent years, performance requirements for photographic silver halide emulsions have become increasingly severe, and higher-level demands have arisen for photographic characteristics such as high sensitivity, low fog, and high gamma. For this reason, various techniques for increasing the sensitivity of photosensitive silver halide emulsions have been developed. For example, JP-A-60-1433
Techniques using a so-called core / shell type emulsion having a high iodine content layer therein as shown in JP-A-31-61, JP-A-61-245151 and JP-A-61-148442 are known.

However, such an emulsion, in its manufacturing method,
In this method, a silver salt aqueous solution and a halogen salt aqueous solution are added to a colloidal aqueous solution in a reaction vessel. In the vicinity of the addition position of each reaction solution, a portion having a high concentration of silver ions and halide ions is generated, and uniform silver halide is formed. It was difficult to produce the particles. Due to this local concentration bias, for example, reduced silver or fogged silver is generated in a high-concentration portion of silver ions, which causes deterioration of fog.

As means for improving such non-uniformity caused by the presence of local high concentration parts of silver ions and halogen ions, JP-A-1-183417, JP-A-1-183644, and JP-A-1-1834
No. 65, 2-166442, etc., a method in which an emulsion composed of fine silver halide grains is supplied to a reaction vessel for growing a crystal of a silver halide emulsion to grow a seed emulsion in the reaction vessel. Is disclosed.

Upon further examination of the above patent, the present inventors have found that fine silver halide grains are very unstable at the time of their formation. That is, the fine particles having a size of 0.02 μm or less are formed and aggregate at the same time, and it is difficult to supply the fine particles to the seed emulsion in the reaction vessel. Even if supplied, ripening occurred between the aggregated fine particles, and almost no fine particles contributed to the growth of the seed particles. On the other hand, 0.02μ
The fine particles having a size exceeding m are relatively stable after formation, but have a wide size distribution, so that large-sized components grow and do not contribute to the growth of seed particles in the reaction vessel. As a result, the resulting emulsion has a broad particle size distribution,
It was not a high-sensitivity, low-fogging emulsion desired by the present inventors.

[Object of the invention]

A first object of the present invention is to provide a silver halide emulsion in which fine silver halide grains have high stability at the time of formation and after formation, and which rapidly contribute to crystal growth of seed grains in a reaction vessel. It is to provide a manufacturing method of.

A second object of the present invention is to provide a method for producing a silver halide emulsion having low fog and high sensitivity, and a silver halide color photographic material using the emulsion.

[Configuration of the invention]

The present inventors have made intensive studies and found that the above object can be achieved by the following constitutions.

That is, (1) an emulsion composed of fine silver halide grains is supplied to a reaction vessel having an aqueous protective colloid solution for growing crystals of the photosensitive silver halide emulsion. A method for producing a part or all of the emulsions, wherein an emulsion comprising the fine silver halide grains is formed in the presence of a compound represented by the following general formula [I].

General formula [I] Wherein, Y is a hydrogen atom, a -SO ₃ M or -COBCOOM.
M represents a hydrogen atom, an alkali metal atom, an ammonium group or an alkyl-substituted ammonium group having 5 or less carbon atoms;
Represents a chain or cyclic group forming an organic dibasic acid. m
And n each represent 0 to 50, and p represents 1 to 100.

(2) A silver halide color photographic material having at least one silver halide emulsion layer on a support,
The photosensitive silver halide emulsion of the silver halide emulsion layer is a silver halide color photographic light-sensitive material produced by the method described in (1).

 Hereinafter, the present invention will be described in detail.

First, the compound represented by the above general formula [I] (hereinafter sometimes abbreviated as the compound of the present invention) which is present at the time of forming the fine silver halide emulsion of the present invention will be described.

Conventionally, when producing a silver halide photographic light-sensitive material,
When the emulsion raw materials are stirred or moved, such as in the step of producing an aqueous gelatin solution, the step of adding a water-soluble halide and a water-soluble silver salt to the aqueous gelatin solution, and the step of coating the emulsion on a support, foaming occurs. The phenomenon is remarkable, and the compound of the present invention has been preferably used as an antifoaming agent therefor. These techniques are described in detail in JP-A-44-9497.

Of course, the present inventors have utilized the compound of the present invention also as an antifoaming agent at the time of forming a silver halide emulsion, but what is important in the present invention is that at the time of forming fine silver halide grains. By the presence of the compound of the invention,
It has been found that silver halide has a great influence on nucleation and subsequent physical ripening.

That is, JP-A-1-183417, JP-A-1-183644, and JP-A-1-183417.
In the prior arts such as 183645 and 2-166442, when the particle size of fine silver halide grains is 0.02 μm or less, remarkable agglomeration occurred during and immediately after formation.
Aggregation was prevented by the presence of the compound of the present invention, and the stability in the state of fine particles was significantly improved.In fine particles exceeding 0.02 μm, a component having a large particle diameter was
When the seed emulsion subsequently grew without dissolving during the crystal growth, the particle size distribution was widened.On the other hand, when the fine particles formed in the presence of the compound of the present invention were used, the particle size was reduced. Even if the thickness exceeds 0.02 μm, the seed emulsion was rapidly dissolved during the growth of the seed emulsion, and a desired silver halide emulsion could be obtained.

From these facts, the compound of the present invention is adsorbed on the surface of silver halide grains at the time of nucleation of silver halide grains, thereby preventing aggregation of fine particles and suppressing Ostwald ripening of fine particles to thereby suppress nucleation after nucleation. It is expected that the spread of the particle size distribution is prevented.

Hereinafter, typical specific examples of the compound of the present invention are shown, but the present invention is not limited thereto.

It is important that the compound of the present invention is present at the time of nucleation of fine silver halide grains, and the effect of the present invention is not obtained at all even if added after nucleation. That is, a method of forming fine silver halide grains in a mixer separate from the reaction vessel in which the seed emulsion crystal is grown is preferably used, but the protective colloid aqueous solution (solution A) is previously placed in the mixer. And a water-soluble silver salt aqueous solution (B
Liquid) and an aqueous solution of a water-soluble halide (liquid C) to form silver halide grains having a desired fine size, the compound of the present invention is added to any of liquids A, B, and C in advance. May be added to all the liquids,
It is preferable to add it to the solution in advance. In the case where nucleation is carried out in a mixer by adding a protective colloid to solution B and / or solution C without using liquid A in advance in the mixer (solutions B 'and C' respectively). The compound of the present invention may be added in advance to either solution B 'or solution C', or may be added to both solutions, but is preferably added to solution C 'in advance.

The amount of the compound of the present invention is 1 × 10 ⁻³ per mol of silver.
１1 × 10 ² g is preferred, and 1 × 10 ² -10 g is more preferred.
Further, the compound of the present invention may be added during the growth of seed emulsion crystals in a reaction vessel. In this case, the compound exhibits its function as an antifoaming agent.

Next, fine silver halide grains (hereinafter sometimes abbreviated as fine grains of the present invention) will be described.

Preparation method of the fine particles of the present invention, JP-A-1-183417,
Reference can be made to the description of JP-A Nos. 1-183644, 1-183645 and 2-166442. However, as described above, the fine particles of the present invention require the presence of the compound of the present invention at the time of nucleation.

The fine particles of the present invention are preferably 0.08 μm or less, and 0.06 μm
The following is more preferred, and the most preferred is 0.02 μm or less.

When the particle size of the present invention exceeds 0.02 μm, the particle size distribution is preferably at most 20%, more preferably at most 15%.

The halogen composition of the fine grains of the present invention is silver bromide, silver iodide,
Silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, any of silver chloroiodobromide, depending on the intended halogen composition of the photosensitive silver halide emulsion according to the present invention, They can be used in any combination.

A method for preparing the photosensitive silver halide emulsion according to the present invention using the fine particles of the present invention is described in JP-A-1-183417.
Nos. 1, 183644, 1-183645, and 2-166442 can be referred to. The features of the methods disclosed in these patents include the following two.

(A) Immediately after the fine particles are formed in the mixer, they are added to the reaction vessel.

(B) Add the previously prepared fine particles to the reaction vessel.

In the present invention, any of the methods (a) and (b) can be preferably used.

As the fine particles of the present invention, low molecular weight gelatin can be used in addition to gelatin having an average molecular weight of 100,000 which is usually used as a protective colloid. At this time, the average molecular weight of the gelatin is preferably 30,000 or less, more preferably 10,000 or less.

The particle size of the fine particles of the present invention can be confirmed by placing the particles on a mesh and using an electron microscope as it is, and the magnification is preferably 20,000 to 70,000.

Next, the photosensitive silver halide emulsion according to the present invention (hereinafter referred to as "the silver halide emulsion")
(Sometimes abbreviated as the emulsion according to the present invention).

The emulsion according to the present invention is obtained by preliminarily presenting an aqueous solution containing a protective colloid and a seed emulsion in a reaction vessel, and supplying the fine particles of the present invention and, if necessary, silver ions and halogen ions to grow the seed emulsion. Things. Here, the seed emulsion can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed emulsion is arbitrary, and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred. When silver iodobromide is used, the silver iodide content is preferably at most 5 mol%.

In the present invention, the aqueous solution containing a protective colloid refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by gelatin or another substance capable of forming a hydrophilic colloid (a substance capable of serving as a binder), and preferably a colloidal substance. An aqueous solution containing protective gelatin.

When gelatin is used as the protective colloid in the practice of the present invention, the gelatin may be either lime-treated or acid-treated.
The details of the method for producing gelatin are described in Arthur Wuice: The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates and the like. Sugar derivatives such as cellulose derivatives, sodium alginate, starch derivatives, etc .; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various kinds of synthetic hydrophilic polymer substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole.

For gelatin, jelly strength 200 in buggy method
It is preferable to use the above.

The amount of gelatin added during the preparation of the emulsion according to the present invention is preferably at least 1% (by weight), particularly preferably at least 1.5%, during core growth.

The silver halide composition of the emulsion according to the present invention is optional,
For example, usable silver halides include silver chloride, silver bromide,
Silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodide, silver chloroiodobromide,
And any silver halide such as a mixture thereof, but silver iodobromide is particularly preferably used. When silver iodobromide is used, the silver iodide content is preferably at least 4 mol%, more preferably 6.0 to 10.0 mol%, as the average silver iodide content of the whole silver halide grains. More preferred.

In this case, it is desirable to use so-called core / shell type grains in which silver iodide is concentrated.

The core / shell type particles are particles composed of a core serving as a nucleus and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell are preferably different from each other, and it is particularly preferable that the core and the shell are formed with the maximum silver iodide content.

The silver iodide content of the core is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 25 mol% or more. The silver iodide content of the outermost shell of the above-mentioned shells, that is, the shell which normally forms the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. It is desirable that the proportion occupied by the core is 2 to 60% of the volume of the whole particles,
More preferably, 5 to 50%.

When the emulsion according to the present invention is an emulsion comprising core / shell type silver halide grains, the silver halide grains may be normal crystals such as cubic, octahedral, or tetrahedral, or may be twins. Alternatively, a mixture thereof may be used, but a normal crystal is preferable.

As the means for forming the emulsion according to the present invention, various methods well known in the art can be used. That is, the single jet method, the double jet method, the triple jet method, and the like can be used in any combination. Also, pA in the liquid phase where silver halide is formed
A method of controlling g and pH in accordance with the growth rate of silver halide can also be used.

The emulsion according to the present invention is partially or entirely formed by supplying the fine particles of the present invention to a seed emulsion to cause crystal growth. The proportion of the emulsion according to the present invention formed by the fine particles of the present invention is preferably 5 mol% or more in terms of Ag amount, and more preferably 15 to 100 mol%. However, the amount of Ag occupied by the seed emulsion in the emulsion according to the present invention is excluded.

The grain size of the silver halide grains is not particularly limited, but preferably has an average grain size of 0.1 to 3 μm. More preferably, it is 0.2 to 2 μm.

The emulsion according to the present invention may be any emulsion such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution.Each emulsion may be a single emulsion or a mixture of several kinds of these emulsions. There may be. When a light-sensitive material is prepared using the emulsion according to the present invention, a monodisperse emulsion is preferable.

Here, as the monodispersed silver halide emulsion, it is preferable that the weight of silver halide contained in a grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains. , More preferably 70% or more, even more preferably 80% or more.
% Or more.

Here, the average particle size is the frequency ni of the particles having the particle size ri.
The product ni × ri ³ and ri ³ is defined as a grain size ri when the maximum (three significant figures, the minimum digit is ON 4 discard 5).

The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains of a shape other than spherical. .

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter or the area at the time of projection on the print (the number of measured particles is zero). Discrimination should be 1,000 or more.)

Particularly preferred highly monodisperse emulsions of the invention are Is defined as 20% or less, and more preferably 15% or less.

Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

As a method for obtaining a more advanced monodisperse emulsion, Japanese Patent Application Laid-Open No.
The growth method in the presence of tetrazaindene disclosed in 122935 can be applied.

In preparing the emulsion according to the present invention, a known silver halide solvent such as ammonia, thioether, or thiourea may be present, or a silver halide solvent may not be used.

In the step of forming and / or growing the silver halide grains, metal ions are formed by using at least one selected from cadmium salts, zinc salts, lead salts, thallium salts, and iridium salts (including complex salts). These metal elements can be added to the inside of the grain and / or on the grain surface, and a reduction sensitization nucleus can be imparted to the inside of the grain and / or the grain surface by placing the metal element in an appropriate reducing atmosphere. .

The silver halide grains may be either grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.

The emulsion according to the present invention may be one in which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or one in which the soluble salts are still contained. When removing the salts, use Research D. Closure (Research D).
isclosure (hereinafter abbreviated as RD)) No. 17643 No. II. More specifically, in order to remove the soluble salts from the emulsion after the formation of the precipitate or after the physical ripening, a Noudel water washing method in which gelatin is gelatinized may be used, and inorganic salts and anionic surfactants may be used. Alternatively, a sedimentation method (flocculation) using an anionic polymer (eg, polystyrene sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used.

 The emulsion according to the present invention can be subjected to chemical sensitization.

Chemical ripening, i.e. the conditions of the chemical sensitization process, e.g. pH, pA
There are no particular restrictions on g, temperature, time, additives, and the like, and the reaction can be performed under conditions generally performed in the art.

For chemical sensitization, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or active gelatin, selenium sensitization using a selenium compound, reduction sensitization using a reducing substance, gold or other A noble metal sensitization method using a noble metal compound or the like can be used alone or in combination.

Known sulfur sensitizers can be used. For example, thiosulfate, allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be used. In addition, U.S. Patent Nos. 1,574,944 and 2,410,689
No. 2,278,947, 2,728,668, 3,501,313,
No. 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-24937, and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount depends on the amount of other additives added during chemical sensitization, pH,
It varies over a considerable range under various conditions such as temperature and size of silver halide grains, but as a guide, about 10 ^-7 mol to about 10 ^-1 mol per mol of silver halide is preferable.

A selenium sensitizer can be used instead of the sulfur sensitizer. Examples of the selenium sensitizer include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethylselenide, and diethyldiselena. Seides such as seides can be used, and specific examples thereof are described in U.S. Pat.
Nos. 574,944, 1,602,592 and 1,623,499.

The amount of addition varies over a wide range as in the case of the sulfur sensitizer, but the standard is about 10 ^-7 per mole of silver halide.
Mol to 10 ¹ moles is preferable.

In the present invention, when a gold sensitizer is used, the valence of gold may be +1 or +3, and various gold compounds may be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acidide, ammonium aurothiocyanate, and pyridyl trichlorogold. Can be.

The addition amount of the gold sensitizer may vary depending on various conditions, ranging from about ^10-7 to ¹ mol per mol of silver halide as a guide.

Gold - gold ions are released from Zerachinato, and can be used a compound which enhances gold ions adsorption to silver halide grains, preferred as such are, R ₂
MX ₄ , R ₃ MX ₆ or MX ₆ (wherein, R represents a hydrogen atom, an ammonium group, or an alkali metal atom, M is pt or pd, M is
Represents Ir or Rh. X represents a halogen atom. ) Is a complex salt of Rh, Pd, Ir, Pt, etc.

Specific compounds include (NH ₄ ) ₂ PdCl ₄ and (NH ₄ ) ₂ PtC
Examples include l ₄ , K ₃ IrBr ₆ , (NH ₄ ) ₃ RhCl ₆ .12H ₂ O, and particularly preferred is ammonium tetrachloropalladium (II) (NH ₄ ) ₂ PdCl ₄ . The amount added is 10 to 10 in stoichiometric ratio (molar ratio) to the gold sensitizer.
A range of 0 times is preferred.

The timing of addition may be any of the steps at the start of chemical ripening, during ripening, and after ripening, but preferably during chemical ripening, particularly preferably at the same time as or before or after the addition of the gold sensitizer.

In the practice of the present invention, reduction sensitization can be used in combination. Although there is no particular limitation on the reducing agent, known stannous chloride, thiourea dioxide, hydrazine derivatives,
Polyamine and the like can be mentioned.

When reduction sensitization is performed, it is usually performed during the growth of silver halide grains, but chalcogen sensitization, gold sensitization and Rh, P
It is preferably carried out after completion of sensitization with a compound selected from noble metal compounds such as d, Ir and Pt.

Silver halide emulsions can be optically sensitized to a desired wavelength range. The optical sensitization method is not particularly limited. For example, a cyanine dye such as a zero methine dye, a monomethine dye, a dimethine dye, a trimethine dye, or an optical sensitizer such as a merocyanine dye is used alone or in combination (for example, supersensitization). It can be optically sensitized. These techniques are described in U.S. Patent Nos. 2,688,545 and 2,912,329.
No. 3,397,060, 3,615,635, 3,628,964,
UK Patents 1,195,302, 1,242,588, 1,293,862
No. 2, West German Patents (OLS) 2,030,326, 2,121,780, JP-B-43-4936, 44-14030, and the like. The selection can be arbitrarily determined according to the purpose and application of the photosensitive material, such as the wavelength range to be sensitized, the sensitivity, and the like.

Such a spectral sensitizing dye is used during the crystal growth, after the completion of crystal formation, before the desalting step, during the desalting step, before and after the addition of the chemical sensitizer, before the end of the chemical sensitization, after the end, and in the preparation of a coating solution. Addition and mixing can be carried out at any time during the preparation of the emulsion, such as before, after preparation and immediately before coating.

In the practice of the present invention, various compounds may be added to the silver halide emulsion at the end of chemical ripening for the purpose of preventing fogging during the production process, storage or development, or stabilizing photographic performance. May be contained.

For example, azoles such as benzothiazolium salts,
Nitroindazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), and the like, Mercaptopyrimidines, mercaptotriazines, for example, thioketo compounds such as oxazolinethione, further, benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives Many compounds known as antifoggants or stabilizers can be added. These compounds are preferably added to the silver halide emulsion during chemical ripening or before coating on a support.

The silver halide emulsion can contain various binders. When containing gelatin as a binder,
As the gelatin, normal photographic gelatin is preferred,
Not only gelatin but also derivative gelatin is included. Examples of the derivative gelatin include a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and an isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. Things etc. are included. Examples of the acid anhydride used in the reaction with gelatin include, for example, maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride.Examples of isocyanate compounds include Phenyl isocyanate, p-bromophenyl isocyanate, p-chlorophenyl isocyanate, p
-Tolyl isocyanate, p-nitrophenyl isocyanate, naphthyl isocyanate and the like.

Compounds having an active halogen atom further include, for example, benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride Sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminobenzenesulfonyl chloride, 2-
Carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2
-Amino-5-methylbenzenesulfonyl chloride,
Phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride and the like are included.

In the silver halide emulsion, a hydrophilic colloid other than gelatin can be used as a binder. For example, colloidal albumin, agar, acacia, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, polyacrylamide, imidized polyacrylamide, casein, for example, vinyl alcohol-vinyl Urethanecarboxylic acid groups such as cyanoacetate copolymers, or vinyl alcohol polymers containing cyanoacetyl groups,
Polyvinyl alcohol-polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, a polymer obtained by polymerization of a protein or a saturated acylated protein and a monomer having a vinyl group, polyvinyl pyridine, polyvinyl amine, polyaminoethyl methacrylate, polyethylene imine, and the like can also be used. .

In the silver halide emulsion, a gelatin hardener can be used, particularly when it is constituted as an emulsion layer, and such a hardener generally reacts with gelatin to cause crosslinking, and as a by-product when exhibiting a hardening action. Which generate an organic or inorganic acid. Releases hydrohalic acid, for example
2,3-dihalogenomalealdehyde acids (U.S. Pat.
No. 19), 2,4-dichloro-s-triazines (U.S. Pat.
3,325,287), chloropyrimidine derivatives (UK Patent 1,1
93,290), polymers containing a chlorotriazine ring in the side chain (US Pat. No. 3,362,827, West German Patent Publication 1,921,363)
), Dichlorophosphamide derivatives (UK Patent 974,72)
No. 3, No. 1,004,658), halomethyl derivatives (UK Patent 99
0,275) phosphonitrile chloride derivative (US Patent
3,186,848) or release phenol derivatives 2
-Phenoxy-3-halogeno-malealdehyde acid derivatives (UK Patent 1,192,775) and the like can be used.

In the case of a silver halide emulsion, especially when it is formed as an emulsion layer, other coating aids, such as antistatic, lubricity improvement, emulsification dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, hardening, sensitization), etc. Various known surfactants may be included for various purposes.

That is, U.S. Pat.Nos. 2,240,472, 2,831,766, 3,15
8,484, 3,210,191, 3,294,540, 3,507,660
No., UK Patents 1,012,495, 1,022,878, 1,179,29
No. 0, 1,198,450, U.S. Pat.Nos. 2,739,891, 2,823,1
No. 23, No. 1,179,290, No. 1,198,450, No. 2,739,891
No. 2,823,123, 3,068,101, 3,415,649,
3,666,478 and 3,756,828, British Patent 1,397,218
No. 3,113,816, No. 3,411,413, No. 3,473,174,
3,345,974, 3,726,683, 3,843,368, Belgian patent 731,126, British patent 1,138,514, and 1,159,82
No. 5, No. 1,374,780, U.S. Pat.No. 2,271,623, No. 2,288,2
No. 26, No. 2,944,900, No. 3,235,919, No. 3,671,247
No. 3,772,012, 3,589,906, 3,666,478,
No. 3,754,924, West German Application Publication (OLS) No. 1,961,683, JP-A-50-117414, JP-A-50-59025, JP-B-40-378
Nos. 40-379 and 43-13822, for example, saponins (steroids), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl or alkylaryl ethers, Polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols , Sugar alkyl esters, also non-ionic surfactants such as urethanes or ethers, triterpenoid saponins, Alkyl carboxylate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinate, sulfoalkyl polyoxyethylene alkyl phenyl ether, Carboxy groups such as polyoxyethylene alkyl phosphates, sulfo groups, phospho groups, sulfate groups, anionic surfactants containing acidic groups such as phosphate groups, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or Amphoteric surfactants such as phosphates, alkyl betaines, amine imides and amine oxides, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary compounds such as pyridium and imidazolium; Cationic surfactants such as ammonium salts and sulfonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Silver halide emulsions can be used as development accelerators in addition to the above-mentioned surfactants in West German Patent Application (OLS) Nos. 2,002,871 and 2,44.
It may contain imidazoles, thioethers, selenoethers and the like described in 5,611, 2,360,878, British Patent 1,352,196 and the like.

In order to apply the emulsion obtained by the present invention to a color light-sensitive material, a combination of cyan, magenta and yellow couplers is contained in each of the red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers. The method and material used for the color photosensitive material may be applied. Here, the coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion.
Also, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor upon development (so-called DIR)
Coupler). Further, the coupler may be such that the product of the coupling reaction is colorless.

As the yellow color coupler, a known open-chain ketomethylene coupler can be used. Among them, benzoylacetoanilide compounds and pivaloylacetoanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used are described in U.S. Patent Nos. 2,875,057, 3,265,506, and 3,408,
No. 194, No. 3,551,155, No. 3,582,322, No. 3,725,072
No. 3,891,445, West German Patent 1,547,868, West German Application Publication (OLS) 2,213,461, 2,219,917, 2,261,361
Nos. 2,414,006 and 2,263,875.

As the magenta coloring coupler, a pyrazolone-based compound, an indazolone-based compound, a cyanoacetyl compound, or the like can be used, and a pyrazolone-based compound is particularly advantageous. Specific examples of magenta coloring couplers that can be used are described in U.S. Pat.Nos. 2,600,788, 2,983,608, 3,062,653,
3,127,269, 3,314,476, 3,419,391, 3,51
9,429, 3,558,319, 3,582,322, 3,615,506
No. 3,834,908, No. 3,891,455, West German Patent 1,810.46
No. 4, West German Application Publication (OLS) No. 2,468,865, No. 2,417,945
No. 2,418,959, 2,424,467 and JP-B-40-6031.

As the cyan coloring coupler, a phenol compound, a naphthol compound, or the like can be used. Specific examples are U.S. Pat.Nos. 2,369,929, 2,434,272, and 2,474,29.
No. 3, No. 2,521,908, No. 2,895,826, No. 3,034,892,
3,311,476, 3,458,315, 3,476,563, 3,5
Nos. 83,971, 3,591,383, 3,767,411, West German Application Publication (OLS) 2,414,830, 2,454,329, JP-A-48-598
No. 38, etc.

As a colored coupler, for example, US Patent 3,476,560
No. 2,521,908, No. 3,034,892, JP-B-44-2016,
Nos. 38-22335, 42-11304, 44-32461, and West German Application Publication (OLS) 2,418959 can be used.

As a DIR coupler, for example, U.S. Patent No. 3,227,554,
3,617,291, 3,701,783, 3,790,384, 3.6
No. 32,345, West German Application Publication (OLS) Nos. 2,414,006, 2,454,
Nos. 301 and 2,454,329 and British Patent 953,454 can be used.

In addition to the DIR coupler, a compound which releases a development inhibitor upon development may be contained in the light-sensitive material. For example, US Pat. Nos. 3,297,445 and 3,379,529, published in West German Application (OL
S) Those described in 2,417,914 can be used. Other JP-A Nos. 55-85549, 57-94752, 56-65134, 56
-135841, 54-130716, 56-1333734, 56-
135841, U.S. Patent 4,310,618, UK Patent 2,083,640
Issue, Research Disclosure 18360 (1979), 1
4850 (1980), 19033 (1980), 19146 (1980),
Couplers described in 20525 (1981) and 21728 (1982) can also be used.

Two or more couplers may be contained in the same layer. Further, the same compound may be contained in two or more different layers.

A known method, for example, the method described in U.S. Pat. No. 2,322,027 is used to introduce the silver halide emulsion layer into the puller. For example, alkyl phthalates (eg, dibutyl phthalate, dioctyl phthalate), phosphates (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid, esters (eg, tributyl acetyl citrate), benzoate ( For example, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl After dissolving in isobutyl ketone, β-ethoxyethyl alkylene acetate, methyl cellosolve acetate, or the like, it is dispersed in a hydrophilic colloid. The above-mentioned high-boiling organic solvent and low-boiling organic solvent may be mixed and used.

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

These couplers are generally used in a silver halide emulsion layer.
It is preferable to add 2 × 10 ^{-3 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^{-2 to} 5 × 10 ^-1 mol, per mol of silver.

Also, as a color antifoggant, hydroquinone derivatives,
Aminophenol derivatives, gallic acid derivatives, may contain ascorbic acid derivatives and the like, specific examples of which are described in U.S. Patent Nos. 2,360,290, 2,336,327, 2,403,721, and 2,4.
18,613, 2,675,314, 2,701,197, 2,704,71
No. 3, 2,728,659, 2,732,300, 2,735,765,
JP-A-50-92988, JP-A-50-92989, JP-A-50-93928,
No. 50-110337 and Japanese Patent Publication No. 50-23813.

As an antistatic agent, diacetyl cellulose, styrene-perfluoroalkyl sodium maleate copolymer,
An alkali salt or the like of a reaction product of a styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid is effective.
Examples of the matting agent include polymethyl methacrylate, polystyrene, and an alkali-soluble polymer. It is also possible to use colloidal silicon oxide.

As the latex added to improve the physical properties of the film, a copolymer of an acrylate ester, a vinyl ester or the like with another monomer having an ethylene group can be exemplified. Examples of gelatin plasticizers include glycerin and glycol compounds, and styrene-
Examples thereof include a sodium maleate copolymer and an alkyl vinyl ether-maleic acid copolymer.

As a support for coating the emulsion obtained by the present invention to obtain a photosensitive material, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, for example, polyethylene There are polyester films such as terephthalate, polystyrene and the like, and these supports are appropriately selected according to the purpose of use of each photosensitive material.

 These supports are subjected to a subbing process as required.

The light-sensitive material using the emulsion obtained by the present invention can be subjected to development processing after exposure by a commonly used known method.

The black-and-white developer is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols and aminobenzenes, and may further contain an alkali metal salt sulfite, carbonate, bisulfite, bromide and iodide. it can. When the light-sensitive material is a color material, color development can be performed by a commonly used color development method. In the reversal method, development is performed first with a black-and-white negative developer, followed by white exposure or processing in a bath containing a fogging agent, followed by color development with an alkali developer containing a color developing agent. There is no particular limitation on the processing method, and any processing method can be applied. For example, typical examples include a method in which bleach-fixing is performed after color development, followed by further washing and stabilization if necessary, or color development. Thereafter, a method in which bleaching and fixing are performed separately, and if necessary, further washing with water and stabilizing treatment can be applied.

Such a photosensitive material can be applied to many uses. For example, it can be used 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.

When applied to a multilayer color photographic material, it can be applied to various layer configurations well known in the art, that is, a normal layer, a reverse layer, and any other layer configurations.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples.
The present invention is not limited by these examples.

Example 1 (Preparation of silver bromide fine particle emulsion) 10.6 mol of silver nitrate and potassium bromide are contained in 5000 ml of a 2.6% by weight gelatin (COL-1: average molecular weight = 8000) solution containing 0.02 mol of potassium bromide. 3500 ml of each aqueous solution were added at an accelerated flow rate (the flow rate at the end was 5 times the initial flow rate) over 28 minutes. The temperature during the preparation of the microparticles was kept at 15 ° C. The obtained silver bromide fine particles were confirmed by an electron micrograph at a magnification of 60,000, and the average particle size was 0.018 μm. This silver bromide fine grain emulsion is designated as MC-1. After the preparation, 10 ml of the fine particles were taken into a test tube and left at 15 ° C., and after 3 minutes, aggregation occurred and completely separated from the supernatant.

To a 2.6% by weight gelatin (COL-1: average molecular weight = 8000) solution containing 0.02 mol of potassium bromide, 3.0 g of the compound I-1 of the present invention was added, and thereafter bromination was carried out in the same manner as MC-1. Silver fine particles MC-2 were prepared.

Further, 2.5 g of I-2 was added in place of the compound I-1 of the present invention, and silver bromide fine particles MC-3 were prepared in the same manner as described below.

The cohesiveness of MC-2 and MC-3 was evaluated in the same manner as MC-1.

 The results are shown in Table 1.

(Preparation of silver iodide fine grain emulsion) To a 1000 ml of a 2.6% by weight gelatin (COL-1) solution containing 0.004 mol of potassium iodide, 250 ml of an aqueous solution containing 1.06 mol of silver nitrate and potassium iodide was added at an accelerated flow rate. (The flow rate at the end was 4 times the initial flow rate). The temperature during the preparation of the microparticles was kept at 15 ° C. When the obtained silver iodide fine particles were confirmed by an electron micrograph at a magnification of 60,000, the average particle size was 0.016 μm. This silver iodide fine grain emulsion is designated as MC-4.

0.3 ml of the compound I-1 of the present invention is added to 1000 ml of a 2.6% by weight gelatin (COL-1) solution containing 0.004 mol of potassium iodide.
After adding 0 g, MC-5 was prepared in the same manner as MC-4.

Further, 0.23 g of I-2 was used instead of the compound I-1 of the present invention.
In addition, MC-6 was prepared in the same manner as described below.

Regarding MC-4 to 6, aggregation was evaluated in the same manner as MC-1.

 The results are shown in Table 1.

The cohesiveness was indicated by "x" when completely separated from the supernatant within 5 minutes after standing, and "o" when no separation from the supernatant occurred even after standing for 3 hours.

As is evident from Table 1, the fine grain emulsion of the present invention comprises:
Aggregation did not occur at all even if left for 3 hours after preparation, and it was confirmed that the compound was stably present.

Example 2 (Preparation of silver bromide fine particle emulsion) 350 ml of an aqueous solution containing 10.6 mol of silver nitrate and potassium bromide was accelerated in 5000 ml of a 2.6% by weight gelatin (COL-1) solution containing 0.02 mol of potassium bromide. The addition was performed at the set flow rate (final flow rate was 5 times the initial flow rate) for 28 minutes.
The temperature during the preparation of the microparticles was kept at 30 ° C. The obtained silver bromide fine particles were confirmed by an electron microscope photograph at a magnification of 60,000, and as a result, the average particle size was 0.047 μm and the particle size distribution was 32.1%. This silver bromide fine grain emulsion is designated as MC-7.

3.1 g of the compound I-1 of the present invention was added to 5000 ml of a 2.6% by weight gelatin (COL-1) solution containing 0.02 mol of potassium bromide.
After adding g, MC-8 was prepared in the same manner as MC-7.

Furthermore, 2.8 g of I-2 was added in place of I-1, and MC-9 was similarly prepared.

 Table 2 shows the results.

As is clear from Table 2, it was confirmed that the fine grain emulsion of the present invention having an average grain size exceeding 0.02 μm had a narrow grain size distribution and high monodispersity.

Example 3 (Preparation of Octahedral Silver Iodobromide Emulsion) Octahedral silver iodobromide emulsion having monodispersed silver iodobromide grains (average grain size: 0.33 μm) (silver iodide content: 2 mol%) as seed crystals Was prepared.

The solution <G-1> was maintained at a temperature of 75 ° C., pAg 7.8 and pH 7.0,
While stirring well, 144.4 ml of a seed emulsion equivalent to 0.34 mol was added. Thereafter, the silver bromide fine grain emulsion (MC-7) and the silver iodide fine grain emulsion (MC-5) were maintained at a flow rate of 7: 3 at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate). The addition took 86 minutes. The fine particles consumed during this time are (MC-
The total of (7) and (MC-5) was equivalent to 1.82 mol.

Thereafter, while maintaining pAg 10.1 and pH 6.0, a silver bromide fine grain emulsion (MC-7) was added at an accelerated flow rate (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes. The fine particles (MC-7) consumed during this period were equivalent to 6.67 mol.

The emulsion obtained had an average particle size of 0.94 μm and a particle size distribution of 30.5 μm.
%, And octahedral silver iodobromide grains having a silver iodide content of 6.26 mol%. This emulsion was desalted by a flocculation method, and adjusted to pH 5.80 and EAg = 100 mV at 40 ° C. This emulsion is designated as EM-1.

In the preparation of EM-1, instead of MC-7, MC-8, MC-9
Was used to prepare EM-2 and EM-3, respectively.

 The results are shown in Table-3.

Emulsion EM-1 obtained using a fine grain emulsion MC-7 prepared without the compound I-1 of the present invention during nucleation.
Is markedly degraded in particle size distribution.
EM-2 and EM-3 obtained using MC-8 and MC-9 have narrow particle size distributions. This is because MC-
8, indicating that MC-9 was rapidly dissolved.

COL-0: General average molecular weight of photographic gelatin = 100,000 COL-1: Low molecular weight gelatin produced by enzymatic decomposition of COL-0 Average molecular weight = 8,000 Example-4 (Preparation of hexagonal tabular silver iodobromide emulsion) Hexagonal tabular silver iodobromide grains having an average grain size of 0.83 µm (aspect ratio 4, silver iodide content 3 mol%) were used as seed crystals. Was prepared.

The solution <G-2> in the reaction vessel was heated to 75 ° C, pAg8.4, pH
After maintaining the temperature at 6.5 and adding 1.10 moles of seed emulsion with good stirring, crystal growth was performed by continuously supplying fine particles while preparing fine particles from a fine particle preparation mixer provided near the reaction vessel. Was. <H-3> in the mixing container
And <S-3> and <G-3> were added under pressure at an accelerated flow rate by the triple jet method over 63 minutes.

The fine particles prepared in the mixer were added to the reaction vessel with an average residence time in the mixer of 30 seconds. During this time, the rotation speed of the stirring blade of the mixer was maintained at 4000 rpm, and the temperature was maintained at 15 ° C (MC-10).

Subsequently, <H-4>, <S-4> and <G-4>
Similarly, the addition took 48 minutes. During this time, the rotation speed of the stirring blade of the mixer was maintained at 3500 rpm, and the fine particles prepared in the mixer were added to the reaction vessel with an average residence time of 20 seconds <MC-11>.

Further, <H-5>, <S-5> and <G-5> were similarly added over 30 minutes. During this time, the fine particles prepared in the mixer were added to the reaction vessel with an average residence time of 19 seconds (MC-12).

Fine particles (MC-10, MC-11, MC-1) formed in the mixer
The average particle diameter was confirmed to be 0.016 μm, 0.016 μm,
It was 0.018 μm.

The emulsion thus obtained has an average particle size of 1.48 μm,
Aspect ratio 3, distribution area 38.2%, silver iodide content 8.
The emulsion contained 63 mol% of hexagonal tabular silver iodobromide grains. This emulsion was desalted by a flocculation method, and adjusted to pH 5.80 and EAg = 100 mV at 40 ° C. This emulsion is designated as EM-4. In the preparation of EM-4, G-3, G-4, G
EM-5 was prepared in the same manner as described below, while adding 0.8 g of the compound I-1 of the present invention to -5 to form fine particles MC-13, MC-14, and MC-15. Furthermore, G-3, G-4, G-5
, 0.6 g of I-2 was added in place of I-1 to obtain fine particles.
While forming MC-16, MC-17, and MC-18, EM-6 was prepared in the same manner as described below.

 The results are shown in Table-4.

As is apparent from Table 4, EM- obtained using the fine particles prepared without the compound of the present invention during the nucleation was formed.
No. 4 shows that EM obtained by using fine particles prepared by allowing the compound of the present invention to be present at the time of nucleation, whereas the seed emulsion used did not grow much and the particle size distribution was significantly deteriorated,
-5 and EM-6 have normal crystal growth and a narrow particle size distribution.

Example-5 (Preparation of photosensitive material sample) Emulsions EM-1 to EM-6 were optimally subjected to gold / sulfur sensitization, and these emulsions were used to prepare a triacetyl cellulose film support having the following composition. Each layer was sequentially formed from the support side to prepare a sample of a multilayer color photographic light-sensitive material.

In all the descriptions below, the amount added in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified. The silver halide and colloidal silver are shown in terms of silver. Further, the sensitizing dye was represented by the number of moles per mole of silver in the same layer.

Multilayer color photographic light-sensitive material sample-1 (using EM-1,4)
Is as follows.

Sample-1 First layer; Anti-halation layer (HC) Black colloidal silver 0.2 UV absorber (UV-1) 0.23 High boiling point solvent (oil-1) 0.18 Gelatin 1.4 Second layer; First intermediate layer (IL-1) Gelatin 1.3 Third layer; low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average particle size 0.471 μm) 1.0 Sensitizing dye (SD-1) 1.8 × 10 ^-5 Sensitizing dye (SD-2) 2.8 × 10 ^-4 sensitizing dye (SD-3) 3.0 × 10 ^-4 cyan coupler (C-1) 0.70 colored cyan coupler (CC-1) 0.066 DIR compound (D-1) 0.03 DIR compound (D-3) 0.01 High boiling point solvent (oil-1) 0.64 Gelatin 1.2 Fourth layer; Medium sensitivity red-sensitive emulsion layer (RM) Silver iodobromide emulsion (EM-1) 0.8 Sensitizing dye (SD-1) 2.1 × 10 ^-5 sensitization Dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-4 Cyan coupler (C-1) 0.28 Colored cyan coupler (CC-1) 0.027 DIR compound (D-1) 0.01 High Boiling solvent (oil 1) 0.26 Gelatin 0.6 Layer 5: High-sensitivity red-sensitive emulsion layer (RH) silver iodobromide emulsion (EM-4) 1.70 Zowa dye (SD-1) 1.9 × 10 -5 Zowa dye (SD-2) 1.7 × 10 ^-4 ring-extended dye (SD-3) 1.7 × 10 ^-4 cyan coupler (C-1) 0.05 cyan coupler (C-2) 0.10 colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.025 High boiling point solvent (oil-1) 0.17 Gelatin 1.2 6th layer; 2nd intermediate layer (IL-2) Gelatin 0.8 7th layer; Low-sensitive green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.471 μm) 1.1 Sensitizing dye (SD-4) 6.8 × 10 ^-5 Sensitizing dye (SD-5) 6.2 × 10 ^-4 Magenta coupler (M-1) 0.54 Magenta coupler (M-2) 0.19 Colored magenta coupler (CM -1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling solvent (oil-1) 0.81 Gelatin 1.8 Eighth layer: Medium green sensitive emulsion layer (GM) Silver bromide emulsion (EM-1) 0.7 Sensitizing dye (SD-6) 1.9 × 10 -5 Sensitizing dye (SD-7) 1.2 × 10 -4 Sensitizing dye (SD-8) 1.5 × 10 -5 Magenta Coupler (M-1) 0.07 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling solvent (oil-2) 0.30 Gelatin 0.8 Ninth layer; High sensitivity green Sensitive emulsion layer (GH) Silver iodobromide emulsion (EM-4) 1.7 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye (SD-7) 1.0 × 10 ^-4 Sensitizing dye (SD-8) ) 3.4 × 10 ^-6 sensitizing dye (SD-4) 2.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-1) 0.04 High boiling solvent (oil- 2) 0.31 gelatin 1.2 10th layer; yellow filter layer (YC) yellow colloidal silver 0.05 color stain inhibitor (SC-1) 0.1 high boiling solvent (oil-2) 0.13 gelatin 0.7 formalin scavenger Jar (HS-1) 0.09 Formalin scavenger (HS-2) 0.07 Eleventh layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average particle size 0.471 μm) 0.5 Silver iodobromide emulsion (average particle size) 0.868 μm) 0.5 sensitizing dye (SD-9) 5.2 × 10 ^-4 sensitizing dye (SD-10) 1.9 × 10 ^-5 yellow coupler (Y-1) 0.65 yellow coupler (Y-2) 0.24 DIR compound (D -1) 0.03 High-boiling point solvent (oil-2) 0.18 Gelatin 1.3 Formalin scavenger (HS-1) 0.08 12th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average particle size 1.24 μm) 1.0 increase Sensitizing dye (SD-9) 1.8 × 10 ^-4 Sensitizing dye (SD-10) 7.9 × 10 ^-5 Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling solvent (oil-2) 0.074 Gelatin 1.30 Formalin Scavenger (HS-1) 0.05 Formalin Scavenger (HS-2) 0.12 13th layer; 1st protective layer (Pro -1) fine grain silver iodobromide emulsion 0.4 (average particle size 0.08 μm, AgI content 1 mol%) UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling solvent (oil-1) 0.07 High boiling point solvent (oil-3) 0.07 Formalin scavenger (HS-1) 0.13 Formalin scavenger (HS-2) 0.37 Gelatin 1.3 14th layer; 2nd protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, coating aid Su-1 and analysis aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST-
1, antifoggant AF-1, each having a weight average molecular weight of Mw: 10,
Two AF-2, 000 and Mw: 1,100,000, were added.

Emulsions EM-2, 3, 5 and 6 were also prepared in the same manner by using each of these emulsions instead of emulsions EM-1 and EM-4 of Sample 1, as shown in Table 5. −2,3
It was created.

Each sample prepared as described above was exposed to wedges using white light, and then subjected to the following development processing.

Color phenomenon 3 minutes 15 seconds 38.0 ± 0.1 ° C Bleaching 6 minutes 30 seconds 38.0 ± 3.0 ° C Rinse 3 minutes 15 seconds 24-41 ° C Settled 6 minutes 30 seconds 38.0 ± 3.0 ° C Rinse 3 minutes 15 seconds 24-41 ° C Stability 3 min 15 sec 38.0 ± 3.0 ℃ Drying 50 ℃ or less The composition of the processing solution used for each process is shown below.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxyamine / 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 (pH = 10.1) <Bleaching solution> Ammonium iron (III) ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to 1 to adjust the pH to 6.0 using aqueous ammonia.

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 and adjust to pH 6.0 with acetic acid.

<Stabilizing solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

Relative fog and relative sensitivity of each of the obtained samples were measured using red light (R) and green light (G), respectively, immediately after sample preparation.

 The results are shown in Table-6.

Relative fog is the minimum density (Dmi
The relative values of n) were shown, with the Dmin values of R and G of Sample-1 being 100.

The relative sensitivity is a relative value of the reciprocal of the exposure amount that gives a density of Dmin + 0.15 in each of the R and G measurements, and is shown as a value where the R and G sensitivities of Sample-1 are 100.

As is clear from the results shown in Table-6, Samples -2 and 3 of the present invention containing emulsions EM-2,3,5 and 6 of the present invention have high sensitivity and low fog. In contrast, the comparative emulsion EM-1,
Sample 1 using 4 was inferior in both sensitivity and fog.

〔The invention's effect〕

As described above, according to the inventions of the present application, a silver halide photographic emulsion and a silver halide color photographic light-sensitive material excellent in sensitivity and fog characteristics can be obtained.

Continuation of the front page (56) References JP-A-2-164719 (JP, A) JP-A-2-166442 (JP, A) JP-A-62-231246 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) G03C 1/015 G03C 1/07 G03C 7/26

Claims (2)

(57) [Claims] An emulsion comprising finely sized silver halide particles is supplied to a reaction vessel having an aqueous protective colloid solution for growing crystals of the photosensitive silver halide emulsion. A method for producing a part or all of the emulsions, wherein an emulsion comprising the fine silver halide grains is formed in the presence of a compound represented by the following general formula [I]. Method. General formula [I] Wherein, Y represents a hydrogen atom, -SO ₃ M or -COBCOOM.
M represents a hydrogen atom, an alkali metal atom, an ammonium group or an alkyl-substituted ammonium group having 5 or less carbon atoms;
Represents a chain or cyclic group forming an organic dibasic acid. m
And n each represent 0 to 50, and p represents 1 to 100. ] 2. A silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein the light-sensitive silver halide emulsion of the silver halide emulsion layer is prepared by the method according to claim 1. A silver halide color photographic light-sensitive material produced.