JPS6346443A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable rapidly processing by incorporating the particle which has a high silver chloride content contg. a high silver bromide phase to at least one layer of silver halide emulsion layers, and by chemically aging the obtd. silver chloride particle in the presence of a nitrogen contg. heterocyclic compd. and an unstable sulfur compd. CONSTITUTION:The silver halide particle having 80-99.5mol% silver chloride content is incorporated in at least one layer of the silver halide emulsion layers, and the phase having a high silver bromide content locally exists in an inner part or a surface of the silver halide particle. The composition of silver bromide in the phase contg. the high silver bromide content is >=70mol%. When the silver halide particle is chemically aged, the aging is effected in the presence of the nitrogen contg. heterocyclic compd. capable of forming a complex compd. with silver, and the unstable sulfur compd. The nitrogen contg. heterocyclic compd. is exemplified by 4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene, etc. The unstable sulfur compd. is exemplified by thiosulfate, etc. Thus, as the silver halide emulsion layer is chemically aged in the presence of the specific compd., the titled material capable of rapidly coloring and having high sensitivity is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material that is suitable for rapid development processing and is B-sensitive.

[Background of the Invention] Silver halide photographic materials generally consist of a support and a photographic layer coated on the support. The photographic layer herein includes a photosensitive silver halide emulsion F15 and a non-photosensitive hydrophilic colloid layer.

When the silver halide photographic light-sensitive material is a color photographic light-sensitive material, three kinds of halides are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on the support. A photographic silver emulsion layer is coated. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and there is a layer between the blue-sensitive emulsion layer and the edge-sensitive emulsion layer. , a bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion.

Furthermore, each emulsion layer has other intermediate layers for various special purposes.
Furthermore, a protective layer is provided as the outermost layer. Furthermore, for example, in light-sensitive materials for color photographic paper, the layers are generally coated in the order of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer from the exposed side, and each layer has a special coating, similar to the light-sensitive material for color negatives. Intermediate layers, protective layers, etc., including an ultraviolet absorbing layer, are provided for the purpose of protection. It is also known that each of these emulsion layers is provided in a different arrangement from the above, and each emulsion layer is generally composed of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use light-sensitive emulsion layers. In these silver halide photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers are typically used to form cyan, magenta and yellow dye images, respectively.
5-pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indacylon or cyanoacetyl magenta couplers and acylacetamide or benzoylmethane yellow couplers are used. These dye-forming couplers are contained in the light-sensitive photographic emulsion layer or in the developer solution. The present invention relates to a silver halide photographic material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, there has been an increasing demand for speeding up color development for various purposes including improving the productivity of photographic prints, and various measures have been taken for this purpose. One method is to use exposed silver halide photographic light-sensitive materials with aromatic i
It is known to use a color development accelerator when development is carried out using a secondary amine type color developing agent. For example, as such a color development accelerator, US Pat.
No. 950, No. 970, No. 2,515,147, No. 2
, No. 496,903, No. 4゜038,075, No. 4.
119.462@, British Patent No. 1,430.998, British Patent No. 1,455,413, JP-A-53-15831, JP-A-55-62450@, British Patent No. 55-62451, British Patent No. 55-
No. 62452, No. 55-62453, No. 51-124
No. 22, Special Publication No. 51-12422, No. 55-49t2
Compounds described in No. 8 etc. have been studied, but most of these compounds have insufficient development accelerating effects, and even among these compounds, even those that exhibit sufficient development accelerating effects,
This method often has the disadvantage of causing fog, and is therefore impractical.

In addition, various penetrants have been studied to promote the penetration of color developing agents into silver halide photosensitive materials, and among these, a method of accelerating color development by adding benzyl alcohol to a color developer is widely used. It is being

However, this method has some drawbacks in terms of rapid processing because, for example, at a processing temperature of 33° C., a sufficiently high coloring temperature cannot be obtained unless the processing is carried out for 3 minutes or more. In addition to the processing temperature, a method of color development by increasing the pH concentration of the color developer has also been proposed, but for example, if the pH is increased to 10.5 or higher, the oxidation of the color developer will be significantly accelerated.
In addition, due to the lack of a suitable buffer solution, the color developing agent is susceptible to I)H changes, which makes it difficult to obtain stable photographic performance and increases the dependence on processing time. was there.

On the other hand, in order to speed up color development, a method is also known in which a color developing agent is incorporated into a light-sensitive material in advance, as described in, for example, US Pat. No. 3,719,492.

However, this method has disadvantages in that the storage stability of the silver halide photographic light-sensitive material is poor, and fog is likely to occur before use, and furthermore, fog is likely to occur during color development processing.

Furthermore, in order to inactivate the amine moiety of a color developing agent, there is a method of incorporating the color developing agent into, for example, a Schiff salt, as disclosed in, for example, U.S. Pat. No. 3,342,559.
Research Disclosure, 1976 NQ 15
159. However, in these methods, color development does not start until after the color developing agent has been alkaline-hydrolyzed, so that the problem is that color development is rather delayed.

Furthermore, JP-A-56-64339 discloses a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material.
-144547, 58-50532, 58-5
No. 0533, No. 58-50534, No. 58-5053
No. 5 and No. 58-50532 disclose that 1-7 lyl pyrazolidones are added to a silver halide color photographic light-sensitive material and processed within an extremely short development time. .

However, the techniques described in these publications are not necessarily satisfactory in terms of obtaining dye images with sufficient color development speed and high color density, and there is still room for improvement. .

Furthermore, it is also known to speed up color development by using a silver chloride emulsion or a silver chlorobromide emulsion with a high silver chloride content as the silver halide emulsion. For example, U.S. Patent Nos. 4□183.756 and 4,225,6
No. 66, JP-A-55-26589, JP-A No. 58-9144
No. 4, No. 58-95339, No. 58-94340,
No. 58-95736, No. 58-106538, No. 5
No. 8-107531, No. 58-107532, No. 5
No. 8-107533, No. 58-108533, No. 8-107533, No. 58-108533, No.
No. 58-125612 and the like have descriptions regarding the above technology. Although the techniques described in these publications were quite satisfactory from the viewpoint of rapid processing performance, they were still unsatisfactory in terms of other photographic performance. That is, when a silver halide photographic light-sensitive material was produced using the above technique, there was a problem in that the sensitivity was particularly markedly reduced.

[Object of the Invention] Therefore, the object of the present invention is to provide a method suitable for rapid color development processing,
Another object of the present invention is to provide a silver halide photographic material with high sensitivity.

[Structure of the Invention] In order to improve the above-mentioned drawbacks, the inventors of the present invention have made intensive studies, and as a result, a specific sensitization technique has been developed for a silver chlorobromide emulsion having a specific grain structure and a high silver chloride content. The present inventors discovered the unexpected fact that by applying this method, it is possible to obtain a silver halide photographic material that maintains excellent rapid processability and is highly sensitive, leading to the present invention. That is, an object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the silver halide grains contained in at least one of the silver halide emulsion layers are: High silver chloride silver halide grains having a high silver bromide content phase and having a silver chloride content of GO to 90.5 mol%,
This is achieved by using a silver halide photographic material whose grains are chemically ripened in the presence of a nitrogen-containing heterocyclic compound and an unstable sulfur compound that form a complex with silver.

[Specific structure of the invention] The present invention will be explained in detail below.

First, the silver halide emulsion according to the present invention will be explained.

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains contained in at least one layer of the silver halide emulsion F1 have a silver chloride content of 80 mol% to C9.5 mol%.
These are silver halide grains having a high chloride limited phase that constitutes the majority of the grains, and a high silver bromide phase that is localized inside or on the surface of the grains.

Here, localization means that the silver halide grains are
This means that when analyzed by linear diffraction, the peaks attributed to the high silver bromide phase exhibit a diffraction pattern that can be clearly distinguished from the peaks attributed to the high silver chloride phase of the high silver bromide-containing phase.

The silver bromide composition of the high silver bromide phase is preferably 70 mol % or more. More preferably, it is 90 mol% or more. Furthermore, the proportion of the high silver bromide phase in one halide grain is 0.
．． It is preferably 5 to 20 mol%, more preferably 1 to 10 mol%.

The silver halide grains having the high silver bromide phase as a localized phase may have a layered structure of the high silver bromide phase and the high silver chloride phase, or silver halide grains having a high silver chloride phase may be formed. A high silver bromide phase may then be epitaxially grown on the crystal surface of the grain without completely covering the crystal surface.

The high silver bromide phase may form two or more localized phases in one silver halide grain. Further, at the boundary between the high silver bromide phase and the high silver chloride phase, the composition may change discontinuously or continuously.

The silver halide grains having a high bromide localized phase of the present invention (hereinafter referred to as "silver halide grains of the present invention") may be used alone or mixed with other silver halide grains. Good too.

When the silver halide grains of the present invention are used in combination with silver octaride grains other than the present invention, the projected area occupied by all the silver halide grains of the silver halide emulsion layer containing the silver halide grains of the present invention is The ratio of the projected area occupied by the silver halide grains of the present invention is preferably 50% or more, more preferably 75% or more.

Such silver halide grains are disclosed, for example, in JP-A-59-162.
Publication No. 540, Publication No. 59-48755 @ Publication No. 60-2
No. 22844, No. 60-222845, No. 6
It can be formed according to the method described in JP 0-136735 and the like.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processing properties and sensitivity, it is preferably 0.2 to 1.6 μm1, more preferably 0.25 to 1.6 μm. The range is 1.2 μm. The particle diameter can be measured by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method JA, S
, T., M.

Symposium on Light Microscopy 195
5, pp. 94-122, or Chapter 2 of "The Theory of Photographic Processes" by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966).

``The diameter of this particle can be measured using the projected area of the particle or an approximate diameter value. If the particles are of substantially uniform shape, the particle size distribution can be expressed fairly accurately in terms of diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is determined by the following equation.

Here, ``i'' represents the particle diameter of each particle, and ni represents the number thereof.

The particle size here refers to the diameter in the case of spherical halogen-1 arsenic particles, and in the case of particles with shapes other than cubic or spherical, the diameter when the projected image is calculated as a circular image of the same area. represent.

The silver halide grains according to the present invention may be blued 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 produced. The method for producing seed particles and the method for producing seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any method such as the facial weight method, the back mixing method, the simultaneous iIR method, or a combination thereof, but the simultaneous mixing method is preferred. Further, as a type of simultaneous mixing method, it is also possible to use the DAg-chondrold double-jet method described in JP-A-54-48521@ and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains according to the present invention may have any arbitrary shape. One preferred example is a cube having a (1oo) plane as a crystal surface.

Also, U.S. Patent Nos. 4.183.756 and 4.22
No. 5,666, Japanese Patent Publication No. 55-26.589, Special Publication No. 5
Specifications such as No. 5-42737, The Journal on Photographic Science (J, Photo
gr, 5ci) 21.

8 by the method described in the literature such as 39 (19γ3).
Particles having shapes such as a face, tetradecahedron, and dodecahedron can also be used. Furthermore, particles having twin planes or irregularly shaped particles may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or! Synthetic ions can be added to the inside of the particles and/or on the surface of the particles using a salt, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be created inside the particles and/or on the surface of the particles. Can be granted.

In the 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 according to 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 grain. Preferably, the particles are particles on which latent images are mainly formed.

The silver halide grains according to the present invention are chemically sensitized in the presence of a nitrogen-containing heterocyclic compound and an unstable sulfur compound that form a complex with silver.

Next, the nitrogen-containing heterocyclic compound that forms a complex with silver used in the present invention will be described in detail.

In the nitrogen-containing heterocyclic compound used in the present invention, the heterocycle includes a pyrazole ring, a pyrimidine ring, a 1.2.4-triazole ring, a 1.2.3-triazole ring, a 1.3.
4-thiadiazole ring, 1°2.3-thiadiazole ring, 1,2.4-thiadiazole ring, 1,2.5-thiadiazole ring, 1°2.3.4-tetrazole ring, pyridazine ring, 1°2. 3-triazine ring, 1,2.4-triazine ring, 1.3.5-triazine ring, these rings are 2
Examples include rings in which ~3 is bonded, such as a triazolotriazole ring, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, and a pentazaindene ring. Heterocycles in which a monocyclic heterocycle and an aromatic ring are condensed, such as a phthalazine ring, a benzimidazole ring, an indazole ring, and a benzothiazole ring, are also applicable. Among these, an azaindene ring is preferred, and azaindene compounds having a hydroxy group as a substituent, such as hydroxytriazaindene, tetrahydroxyazaindene, hydroxypentaazaindene compounds, and the like are more preferred. The heterocycle may have a substituent other than a hydroxy group. Examples of the redeemable group include an alkyl group, a redeemable alkyl group, an alkylthio group, an amiLL hydroxyamino group, an alkylamino group, a dialkylamine group, an arylamim Lcarboxy group, an alkoxycarbonyl group,
It may have a halogen atom, a cyano group, etc.

Specific examples of the nitrogen-containing heterocyclic compound according to the present invention are listed below, but the present invention is not limited thereto.

N-12,4-dihydroxy-6-methyl-1゜3a,
7-triazaindene N-22,5-dimethyl-7-hydroxy-1°4.7
a-1~Riazaindene N-35-amino-7-hydrooxy-2-methyl-1,
From 4,7a-triazaindene, 1, in the lower part.

7-tetrazaindene N-54-hydroxy-1,3,3a, 7-tetrazaindene N-64-hydroxy-6-phini2A/ -1,3,3
at7-tetrazaindene N-74-methyl-6-hydroxy-1,3,3m.

7-Tetrazaindene N-82,6-dimethyAI-4-hydroxy-1,3゜3a, 7-tetrazaindene N-94-hydroxy-5-ethyl-6-methy/I/
-1,3,3m, 7-tet2zaindene N-102
,6-dimethe/l/ + 4-hydroxy-5-ethyl-1,3,3a, 7-tetrazaindene N-114-hydroxy-5,6-dimethyl-1.3゜3a, 77teto2zaindene N- 122,5,6-)rimethyl)y -4-hydroxy-1,3,3m,7-tetrazaindene N-132-methy/i/-4-hydroxy-6-phenyl-1,3,3m, 7 -Tetrazaindene N-14
4-hydroxy-6methyl/'-1,2,3a a
7-tetrazaindene N-154-hydroxy-6-nityl 1.2.3a
, 7-tetrazaindene N-164-hydroxy-6-phenylene/l'-1,2
, 3a.

7-Tetrazaindene? J-174-hydroxy-1.2.3a, 7-tetrazaindene N-184-methyl-6-hydroxy-1,2,3a
, 7-tetrazaindene N-197-hydroxy-5-methyl-1,2,3,4
,6,-pentazaindene N-205-hydroxy-7-methy/l/ -1,2,
3,4,6-indene N-227-hydroxy-5-methyl-2-phenyl-
! , 2.3,4.6-pentazaindene N-z3's-
Dimethylamino-7-hydroxy-2-phenyl 1.
2.3,4.6-pentazaindene N-z41-phenyl-5-mercapto-1,2,3,
4-teto2zole N-251C3-acelylno'4nophenylno5 norcapto 1L, 3.4 Tetrazole 846 1
(4 methoxyphenyl 7)5 mercapto-1,1,
3,4 Tetrazole N-276-7 Minopurine N-28 Benzotriazole N-2q 6-nidrobenzi, Midazole N-30
3-F-2-Methylbenzothiacylylam p-toluenesulfonate N-511-Methylquinoline N-32 Benzothiazo-'N-33 Benzoxazole N-3+ Benzoselenazole N-35 Benzimidazole N-36 7 Toteazole'N-37 7 Toselenazole N-38 7 Toimidazole N-39 Rhodanine N-402°-Thiohydantoin N-41' 2-Thio-2,4-oxazolidinedione N-443-Benzyl-2-mercapto Benzimidazole N-43 2-Mercapto-1-methylbenzothiazole N-44 5-(m-nitrophenyl)tetrazole N-45 2,4-dimethylthiazole N-46 1-Methyl-5-ethoxybenzothi 7°C
L-N-472-Methyl-l-7-Tothiazole N-431
-ethyl/I/-5-mercagutotetrazole N-4q 5-methylbenzotriazole N-505
-Phenyltetrazole N-51"1-methyl-2-mercapto-5-benzoylamino-1,3,5-triazole N-521-benzoyl-2-mercapto-5-acetylamino-1,3
,5-)Ryazo-ru N-532-mercapto-3-aryl-4-methy-6-hydroxypyrimidine N-542,4-dimethyloxazole and remainder 1' N-55i-methyl-5 -Phenoxybenzoxazole N-562-ethyl-β-naphthoxazole N=5'
l 2-mercapto-5-aminothiadiazole N-582-mercapto-5-aminooxadiazole N-5'12-mercap 1-5-aminoselenadiazole The above nitrogen-containing heterocyclic compound according to the present invention is: It can react with silver halides to form silver complexes. The above-mentioned nitrogen-containing heterocyclic compound can be added to a silver halide emulsion according to the present invention by dissolving the compound in a suitable solvent such as water or an aqueous alkaline solution. The unstable sulfur compound can be added to the silver halide emulsion at the time of sulfur sensitization using the unstable sulfur compound, but the optimal time is just after the unstable sulfur compound is added to the silver halide emulsion or before the addition of the unstable sulfur compound. It is. The amount of the nitrogen-containing heterocyclic compound used in the present invention varies depending on various conditions, but is in the range of 10@-7 mol to 10@-1 mol per mol of silver halide.

The unstable sulfur compound used in the present invention is a sulfur-containing compound that has the property of forming a silver salt when reacting with silver halide, and further forming silver sulfide under conditions such as strong alkalinity. , such as thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate,
Mention may be made of sulfur sensitizers such as cystine.

The amount m of the sulfur sensitizer, which is an unstable sulfur compound, used in the present invention varies depending on various conditions, but is in the range of 10@-7 mol to 10@-1 mol per mol of silver halide. Further, when the above-mentioned sulfur sensitizer is added to an emulsion, it may be added after being dissolved in water or an alcohol such as methanol or ethanol.

According to the present invention, chemical ripening using the sulfur sensitizer according to the present invention is carried out in the presence of the nitrogen-containing heterocyclic compound.

Regarding such a sensitization method, for example, British Patent No. 1,
No. 315,755, JP-A-58-126526, and other specifications and publications, but these descriptions all involve gold-sulfur sensitization methods or gold-sulfur sensitization methods that are different from the present invention.
This relates to a selenium sensitization method, and the effects of the present invention cannot be obtained.

Furthermore, JP-A No. 60-232545 describes a technique for performing sulfur sensitization in the presence of a nitrogen-containing heterocyclic compound; This article relates to silver bromide, and from the contents of the description, the effects of the present invention, that is, the specific effects obtained in a silver halide emulsion with a high silver bromide phase and a high silver chloride content, cannot be predicted at all. Met.

On the other hand, the nitrogen-containing heterocyclic compound according to the present invention is used at the end of chemical ripening of a silver halide emulsion or at a later stage for the purpose of preventing fog and improving the stability over time or storage of silver halide light-sensitive materials. Although it is well known in the art that the emulsion is used by being added to the emulsion, the effect of the present invention cannot be obtained by such an adding method.

The emulsion of the present invention can be spectral sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photography industry. Sensitizing dyes may be used alone, but two or more types may be used in combination. Together with the sensitizing dyes, they are compounds that do not themselves have a spectral sensitizing effect or do not substantially absorb visible light. A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the 7L agent.

When the silver halide emulsion according to the present invention is used as a blue-sensitive emulsion, it is preferable to perform spectral sensitization with a j-sensitizing dye represented by the following formula [A].

- Clothes cost [△] Below margin 1 - Clothes cost [In A1, Zll, Z, +z are respectively benzoxazole nucleus, na7'F oxazole nucleus, benzoselenazole nucleus, na7) selenazole nucleus, benzothiazole nucleus, Represents the atomic group necessary to form a 7F thiazole nucleus, bencyimiguzole nucleus, na7toimidazole nucleus, pyridine or quinoline nucleus, but these heterocycles also include those with substituents* ZI+ and ZI
Examples of the substituent on the heterocycle formed by 2 include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, and an alphkyl dicarbonyl group. Among these substituents, preferred substituents are a halogen atom, A cyano group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and preferred substituents are a halogen atom, a cyano group, a methyl group, an ethyl group, a nodoxy group, or a nidoxy group, and R2+ and VR2z each represent a balkyl group, an alkenyl group, or an aryl group, preferably an alkyl group, more preferably an alkyl group substituted with a carboxyl group or a sulfo group, and the most preferred is an alkyl group substituted with a carboxyl group or a sulfo group. ±sulfoalkyl group having 1 to 4 carbon atoms. Main RB is selected from hydrogen atom, methyl group, and ethyl group. Rewards the Xe1th anion, l is 0 or 1.

Among the sensitizing dyes represented by the general formula [A] below, a particularly useful dye is the sensitizing dye represented by the following formula [A'].

General formula [A'] Here, Y. and Y2 each represent an optionally substituted benzene ring or an atomic group necessary to complete the naphthalene ring. The benzene ring and naphthalene ring formed by Yl and Y2 include those with substituents, and! :! The L substituent is preferably a halogen atom, hydroxyl group, cyano group, heptalyl group, alkyl group, alkoxy group or alkoxycarbonyl group. More preferred substituents are a halogen atom, a cyano group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and a most preferred substituent is a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, or an ethoxy group. It is the basis.

R21, R12, Ruff, X and l are of the general formula [
This is the same as shown in A].

A specific example of the sensitizing dye represented by the general formula [A] used in the present invention is shown for dogs.

Margin below -Cost of clothes [heko] A-1 He-9 to-10 Heh 12 CH.

8-15 8-16 A-17 Δ-18 8-20 Δ-22 8-23 8-24 When the silver halide emulsion according to the present invention is used as a green-sensitive emulsion, it is represented by the following formula [B]. It is preferable to perform spectral sensitization using a sensitizing dye.

General formula [B] In the formula, Z2, and Z + z each represent an atomic group necessary to form a benzene ring or a 7talene ring fused to an oxazole, and represent the heterocyclic nucleus to be formed. may be substituted with various substituents, and these preferred substituents are a halogen atom, an aryl group, a furkyl group, or an alkoxy group. More preferred substituents are a halogen atom, a 7-enyl group, and a methoxy group, and the most preferred substituent is a phenyl group.

According to a preferred embodiment of the present invention, Z and Z12 together represent a benzene ring fused to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5-position, or The 5-position of one benzene ring is substituted with a phenyl group, and the 5-position of the other benzene ring is substituted with a halogen atom.

R21 and R22 each represent a fulkyl group, a fulkenyl group, or an alkyl group, preferably an alkyl group, and more preferably, R2+ and R22 are
Each is an alkyl group substituted with a carboxyl group or a sulfo group, most preferably having 1 to 4 carbon atoms.
is a sulfoalkyl group. Most preferred is a sulfoethyl group.

R23 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

X and O represent anions, such as chlorine, odor CH, S
o, , C2H% So4, etc.') Pa ions are mentioned. n represents 1* or 0, provided that n represents O if the compounds form an inner salt.

Specific examples of the sensitizing dye represented by the general formula [B] that are preferably used in the present invention are shown below.

[B-11 -”, hereafter -' [8-2] [8-31 [8-4] [8-5] [B-6] [8-7] [8-8] [ B, -101 [(3, -11] Margin below When the silver halide emulsion according to the present invention is used as a red-sensitive emulsion, a sensitizing dye represented by the following formula [C] or a sensitizing dye represented by the following formula [D It is preferable to carry out spectral sensitization using a sensitizing dye represented by the following.

- Formula [C] (X○)1-1 General formula [D] (xe)l-1 In the formula, R represents a hydrogen atom or an alkyl group, and R, to R1 represent an alkyl group and an aryl group, respectively. ,Z
+, Zz, Z< and Z represent the atomic group necessary to form a benzene ring or a 7-talene ring condensed to a thiazole ring or selenazole ring, respectively, and Z is a carbonization group necessary to form a 6-shell ring. Reward a group of hydrogen atoms, l is 1
or 2, Z represents a sulfur atom or a selenium atom, and xe represents an anion.

In the above formula, examples of the alkyl group represented by R include a methyl group, an ethyl group, and a propyl group, and R is preferably a hydrogen atom, a methyl group, and an ethyl group. Particularly preferred are a hydrogen atom and an ethyl group.

Further, R+, R2, R1 and [/R, are each a linear or branched alkyl group, and this alkyl group may have a substituent (for example, methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxy Ethyl, acetoxyethyl, carboxymethyl, carboxyethyl, nidoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, β-hydroxy-7-sulfopropyl, sulfatepropyl, allyl, benol, 4) or aryl group, this aryl The group may have a substituent (for example, phenyl, carboxyphenyl, sulfophenyl, etc.), 2. ．． 2.
．． 2. The heterocyclic nucleus formed by and Z, even if it has a substituent, r! Preferred mono-substituent groups are halogen atoms, aryl groups, alkyl groups, and alkoxy groups, and more preferred are halogen atoms (eg, chlorine atoms), phenyl groups, and methoxy groups.

X is an anion (for example, Cj!, Br, I.

, where l weakens 1 or 2.

However, when the compound forms an inner salt, l represents 1.

Typical co-image examples of sensitizing dyes represented by general formulas [C1 and [D] preferably used in the present invention are shown below.

□, below margin C-2 O B, θ below margin ゝ/ -I D-I D-▗□'' bottom margin - ne above - formula [A], [B], EC] * or The amount of the sensitizing dye represented by [D] is not particularly limited, but it is preferably used in the range of 1 x 10''1 to IX10-1 mol per 1 mol of halogenated dye, more preferably 5
X 1 0-' ~ 5 x 10 moles.

The method of adding the sensitizing dye can be any method well known in the art.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, nityl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), and in some cases diluted with water; Mainly in certain cases they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibrations for this dissolution.

Furthermore, the sensitizing dye used in the present invention is disclosed in US Pat.
69,987, in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added. Similarly, a method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added. Also, what are the sensitizing dyes used in the present invention? It can be added to the emulsion in the form of a dispersion by the dissolution/dispersion method. Other addition methods include U.S. patent power 2.912,3
No. 45, No. 3.342,605, No. 2,996,
The methods described in No. 287, No. 3.42, and No. 835 may also be used.

The sensitizing dyes to be contained in the silver halide emulsion of the present invention may be dissolved in the same or different solvents, and these solutions may be mixed or added separately before being added to the silver halide emulsion. If they are added separately, the order, time, and interval can be arbitrarily determined depending on the purpose.6 The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion manufacturing process. However, it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

Margins below Although it is advantageous to use gelatin as the binder (or protective colloid) for the silver halide emulsion of the present invention,
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 a hardening agent to the processing solution so that it 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 a 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, aminephenol derivatives, etc.). The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler in 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.

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

The dye image-forming coupler used in the present invention is not particularly limited, and various couplers can be used, but the compounds described in the following patents are representative examples.

Yellow dye image-forming couplers include 4-equim or 2-equivalent couplers of the acylacetamide type and benzoylmethane type, and these are disclosed, for example, in U.S. Patent No. 2,778.
, No. 658, No. 2,875,057, No. 2,90
No. 8,573, No. 2,908,513, No. 3, 2
No. 27.155, No. 3.227.550@, No. 3.
No. 253.924, No. 3.265.506, No. 3
．． 277, 155, 3.341.331, 3,369,895, 3,384,657, 3,408,194, 3,415,652,
Same No. 3,447.928, Same No. 3,551,155
No. 3.582.322, No. 3.725.0
72, German Patent No. 1.547.868, German Patent No. 2.
057.941@, same No. 2.162,899, same No. 2
, No. 163,812, No. 2,213,461@, No. 2,219,917, No. 2,261,361, No. 2,263,875, Special Publication No. 13576/1976,
JP 48-29432, JP 48-66834, JP 49-10736, JP 49-122335, JP 5
No. 0-28834, No. 50-132926, No. 55-
It is described in each specification of No. 144240 and No. 56-87041.

The magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers such as 5-pyrazolones, pyrazolotriazoles, pyrazolinobenzimidazoles, indacilones, and cyanoacetyls, and these are: For example, U.S. Patent No. 2□600.788,
3.061.432, 3.062.653, 3,127,269, 3,311.476
M, No. 3,152,896, No. 3.7119.3
No. 91, No. 3.519.429, No. 3.558.
No. 318, No. 3,684.514, No. 3.705
．． No. 896, No. 3.8H, No. 680, No. 3.907
．． No. 571, No. 3.928.044, No. 3,93
0,861, 3.930,816, 3.9
33.500, JP-A-49-29639, JP-A-49-29639
111631@, No. 49-129538, No. 51-
No. 112341, No. 52-58922, No. 55-62
No. 454, No. 55-118034, No. 56-386
．． No. 13, No. 56-135841, Special Publication No. 1977-60
No. 479, No. 52-34937, No. 55-29421
No. 55-35696, Aida Patent No. 1.247.4
93@, Specifications of Belgian Patent No. 792.525, West German Patent No. 2.156 and 111, Japanese Patent Publication No. 4G-6
No. 0479, JP-A-59-125.732@, JP-A-59-2
No. 28.252, No. 59-162.548, No. 59-
No. 171,956, No. 60-33.552, No. 60-
Publications No. 43.659, West German Patent 1, 070.03
No. 0 and U.S. Patent No. 3,725,067.

Cyan dye image-forming couplers include phenolic,
A naphthol-based 4-or 2-original cyanide image-forming coupler is typical, and U.S. Patent No. 2.306.4
10@, No. 2,356,475, No. 2.362,
No. 598, No. 2,367.531, No. 2,369
, No. 929, No. 2.423, 73o@, No. 2.11
No. 74,293, No. 2,476.008, No. 2.
No. 498.466, No. 2,545.681, No. 498.466, No. 2,545.681, No.
2.728.6130, 2.772.162, 2,895,826, 2.976, 146
No. 3,002.836, No. 3,419.3
No. 90, No. 3.446.622, No. 3.476
, No. 563, No. 3.737.316, No. 3,15
8,308, British Patent No. 3.839.044N, British Patent No. 478,991, British Patent No. 945.542, British Patent No. 1.0
No. 134,480, No. 1.377.233, No. 1
, 388,024 and 1,543.040, as well as JP-A-47-37425 and JP-A-50-1.
01354, No. 50-25228, No. 50-112
<No. 138, No. 5O-117I+22, No. 50-1
No. 30441, No. 51-6551, No. 51-3764
No. 7, No. 51-52828, No. 51408841,
No. 53-109630, No. 54-48237, No. 5
No. 4-66129, No. 54-131931, No. 55
-32071, 59-146050, 59-3
It is described in publications such as No. 1953 and No. 60-117249.

It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which does not expand the coupler group and has a carbon number of 8 or more. Either a 4-equivalent case, in which four silver ions need to be reduced, or a 2-equivalent case, in which only two silver ions need to be reduced, may be used.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be treated with various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and usually a high boiling point solvent with a water point of about 150°C or higher is mixed with a low boiling point and Or, by dissolving it in combination with a water-soluble Ia solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After emulsification and dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing a low boiling point solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, trimesic acid esters, etc., which do not react with the oxidized form of the developing agent, and have a boiling point of 150°C or higher. Orange solvent is used.

Anionic surfactants and nonionic surfactants are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water mechanically or using ultrasonic waves. , cationic surfactants can be used.

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 product of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifogging agents are used to prevent deterioration in quality and noticeable graininess.

The color antifoggant 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.

Hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain ultraviolet absorbers 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. May contain.

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 reduces the gloss of the photosensitive material, increases the additivity, and provides a layer between the photosensitive materials. A matting agent can be added to prevent sticking.

A lubricant can be added to reduce the sliding friction of the photosensitive material using the halogenated 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, sensitization, etc.).

The photosensitive material r3t using the silver halide emulsion of the present invention is a photographic emulsion layer, and other materials include a flexible reflective support such as paper laminated with baryta or α-olephne polymer, synthetic paper, etc., and cellulose acetate. , cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate°
It can be applied to films made of semi-synthetic or synthetic polymers such as polycarbonate, polyamide, etc., and rigid bodies such as glass, synthetic materials, and ceramics.

The silver halide material of the present invention may be applied to the surface of the support by corona discharge, ultraviolet irradiation, or flame treatment, if necessary. After applying the hat,
Direct or (support surface adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, *m characteristics,
and/or to improve other properties) 1 or 2
It may be applied via the above lower t[.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the 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 lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beams, and X-rays. Any known light source can be used, such as light emitted from a phosphor excited by , gamma rays, alpha 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 subjected to color development treatment known in the art to form a double layer.

The color development agent used in the color developer in the present invention includes known agents that are widely used in various color photographic processes.

These developers include amine phenol and p-phenylene diamine 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. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 a for the color development liquid 12, preferably about 1 g to about 15 a for the color development liquid 11.
Use at a concentration of

Typical color developing agents used in color developing solutions include aromatic primary amine compounds and P-phenylenediamine compounds, with preferred examples being N-, N-
Noethyl-P-7 22dine diamine ma salt, N-ethyl-P-phenylenediamine/[[,N,N-tumethyl-P
-phenylenediamine hydrochloride, 2-7 minnow 5-(N-
Ethyl-N-dotecylamino)-toluene, N-ethyl-N-(β-notanesulfonamidoethyl)-3-/thiru-4-aminoaniline sulfate, N-ethyl-N-β-
Hydroxyethylamine/aniline, 4-7 minnow N-(
2-Methoxyethyl)-N-ethyl-3-methylaniline-P-)luenesulfonate, N,N-diethyl-3
-Methyl-4-aminoaniline, N-ethyl-N-(β
-Hydroxyethyl)-3-methyl-4-7mino-7-niline and the following margins. These color developing agents may be used alone or in combination of two or more, and
1Mi or two or more of these color developing agents may be used in combination with other black and white developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-P-amino/7-ethyls.

This color developing agent may be contained in the silver chloride color photographic light-sensitive material of the present invention. In this case, the amount of this color developing agent added is 0.2 moles per ii mole of halide contained in the silver chloride color photographic light-sensitive material. In the range of 2 mol to 2 mol,
Preferably it is in the range of 0.4 mol to 0.7 mol.

When the silver halide color photographic light-sensitive material of the present invention is subjected to color development processing, N-ethyl-N-(β-notanesulfonamidoethyl) -3-/f is particularly selected from among the above compounds as a color developing agent. Particularly preferred is syl-4-fumianiline sulfate.

In addition to the color developing solution mentioned above, the color developing solution may include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, etc. ! I
'tAlkali agents such as sodium phosphate, potassium carbonate, potassium hydrogen carbonate, N,N-diethylhydroxylamine, N,N bis(methoxy).

Preservatives such as diethyl) hydroxylamine, triethanolamine, jetanolamine glycose, potassium sulfite, organic solvents such as methanol, ethanol, butanol, ethylene glycol, diethylene glycol, development with citrazic acid and polyethylene glycol, etc.: J1
Various photographic additives known in the photographic field, such as a moderating agent, a heavy metal ion masking agent, and a development accelerator, may be included as necessary.

In the color developing solution preferably used for processing the light-sensitive material of the present invention, hydroxylamine, which has been conventionally often used as a preferable TD agent, is added for its silver developability to high silver chloride emulsions. It is preferable not to.

In addition, sulfite ions such as sodium sulfite and potassium sulfite as preservatives of the color developing solution are used in relatively large amounts (for example, when the color developing solution contains benzyl alcohol, which is a coloring property improver). Approximately 0.01 per
However, if the color developer contains only about 0 to about 5 mQ of benzyl alcohol per 1a of the color developer, the sulfite ion concentration will be lower than the color developer tQ. It is necessary to reduce the amount to about 0.004 mol or less per unit.

1'', Below Margin -7' The silver chloride color photographic light-sensitive material of the present invention is developed with a color developing solution containing no water-soluble bromide or a very small amount of water-soluble bromide. When containing excess water-soluble bromide,
The bromide ion concentration in the zero color developing solution, which sharply reduces the development speed of silver chloride color photographic light-sensitive materials and makes it impossible to achieve the object of the present invention, is expressed in terms of potassium bromide.
The amount is approximately 0.1 g or less, preferably 0.05 g or less per color developer 11.

The photosensitive material of the present invention is continuously subjected to color development.
During continuous processing while filling the color developing solution, if a minute amount of bromide ion is released from the color photosensitive material as a result of development, a minute amount of bromide ion will be dissolved in the color developing solution. However, in this case, the bromide ion (4) in the color developing solution is selected by appropriately selecting the replenishment ratio of the color developing solution replenisher to the total amount of bromide contained in the photosensitive material.
It is preferable to keep it within the above range.

The effects of the present invention are particularly significant when a water-soluble chloride is used as a development regulator in the color developing solution.

The water-soluble chloride used is used in an amount of 0.5 g to 5 g, preferably 1 g to 3 g, per 11 parts of the color developer in terms of potassium chloride.

The color developing solution may further contain a development inhibitor described in W 58-95345 as long as it does not impair the present invention. Preferably, adenine and guanine are used in the color developing solution in an amount of 0 to 0.02 g/1.

The pH of the developer of the present invention is preferably 9.5 or higher, more preferably 13 or lower. Conventionally, it has been known that development is accelerated by increasing the pH of the two liquids, but the silver halide color photographic light-sensitive material of the present invention has sufficient rapid developability even when the pH is 11 or less. is obtained.

The temperature of the color developing solution is 15-45°C, preferably 20-40°C.
' Do it between C.

The following margins The silver halide photosensitive t1 rice grains of the present invention, after color development,
Bleached and fixed. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (II [), cobalt (■), and bleach (
Polyvalent gold compounds such as I[), especially complex salts of these polyvalent metal cations with II M, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid,
Gold fi fil j such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid! Alternatively, ferricyanates, chromates, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, and thioether.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment can contain a pHIII agent, a chelating agent, an anti-spill agent, and the like. For these specific conditions, reference may be made to JP-A-58-134636 and the like.

The following margin (Example-1) A TI4 acid silver aqueous solution was prepared according to the method described in JP-A-59-45437 under the conditions of 60°C in the presence of inert gelatin, l)Ag -7,8°. A monodisperse silver chlorobromide emulsion (EM-1
)It was created. As a result of electron microscopy v1 observation, EM-1 had an average particle diameter (sphere equivalent) of 0.75 μm and a tetradecahedral shape.

Next, a silver chloride emulsion (EM-2) was prepared in the same manner as EM-1 except that pAg was 7.0 and a sodium chloride aqueous solution was used as the halide aqueous solution. EM-2 has an average particle size of 0
．． It had a cubic shape with a thickness of 8 μm.

Next, 0A (1-7,0,60
EM-3 was prepared by reacting a silver nitrate aqueous solution, a sodium chloride aqueous solution, and a potassium bromide aqueous solution under the conditions of .degree. C. according to the method described in JP-A No. 59-48755. As a result of analyzing EM-3 by X-ray diffraction, peaks belonging to pure silver chloride and pure silver bromide appeared separately. In addition, regarding EM-3, X-ray microanalysis (X
As a result of further analysis by MA) and X-ray photoelectron spectroscopy (XPS), the silver halide grains contained in EM-3 were found to have pure silver chloride inside and 97% silver bromide on the outside surface.
It has a structure covered with silver chlorobromide containing
It was found that mol%.

Next, for EM-1, EM-2, and EM-3, the first
M sodium, blue-sensitive sensitizing dye (A-3) and Table-
Chemical ripening was carried out using the exemplified compound (N-6) in the amount shown in 1. At the end of the chemical ripening, 1 x 1o-2 mol of the exemplified compound (N'-
6) was added to prepare EMB-1 to EMS-9.

Margin Table 1 Below, the following margins were used to prepare silver halide photographic TA photosensitive I materials of the following composition, and samples 1 to 9 were used, respectively.

(T1-1) (Y・-1) For Moritsugu Samples 1 to 9, perform the method shown below (from 2, Sensi 1 to Me1 to I).

[1 Sight Me 1 Review & l Ti] Each sample was exposed to white light through an optical wedge using a photosensitive fft <Roku Konishi Shoko S (Model MKS-7), and the following was done. I treatment was performed.

[Processing process] Temperature Time Color development 34.7± 03°C 50 seconds, +oo seconds Bleach fixation 34.7± 0.5°C 5 seconds Stabilization 30-34°C 90 seconds Drying 60-80'' C60 seconds [Color developer] Pure water 80〇-Ethylene glycol 101QN,N-diethylhydroxylamine 10 (Potassium monochloride
29N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30G optical brightener (4,4'
- Diaminostilbendisulfonic acid derivative) 1Q Add water to reduce the total M to 1f! Then, adjust the pH to 10.08.

(Bleach-fix solution) Ethylene thiamine 1 hela ferric ammonium acetate dihydrate 600 ethylenediaminetetraacetic acid 39 Ammonium thiosulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.5 t O@ with potassium carbonate or glacial acetic acid Adjust to 7.1 and add water to make the total number of times 12.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1g1-hydroxyethylidene-1,1-diphosphonic acid 20 Add water to make 1 section, and DH with sulfur M or potassium hydroxide. 7.0
Adjust to.

The reflection density of the obtained sample was measured using a 3-axis running meter PI'' A-65 (manufactured by Konishiroku Photo Industry Co., Ltd.).

Sensitivity is expressed as the reciprocal of the exposure amount required to obtain a density of 0.8, and the sensitivity at a color development time of 100 seconds in trial 1 is
100! It is shown as the relative sensitivity of Kotoki. Table 2 of the results
Shown below. Also, DIllax in the table indicates the anti-corrosion of each sample. )−! Shows the highest H1 degree.

Margin Table-2 Below Table-2 shows that even if the chemical sensitization method according to the present invention is applied to an emulsion containing 100 mol% silver chloride? Ai sensitization was not achieved,
It can be seen that the effects of the present invention are specifically obtained when the silver halide grains of the present invention are combined with the sensitization method of the present invention.

(Example-2) A green-sensitive sensitizing dye (8-4) was used as an ideal dye, and an example/illustrative compound (N-
2), and the other conditions were the same as in Example-1.
10 to 18 were created.

The obtained samples 10 to 18 were evaluated in the same manner as in Example 1. The results are shown in Table-3.

Table 3 shows that, as in Example 1, the effects of the present invention can be obtained only by the combination of the silver halide grains of the present invention and the sensitization method of the present invention.

Table-3 Below margin (Example-3) Red-sensitive sensitizing dye (C-6) was used as the sensitizing dye, and exemplified compound (N-24) was used as a compound capable of forming a complex compound with silver. A sample was prepared and evaluated in the same manner as in Example 2, except for the use, and almost the same results were obtained.

(Example 4) EM-4 was prepared in the same manner as EM-3, except that the addition rates of the silver nitrate aqueous solution and the halide aqueous solution during the formation of silver halide grains were finely adjusted. EM-4 has an average particle size of 0.6μ
It had a cubic shape of m, and as a result of analysis, it was found that it had a silver halide composition distribution almost the same as EM-3.

Divide EM-4 into two parts and add green-sensitive sensitizing dye (B
-6) was chemically sensitized under the same conditions as EMS-6 except that a red sensitizing dye (D-2) was used on the other side (a sensitization method not included in the present invention). 1 and E
MR-1 was created.

Next, EMS-1 to 9 prepared in Example-1 were used as blue-sensitive emulsions, and the above-mentioned EMG-15 and EMR-1 were used as green-sensitive emulsions and red-sensitive emulsions, respectively. Samples 19 to 27 were prepared. Table 5 does not show the correspondence between the emulsions used and the samples.

Samples 19 to 27 were evaluated for rapid processability and blue light sensitivity.

Rapid processability was evaluated by performing the same exposure process and density measurement as in the sensitometric evaluation in Example 1, except that the color development time was changed to 50 seconds and 100 seconds.

Below is the margin table-4 (M-1) Ct Ct (C-1) C, H, □ (1) (C-2) 9-''・, Below is the margin j Table-5 Rapid processability is the most developable The highest density (1) max) of the blue-sensitive emulsion layer (first layer), which has poor The movement of DgIIIa× from seconds to 100 seconds is small.

Blue sensitivity was evaluated in the same manner as in Example-1. The results are shown in Table 5. Table 5 shows that simply using a silver halide emulsion with a high silver chloride content satisfies rapid processability but is insufficient in terms of sensitivity. On the other hand, it can be seen that the groove bottom according to the present invention satisfies both rapid processing performance and high sensitivity at the same time.

'KJ4 Example-5 Similarly to EM-3 used in Example-1, blue-sensitive, green-sensitive and red-sensitive unchemically sensitized emulsions for silver halide emulsion were prepared as follows.

As a result of X#1 diffraction, peaks corresponding to pure silver chloride composition and pure silver bromide composition were detected in the above three types of silver halide emulsions.

The obtained unchemically sensitized emulsion was chemically ripened to the optimum sensitivity point using the nitrogen-containing heterocyclic compound, chemical sensitizer, and sensitizing dye shown in Table 6, and then N-25 was added as a stabilizer. was added in an amount of 10-7 mol per mol of silver halide.

Samples 28 to 30 were then prepared with the layer configurations shown in Table 7. (The amount added is shown per 1 2 pieces of Yokaimaru material.) Sample 2
Table 8 shows the photosensitive silver halide emulsions used in Nos. 8 to 30.
It was shown to.

(l '(-1 Il Q-1 8711-I Tll-l 5 T13-3 STn-Mu Δll A1-2 Margin below Table-8 The obtained sample was evaluated in the same manner as in Example-3.

(IL) Here, a color developing solution having the following composition was used, and the blue sensitivity, fog, and maximum 1 sentence were evaluated when the color development time was 45 seconds.

The results are shown in Table 9. From the results shown in *-9, Samples 29 and 30 in which the exemplified heterocyclic compound was added to the chemical ripening chamber.
It can be seen that the sample has a low Capri value and the highest concentration, and is highly sensitive.

Color developer composition Pure water 800yl Triethanolamine 1og 1. N-noethylhydroxylamine 5g potassium bromide
0.0+,.

Potassium chloride 2g Potassium sulfite 0.3g 1-hydroxyethylidene-1-nophosphonic acid 1,0° ethylenenoaminetetraacetic acid 1.0g Catechol-
3,5-nosulfonic acid disodium salt 1,0゜N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7mi/aniline sulfate
4.59 potassium carbonate
279 Fluorescent Brightener (4,4'-) 7 stilbene cis sulfonic acid derivative Add 1 g of water to set IZ and adjust pl+: 10.1 to 'I!4.

Table-9

Claims (1)

[Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide grains contained in at least one of the silver halide emulsion layers are silver chloride grains having a high silver bromide content phase. Content rate 80~
99.5 mol% high silver chloride silver halide grains, characterized in that the grains are chemically ripened in the presence of a nitrogen-containing heterocyclic compound and an unstable sulfur compound that form a complex compound with silver. A silver halide photographic light-sensitive material.