JPS62257145A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having high sensitivity and excellent pressure resistance as well while maintaining an excellent quick processability by applying a specific sensitization method to a specifically composed silver halide. CONSTITUTION:At least one layer of the silver halide emulsion layer contains the silver halide particles contg. >=80mol% silver chloride chemically sensitized in the presence of a silver halide solvent and unstable sulfur compd. The preferably usable silver halide particles are the silver halide particles contg. 80-99mol% silver chloride and have the high silver chloride phase constituting the greater particles of the particles and the high silver bromide phase localized to exist in or on the particles. The localized phase refers to the phase to exhibit the diffraction pattern in which the peak belonging to the high silver bromide phase can be distinctly discriminated from the peak belonging to the high silver chloride phase except the high silver bromide phase when the silver halide particles are analyzed by an X-ray diffraction method.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a silver halide photographic material, and more specifically, a silver halide photographic material that is suitable for rapid development processing, has high sensitivity, and has excellent pressure resistance. Regarding.

[Background of the Invention] Generally, silver halide photographic materials consist of a support and a photographic layer coated on the support. The photographic layer herein includes a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer.

For example, when the silver halide photographic light-sensitive material is a color photographic light-sensitive material, three kinds of halides are selectively sensitized to have sensitivity to blue light, green light, and red light on the support. A silver photographic 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 green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion layer.

Furthermore, each emulsion layer has other intermediate layers for various special purposes.
Furthermore, a protective layer is provided as the outermost layer. In addition, 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. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers is provided in a different arrangement from the above, and roughly each emulsion layer is composed of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use transparent 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 developed. A dye image is formed by reaction of the oxidation product with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-
Pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indacylon or cyano-7cetyl 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. As one method, it is known to use a color development accelerator when developing an exposed silver halide photographic light-sensitive material using an aromatic primary amine color developing agent. For example, as such a color development accelerator, US Pat.
, No. 950, No. 970, No. 2.515.147, No. 970, No. 2.515.147, No.
2.496.903, 4, 038.075, 4
．． No. 119.462, British Patent No. 1,430°998,
No. 1,455,413, Japanese Unexamined Patent Publication No. 15831/1983,
No. 55-62450, No. 55-62451, No. 55
-62452, 55-62453, 51-12
No. 422, Special Publication No. 51-12422, No. 55-497
The compounds described in No. 28 etc. have been studied, but most of these compounds have insufficient development accelerating effects, and even those compounds that exhibit sufficient development accelerating effects often cause fogging. It had the disadvantage of being 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 in which benzyl alcohol is added to a color developing solution to accelerate color development 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 color density 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 is also proposed by increasing the temperature of the color developing solution by -111 degrees.
．． If it is more than 5, the oxidation of the color developing agent will be significantly accelerated, and the color developing agent will be susceptible to IIH changes due to lack of suitable liquid resistance, making it difficult to obtain stable photographic performance. , there is a problem that the processing time becomes highly dependent.

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 raw storage stability of the silver halide photographic light-sensitive material is poor, fogging occurs before use, and furthermore, fogging easily occurs 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 a Schiff salt, for example, as disclosed in U.S. Pat. No. 3,342,559.
Research Disclosure, 1976 N 0.1
5159. 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 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and JP-A-57-64339 describes
No. 144547; JS8-50532, No. 58-
No. 50533, No. 58-50534, No. 58-505
No. 35 and No. 58-50534 disclose that 1-7 lyl pyrazolidones are added to a halogenated 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-IH533, 1058
-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, they were still unsatisfactory in other aspects of photographic performance. That is, it has been found that when a silver halide photographic light-sensitive material is produced using the above technique, it has the drawbacks of a significant decrease in sensitivity and deterioration in pressure resistance.

The most well-known method for improving sensitivity is to increase the grain size of silver halide grains, but as the grain size of silver halide grains increases, the development speed decreases.
It is well known in the art that the suitability for rapid processing deteriorates, and even if the development speed of silver halide grains improves, there is no advantage if the sensitivity decreases. That is, a sensitization method that does not depend on an increase in particle size is essential.

Moreover, pressure resistance is also an important property for facilitating the handling of photosensitive materials.

Generally, various pressures are applied to photosensitive materials.

That is, during the production of photosensitive materials (e.g. cutting process), during use of photosensitive materials (e.g. crimping in cameras, bending when handled by humans), and also during processing of photosensitive materials (e.g. transportation in automatic processors). be.

When various pressures are applied to the photosensitive material in this way, pressure is also applied to the silver halide grains in the photosensitive material through the gelatin binder, resulting in undesirable phenomena such as pressure fogging, pressure sensitization, or pressure desensitization. , which deteriorates ease of handling.

This phenomenon has long been well known as the photographic pressure effect, for example, as described by T.H.
ames): The Theory of the Photographic Process (see below)
he P hQtQ(JraDhiCP reces
s), 4th edition.

Macmillan Publishers, New York, Section 24 and D. Deutrich, F. Glanzel and E. Moyser.

Granzer and E, Mo1sar)
: Journal of Photographic Science (J.

Phot, Sci, ), 21, 221
(1973) and others.

Further, pressure may be applied to the photosensitive material in either a dry state or in a wet state during development processing, and it is necessary to improve pressure resistance in both states.

For this reason, attempts have been made to provide photosensitive materials that are less affected by pressure. For example, JP-A-53-1
No. 3923 contains a high boiling point solvent in the coupler-containing layer in an amount of 20% by weight or more of the binder.
In Japanese Patent Publication No. 50-36978, a coupler and conversion emulsion were used, and in Japanese Patent Application Laid-open No. 149933-1987, a technique was introduced to reduce pressure by incorporating a polyol into the crystal surface of host grains. , a method of improving pressure resistance using silver halide grains in which silver halide crystals having different silver halide compositions are epitaxially grown is described, but in both cases it is difficult to achieve the object of the present invention described below. It wasn't enough.

In order to improve the drawbacks of using silver halide grains with a high silver chloride content as described above, the present inventors have conducted intensive studies and found that a specific sensitization method has been developed for silver halide grains with a specific composition. The inventors have discovered the unexpected fact that by applying this method, it is possible to obtain a silver halide photographic material that maintains excellent rapid processability, has high sensitivity, and has excellent pressure resistance, and has led to the present invention. Ta.

[Object of the Invention] Accordingly, the object of the present invention is to provide a silver halide photographic material that is suitable for rapid color development processing, has high sensitivity, and is highly resistant to pressure.

[Structure 1 of the Invention The above 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 at least one of the silver halide emulsion layers contains silver halide. This is achieved by a silver halide photographic material whose Rft@ is defined as containing silver halide grains having a silver chloride content of 80 sol% or more that have been chemically sensitized in the presence of a solvent and an unstable sulfur compound.

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

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

In the silver halide photographic material of the present invention, the silver halide grains contained in at least one of the silver halide emulsion layers have a silver chloride content of 80 mol % or more. Preferably, the silver chloride content is 90 mol% or more. Further, the content of silver iodide is 1 mol% or less, preferably 0.
．． It is 5 mol% or less. More preferred is silver chlorobromide or silver chloride having a silver bromide content of 10% or less.

The silver halide grains preferably used in the present invention are silver halide grains having a silver chloride content of 80 mol % to 99 mol %, and include a high silver chloride phase that constitutes the majority of the grain, and It is preferable to have a high silver bromide phase localized on the surface.

Localization here means that when the silver halide grains are analyzed by X-ray diffraction, a peak that belongs to the high silver bromide phase is located in a high silver chloride phase other than the high silver bromide phase! 1! It refers to a diffraction pattern that can be clearly distinguished from the peak to which it belongs.

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

The silver halide grains having a localized high silver bromide phase may have a layered structure of the high bromide phase and the silver oxidide phase, or silver halide grains comprising a high silver chloride phase may be formed. Later, an island silver bromide phase may 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 localizations 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.

Silver halide grains having a high bromide localized phase that are preferably used in 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. It may also be used.

Such silver halide grains are disclosed in, for example, JP-A [59-162]
No. 540, No. 59-4111755, No. 60
-222844 publication, 60-222844 publication,
It can be formed according to the method described in Publication No. 5o-i36735@.

When the silver halide grains of the present invention are used in combination with silver halide 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.

The particle 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 processability and sensitivity, it is preferably 0.2 to 1.6 μm, 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 Microscope 195
5, pp. 94-122, or chapter 2 of [Theory of Photographic Process], co-authored by Mies and σ James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as 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 monodispersed 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 defined by the following equation.

Change 'JJt 姐姐S/r) = Criminology Section 11 Average Particle Size Here, ri is the particle size on each side of the particle, and ri represents the number of particles. The particle size referred to here refers to the diameter in the case of spherical silver halide grains, and the diameter in the case of grains with shapes other than cubic or spherical.
It represents the diameter when the projected image is converted into a circular image with the same area.

The silver halide grains according to the present invention may be obtained by any of the acid method, the mountain method, and the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as an irradiation temperature method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, a form of simultaneous mixing method is JP-A-1
IIA (1) described in No. 1354-48521 etc.
-Con I-Roll Doda Double Jeet! - method can also be used.

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.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent No. 4.183.756, U.S. Patent No. 4,22
No. 5,666, JP-A No. 55-26589, Special Publication No. 55-Sho.
-42737, etc., and The Journal of...
Photographic Science LJ, Photq
r, 5ci), 21.

8 by the method described in the literature such as 39<1973).
Particles having shapes such as a face, tetradecahedron, and dodecahedron can also be prepared and 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,
Adding metal ions using lead salts, thallium salts, iridium salts or complex salts, rhodium salts or lead salts, iron salts or lead salts,
It can be encapsulated inside the particle and/or on the particle surface,
Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

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 emulsion according to the invention is chemically sensitized in the presence of a silver halide solvent and an unstable sulfur compound.

The silver halide solvent used in the present invention includes:
Compounds that react with silver halide to form water-soluble silver salts are used, but in the case of sulfur-containing compounds, compounds that do not form silver sulfide are used. For example, ammonium thiocyanate or alkali metal salts (potassium thiocyanate, sodium thiocyanate), thiourea derivatives (tetrasubstituted thiourea such as tetramethylthiourea, which does not react with silver salts to form silver sulfide), etc. are preferably used. However, ammonia, amine derivatives (triethylenetetramine),
Compounds capable of forming a complex with silver halide, such as nitrogen-containing heterocyclic compounds such as pyridine and imidazole, and derivatives thereof, can also be used.

Next, typical examples of the above silver halide solvent will be shown, but the invention is not limited thereto.

Yo, (°Fuyuyama (exemplary compound) KNCS ?NaNCS N+(
4NC5-1 In the present invention, thiocyanates such as ammonium thiocyanate, potassium thiocyanate, and sodium thiocyanate are particularly preferably used as the halogenated ia solvent.

The silver halide solvent used in the present invention may be added before chemical ripening of the silver halide photographic emulsion or may be added during the chemical ripening. The above solvent can also be mixed with an unstable sulfur compound and added to the emulsion.
It is preferable to add it separately from the unstable sulfur compound.

In this case, it does not matter which order of addition is added first.

In the present invention, the amount of the silver halide solvent added can vary widely depending on the type of solvent and the desired effect, and is generally about 1 x 10' mol to 1 mol per mol of silver halide.
It is used in the range of X10-1 mol, preferably about 1
X 10-"mol-1x The unstable sulfur compound preferably used in the present invention is a compound that forms a silver salt when reacting with silver halide, and further forms silver sulfide under conditions such as strong alkalinity. A sulfide-containing metal object having the properties,
For example, thiosulfate, furylthiocarbamide, thiourea,
Mention may be made of sulfur sensitizers such as allyl isothiacyanate, cystine, and the like.

The amount 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 invention, the silver halide grains according to the invention are chemically sensitized in the presence of the silver halide solvent described above and the unstable sulfur compound described above. In this case, other sensitization methods such as gold sensitization, selenium sensitization, reduction sensitization, etc. can be used in combination as necessary, but in order to obtain more significant effects of the present invention,
It is preferable not to use the above sensitization methods in combination.

Regarding such sensitization method, for example, Japanese Patent Application Laid-Open No. 58-3074
No. 7, No. 60-225145, etc. have a description,
These are all related to methods for sensitizing silver chlorobromide emulsions having a high silver bromide content, and suggest improvements in the high sensitivity and pressure resistance of silver halide grains with a high silver chloride content according to the present invention. There is no mention of that.

Although it is unclear why the sensitization method of the present invention is specifically effective for the silver halide grains of the present invention, in general, silver halide emulsions with a high silver chloride content have only one interstitial silver ion. However, by applying the silver halide solvent according to the present invention,
It can also be considered that the surface of the silver halide crystal was appropriately decorated and became easily sensitized. Regarding the pressure resistance, it seems that the silver halide solvent acted on the silver halide grains and changed their properties.

The emulsion of the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and can control the sensitizing effect of the sensitizing dye. You can let me.

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 sensitizing dye represented by the following general formula [A].

The remaining white ζb, , ke general formula [A] In the general formula [A], zll and Z+2 are respectively pendioquinazole nucleus, naphthoxazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzothiazole nucleus, naphthothiazole. group, benzimidazole nucleus,
It represents the atomic group necessary to form a naphthoimidazole, pyridine or quinoline nucleus, and these heterocycles also include those having substituents. Substituents of the petero ring formed by Z++ and 212 include halogen atoms,
Examples include a hydroxyl group, a cyamic aryl group, an alkyl group, an alkoxy group, and an afrecoxycarbonyl group. Among these substituents, preferred substituents are a halogen atom, a cyano group, an aryl group, and an alkyl group having 1 to 6 carbon atoms. or an alkoxy group, and particularly preferred substituents are a halogen atom, a cyanomethyl group, an ethyl group, a methyl-hexyl group, or an hydroxyl group.

R21 and R22 each represent an alkyl group, an alkenyl group, or an aryl group, preferably an alkyl group or an alkyl group substituted with a sulfo group, and most preferably a sulfoalkyl group having 1 to 4 carbon atoms. . Further, R 23 is selected from a water-based atom, a methyl group, and an ethyl group.

Xe represents an anion, and 2 does not represent 0 or 1.

Among the sensitizing dyes represented by the general formula [A1], particularly useful dyes are the sensitizing dyes represented by the following general formula [A'].

General Formula [A'] Here, Yl and Y2 each represent an atomic group necessary to complete a benzene ring or a naphthalene ring which may be substituted.

The benzene ring and naphthalene ring formed by Yl and Y2 include those having a substituent, and the substituent is preferably a halogen atom, a hydroxyl group, a cyano group, an aryl group,
It is an alkyl group, an alkoxy group or an alkoxycarbonyl group. More preferred substituents are a halogen atom, a cyam L aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred substituents are a halogen atom,
A cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.

R21, R22, R23, XO and 2 are general formula [A]
This is the same as shown in .

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

j (hereinafter °Margin general formula [to] (CH2) 280 s Na ^-5 To-6 8-9 To-10 Knee 13 H3 Ha, -15 ^-18 8-20 8-22 △-23 To the present invention When such a silver halide emulsion is used as a green-sensitive emulsion, it is preferable to spectral sensitize it with a sensitizing dye represented by the following general formula [81].

General Formula [8] In the formula, Z+1 and Z12 each represent an atomic group necessary to form a benzene ring or a naphthalene ring fused to an oxazole. The heterocyclic nucleus formed may be substituted with various substituents, and these preferred substituents are halogen atoms, aryl groups, alkyl groups, or alkoxy groups. More preferred substituents are a halogen atom, a phenyl group, and a methoxy group, and the most preferred substituent is a phenyl group.

According to a preferred embodiment of the present invention, Zo and z12 together represent a benzene ring fused to an oxazole ring, and the 5-position of at least one of these benzene rings is substituted with a phenyl group, or 1 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 an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group. 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.

×10 represents an anion, such as chlorine, Jl element, CH
Examples include anions such as 3504, C2, and H2SO4. n represents 1 or 0. However, when the compound forms an inner salt, n represents O.

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 Below margin [B-2] [8-3] [B-4] [B-6] [8-73 [8-8] [B-101 [6-11] Halogenation according to the present invention When a silver emulsion is used as a red-sensitive pre-L agent, it is preferable to perform spectral sensitization with a sensitizing dye represented by the following general formula [C] or a sensitizing dye represented by the following general formula [, D].

General formula [C] General formula [D] In the formula, R represents a hydrogen atom or an alkyl group, R1 to R+ represent an alkyl group and an aryl group, respectively, and Z
+, Z2, Z4 and Z5 each represent an atomic group necessary to form a benzene ring or naphthalene ring condensed to a thiazole ring or selenazole ring, and z3 represents a hydrocarbon atomic group necessary to form a 6-membered ring. where i is 1
or 2, 2 represents a sulfur atom or a selenium atom, and Xθ represents an anion.

In the above general formula, the alkyl group represented by R includes 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, R1, R2, R3 and R4 are each a linear or branched alkyl group, and this alkyl group may have a substituent. (e.g. methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl, carboxymethyl, carboxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfoethyl, sulfobutyl, β-hydroxy-γ-sulfopropyl, sulfatebu-Ovir, furyl) , benzyl, etc.) or an aryl group, and this aryl group may have a substituent. (
(for example, phenyl, carboxyphenyl, sulfophenyl, etc.), and the heterocyclic nucleus formed by zl, z2, Z4 and z5 may have a substituent, and preferred substituents are halogen. Atom, aryl group, alkyl group, or alkoxy group, and more preferably a halogen atom (for example, a chlorine atom), a phenyl group, or a methoxy group.

X represents an anion (for example, C1, Br, !, SO+, etc.), and l represents 1 or 2.

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

Hereinafter, the general formulas [ ] and [
, 01 are shown below.

Below margin 1 1 o 10
0
U-G C-12 C-13 e [)-Z p-now v-5 D-7 Attack 〒Each white ffi: 1! '- The amount of the sensitizing dye represented by the above general formula [A], [B], [C] or [,0] is not particularly limited, but is approximately 1X10' to 1X, 10- per mole of silver halide. It is preferably used in a range of 3 mol, more preferably 5
A method well known in the art can be used to add the sensitizing dye in an amount of 10-6 to 5 x 10-4 moles.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), in some cases diluted with water, and If necessary, they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibration for this dissolution.The sensitizing dye used in the present invention can be obtained by dissolving the dye in a volatile organic solvent, as described in U.S. Pat. No. 3,489,987, etc. A method of dispersing the solution in a hydrophilic colloid and adding this dispersion, Japanese Patent Publication No. 46-2418
As described in Japanese Patent No. 5, etc., 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. Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method. Other addition methods are as follows: Unopened Patent Nos. 2 and 9
No. 12,345, No. 3,342,605,
Methods described in Japanese Patent No. 2,996,287 and Japanese Patent No. 3,425.835 can 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 prior to addition to the silver halide emulsion. . When adding them separately, the order, time, and interval can be arbitrarily determined depending on the purpose. In the present invention, the sensitizing dye used is added to the emulsion at a certain time. It may be added at any time during the agent production process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

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

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

For photographic emulsion layers and other water-based colloid layers of light-sensitive materials using the silver halide emulsion of the present invention, a hardening agent that warms binder (or protective colloid) molecules and increases film strength may be used alone or in combination. It is hardened by. The hardener is li! in the processing solution. Although it is desirable to add an amount of the photosensitive material that can be hardened to such an extent that there is no need to add a film agent, it is also possible to add a hardener to the processing solution.

As the hardening agent used in the present invention, the following general formula [I]
Alternatively, it is preferable to use a compound represented by the general formula [I[].

General formula [I] [wherein R1 is a chlorine atom, a hydroxy group, an alkyl group,
Alkoxy group, alkylthio group, -0M group (M is a monovalent metal atom), -NR'R'' group (R' and Rn are a hydrogen atom, an alkyl group, and an aryl group, respectively) or -NHC
OR' represents a group (R' is a hydrogen atom, an alkyl group, or an aryl group), and R2 represents the same group as R1 above except for a chlorine atom. ] General formula [II] [wherein R3 and R4 are each a chlorine atom, hydroxy group, alkyl group, alkoxy group or -OM group (M
represents a monovalent metal atom). Q and Q' each represent a linking group selected from -0-1-S-1-NH-, an alkylene group or an arylene group. 1 and 雫 represent O or 1, respectively. Next, typical examples of the 5I membrane agent according to the present invention represented by the general formulas [I] and [II] will be described.

Below margins (I-1) (I-2) (I
-3> (I-4) (I-5
) (I-6) (I-7)
(I-8) (I-9) N11C*1mu(,t Ct (II-2) (TI-3> (II-4) (I[-5) CL CL (II-6) (I-8 ) (n-9) The general formula [II or [II
In order to add the 5JilJ agent shown by to the silver halide emulsion layer and other constituent layers, water or a water-miscible solvent (
For example, it may be dissolved in methanol, ethanol, etc.) and added to the coating liquid for the above-mentioned constituent layer. The addition method may be either a batch method or an in-line method. The timing of addition is not particularly limited, but it is preferably added immediately before coating.

These hardeners have a concentration of 0.5 to I per 1 g of coated gelatin.
QOmg, preferably 2.0-50-g is added.

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.

For the purpose of improving the dimensional stability of photographic emulsion layers and other hydrophilic colloid layers of photosensitive materials using the silver halide emulsion of the present invention, dispersion power of water-insoluble or sparingly soluble synthetic polymers (
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 for the blue light-sensitive emulsion layer. However, 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 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- or 2-equivalent couplers of the acylacetamide type and benzoylmethane type; these are described, for example, in U.S. Pat. No. 2,778.
, No. 658, No. 2,875,057, No. 2,90
No. 8,573, No. 2,908,513, No. 3, 2
27゜155, same No. 3.227.550, same 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, '415.652, '3.447.928, '3,551,155
No. 3,582,322, No. 3.725.07
2, German Patent No. 1,547,868, German Patent No. 2,0
No. 57,941, No. 2,162,899, No. 2,
No. 163.812, No. 2,213,461, No. 2
, No. 219,917, No. 2,261,361, No. 2,263,875, Japanese Patent Publication No. 1976-13-76, Japanese Patent Publication No. 48-29432, No. 48-66834, No. 4
No. 9-10736, No. 49-122335, No. 50
-28834, 50-132926, 55-1
No. 44240 and No. 56-87041, No. 8 Mei 1Bm.

The magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers of the 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indacylon type, and cyanoacetyl type. Patent No. 2,600,788,
No. 3,061,432, No. 3,062,653, No. 3,127,269, No. 3,311゜476
No. 3,152,896, No. 3,419,39
No. 1, No. 3,519,429, No. 3.558.3
No. 18, No. 3,684.514, No. 3.705.
No. 896, No. 3.888.680, No. 3,907
, No. 571, No. 3.928.044, No. 3,93
0,861, 3.930.816, 3.9
No. 33,500, JP-A-49-29639, JP-A-49-29639
No. 111631, No. 49-129538, No. 51-
No. 112341, No. 52-58922, No. 55-62
No. 454, No. 55-118034, No. 56-386
No. 43, No. 56-135841, Special Publication No. 46-60
No. 479, No. 52-34937, No. 55-29421
No. 55-35696, British Patent No. 1, 247.
No. 493, Belgian Patent No. 792,525, West German Patent No. 2, Specifications of No. 156.111, Japanese Patent Publication No. 1973-
No. 60479, JP-A-59-125732, JP-A-59-125732
No. 228252, No. 59-162548, No. 59-1
No. 71956, No. 60-33552, No. 60-436
No. 59, West German Patent No. 1,070,030, and US Patent No. 3,725,067.

Cyan dye image-forming couplers include phenolic,
Naphthol type 4-equivalent or 2-equivalent type cyan dye image-forming couplers are typical, and U.S. Patent No. 2,306,4
No. 10, No. 2.356.475, No. 2.362,
No. 598, No. 2,367.531, No. 2,369
, No. 929, No. 2.423.730, No. 2.47
No. 4.293, No. 2,476.008, No. 2,4
No. 98,466, No. 2,545゜687, No. 2,
No. 728,660, No. 2.772.162, No. 2
．． No. 895.826, No. 2,976, No. 146, No. 3. O゛02.836, same No. 3,419,390,
3.446.622, 3.476, 563, 3,737,316, 3.758, 308
No. 3.839.044, British Patent No. 478.9
No. 91, No. 945.542, No. 1,084,48
No. 0, No. 1, 377, 233, No. 1.388.0
24 and 1,543°040, as well as JP-A Nos. 47-37425 and 50-10135,
No. 50-25228, No. 50-112038, No. 50-117422, No. 50-130441, No. 51-6551, No. 51-37647, No. 51-5
No. 2828, No. 51-108841, No. 53-10
No. 9630, No. 54-48237, No. 54-6612
No. 9, No. 54-131931, No. 55-32071, No. 59-146050, No. 59-31953, and No. 60-117249.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is fine.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied to a previously unknown method of dispersing hydrophobic additives such as couplers, and is usually mixed with a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary with a low-boiling point and Alternatively, it is dissolved using a water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, 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 the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoates, alkylamides,
71 points 15 such as fatty acid esters and trimesic acid esters
A solvent having a temperature of 0° C. or higher is used.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

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

The color antifoggant may be used in the emulsion layer itself, or may be used 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.

The hydrophilic colloid layer such as the protective 1L intermediate layer of the photosensitive material of the present invention contains an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It's okay to stay.

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, improves the ease of writing, and provides a layer between the photosensitive materials. A matting agent can be added to prevent sticking.

Sliding of photosensitive materials using the silver halide emulsion of the present invention I!
Lubricants can be added to reduce chafing.

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.).

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

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

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

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

An image can be formed using the silver halide photographic material of the present invention by subjecting it to a color development treatment known in the art.

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

These developers include amine phenol and p-phenylene diamine derivatives. These compounds are more stable than the free state and are therefore generally in salt form, such as the hydrochloride or liJ! Used in acid salt form. In addition, these compounds are generally used in an amount of about 0.1 g to about 30 g per liter of color developing solution.
It is preferably used at a concentration of from about 1 g to about 15 g per color developer.

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

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-diethyl-p-phenylenediamine hydrochloride,
, N-1 dimethyl-p-phenylenediamine salt M3s,
2-amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
4-Amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention.

For example, alkali hydroxylamines such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners. It is also possible to optionally contain agents and the like.

The color developer usually has an I)H value of 7 or higher, most commonly from about 10 to about 13.

The temperature of the color developer is not particularly limited, but it is usually carried out at a temperature of 25 to 45°C in consideration of shortening processing time, influence on photographic performance, stability of the color developer, etc.

In the case of color development of the silver halide photographic light-sensitive material of the present invention, in the above color developer composition, if benzyl alcohol is not substantially used and the color development is completed in a short time (for example, 1 minute or less), the color development of the present invention can be carried out. This is preferable because the effect becomes more pronounced.

The silver halide photographic light-sensitive material according to the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its breaker, and may be processed in an alkaline activation bath. The color developing agent brecaser is a metal compound that can produce a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a phosphoric acid amide derivative precursor. , sugar amine reactant precursor, and urethane type precursor. The precursors of these aromatic primary amine coloring agents are:
For example, U.S. Patent No. 3.342.599, U.S. Pat.
7.114, 2.695.234@, 3.7
No. 19.492, each town of British Patent No. 803.783
11! , JP-A-53-185628, JP-A No. 54-790
35 issues of each publication, Research Disclosure Magazine 15
It is described in No. 159, No. 12146@, and No. 3924.

These aromatic first-handling amine color developing agents or their precursors need to be added in such amounts that sufficient color development can be obtained when activated. The amount varies depending on the type of light-sensitive material, but is generally between 1 and 5 moles, preferably between 0.5 and 3 moles, per mole of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc.
It can be added as an emulsified dispersion using a high boiling point organic solvent such as dioctyl phthalate or tricresyl phosphate, or it can be added by impregnating a latex polymer as described in Research Disclosure No. 14850. .

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment.

Many compounds are used as bleaching agents, but iron (
m), cobalt (■), copper (I[), etc., in particular complex salts of these polyvalent metal cations with mono-acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N
- Aminopolycarboxylic acids such as hydroxyethylethylenediaminediacetic acid, gold B complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or ferricyanine salts, dichromates, etc. alone or as appropriate; A combination is used.

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 pH adjuster, a chelating agent, an anti-spill agent, and the like. These specific conditions are described in Japanese Unexamined Patent Publication No. 5
8-134 et al. No. 36, etc. can be referred to.

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

(Example-1) EIA (
While maintaining It at 1.8, a nitric acid aqueous solution (concentration 1, O
a + ol/ fl ) and a halide aqueous solution consisting of potassium bromide and sodium chloride (KBr ta degree 0.8 m
ol/j! , Na C/! 1 degree 0.2 n+ol/
1) was added over 120 minutes to create a monodisperse silver chlorobromide emulsion (EM-1>) with a silver chloride content of 20 mol%.
As a result of electron microscopy observation, M-1 has an average particle diameter of 0.76.
It had a tetradecahedral shape in terms of μ- (sphere equivalent).

Next, a silver chloride emulsion (EM-2) was prepared in the same manner as EM-1 except that I) A-7.0 and a sodium chloride aqueous solution (1,0a+ol/fl) were used as the halide aqueous solution. EM-2 has an average particle size of 080μIII (sphere equivalent)
It was a monodispersed cubic emulsion (silver chloride 100 mol %).

Next, in a 5% aqueous solution of ossein gelatin, p
While maintaining Ag at 7.0, a nitrate-silver aqueous solution (concentration 1.0 mol/fl) and a sodium chloride aqueous solution (
11 degrees (1.0 mol/l) was added over 90 minutes, and the silver chloride particles had an average particle size of 0.79 μl1 (in terms of spheres).
After the silver nitrate aqueous solution and potassium bromide aqueous solution (concentration 1.0 mol/l) are further added to grow silver bromide on the surface of the silver chloride particles,
It was named EM-3. As a result of electron microscopic observation, EM-3 was found to be a cubic monodisperse emulsion with an average particle size of 0.81 μl 1 liter (in terms of spheres).

Furthermore, 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 (XM
As a result of further analysis by A') and xi 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 1! of the outer shell! It was found that the proportion of silver bromide in one silver halide grain was about 5 mol %.

Next, a silver chloride emulsion was prepared by the same method as EM-2, and then a potassium bromide aqueous solution (concentration 1.0 mat/l) corresponding to 90 mol% of the silver nitrate used to form the emulsion was added.
) was added to the above silver chloride emulsion and then left at 60° C. for 30 minutes to obtain EM-4. When EM-4 was analyzed in the same way as EM-3, it was found that the particles had an average particle size of 0.85 μm and were close to spherical, and the particle surface was almost 100% silver bromide.
However, the silver bromide content of the entire grain was about 89 mol%.

Further, in the measurement with an x11 diffractometer, the separation between the respective peaks attributed to silver chloride and silver bromide was poor, and the shape of the spectrum was so-called tailed.

Next, part of the above EM-1 to EM-3 was divided, and sodium thiosulfate (silver halide 1
4II1g per mole) and an exemplary sensitizing dye (A-2, 5011+I per mole of silver halide) as a blue-sensitive sensitizing dye.
+) to chemically sensitize the blue-sensitive emulsion E.
MS-1, EMB-3 and EMS-5 were created.

Next, using other parts of EM-1 to EM-3, 30 mo of silver halide solvent [exemplified compound (2)] per mole of silver halide is added during 5 minutes of addition of sodium thiosulfate. Other than that, EMB-2, EMB-4 and EM
S-6 was created.

Next, using EM-4, chemical sensitization was performed under the same conditions as EMB-1 to EMS-3 to create EMS-7.

Next, using EMB-1 to EMS-7 as blue-sensitive emulsions, silver halide photographic materials having the following configurations were prepared and designated as Samples-1 to Sample-7, respectively.

(Y-1) Next, try F! -1 to W (\) Sensitometric evaluation was performed by the method not shown below in order to evaluate sensitivity and rapid processability.

[Sensi I-Metori 1 Evaluation] A photosensitive needle (Konishi Roku Photo Industry Co., Ltd. IKs-
7 type), exposure was performed with white light through an optical wedge, and the following treatments were performed.

[Processing process] Temperature Time Development color development 34.7±0.3℃ 40 seconds, 80 seconds bleach fixing 34.7±0.5℃ 50 seconds stabilization
Dry for 90 seconds at 30-34℃ 60-8
0℃ 60 seconds [Color developer] Pure water
8001Q ethylene glycol
10i12N,N-diethylhydroxylamine
10 potassium chloride 2gN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
3013 optical brightener (4,4'
-Diaminostilbendisulfone a derivative>
1 (Add 1 water to make the total volume 12, DHlo, 08
Adjust to.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 6Q (1 ethylenediaminetetraacetic acid 3g ammonium thioIII! acid (70% solution) 10 (h12 ammonium sulfite (40% solution) 27.5tQ potassium carbonate or glacial acetic acid Adjust the pH to 7.1 and add water to bring the total to 1r.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1Q 1-hydroxyethylidene-1,1-diphosphonic acid 2Q Add water to make 1i, add sulfuric acid or potassium hydroxide to o)-1 7.
Adjust to 0.

The reflection density of the obtained sample was measured using a densitometer PDA-65 [manufactured by Konishiroku Photo Industry Co., Ltd.].

The sensitivity was expressed as the reciprocal of the exposure amount required to obtain a reflection density of 0.8, and evaluated as a relative value at a color development interval of 40 seconds. The results are shown in Table-1.

The rapid processability was evaluated by the maximum reflection density ([)WaX) at 40 seconds and 80 seconds between color development R. In this case, it is determined that there is sufficient laX even at 40 seconds, and the smaller the movement of WaX from 40 seconds to 80 seconds is, the better the rapid processing performance is. The results are shown in Table-1.

Next, the pressure resistance of Samples-1 to 7 was evaluated by the method shown below.

[Evaluation of pressure resistance] ■ Pressure resistance when dry (pressure before B light) After leaving the sample at 25°C and 40% relative humidity for more than 2 hours, a ball point needle with a sphere diameter of 0.11111 was placed perpendicular to the sample surface. , while moving the sample surface in parallel at a speed of 1 CI/Sec, the ball point needle was simultaneously moved from 0 to 10
0 (invasion 1!lf applied by continuously changing the load of J
After uniform exposure was performed so that the color density after the f1 process was 0.1 to 0.3, the same development process as in the sensitometric evaluation described above (color development for 40 seconds) was performed. The obtained sample was visually observed to evaluate the degree of decrease of 31 degrees and increase in concentration due to pressure. The evaluation scale is as follows.

0: Excellent with almost no density change.

Δ...Small concentration change is observed.

X: Concentration changes are large and poses a practical problem.

■ Pressure resistance during drying (pressure after exposure) Evaluate in the same manner as the pre-exposure pressure in (■) except that exposure is applied before applying pressure.

■ Pressure resistance when wet A sample was uniformly exposed to light so that the color density after development was 0.1 to 0.3, and the sample was incubated at 35°C using the color developer described above.
While performing color development, a ball point needle with a spherical diameter of 0.3111 is placed perpendicular to the sample surface in the color developer solution, and while the sample surface is moved in parallel at a speed of 1 cm/sec, the ball point needle is placed at the same time. The development process was carried out in the same manner as in the sensitometric evaluation described above, except that a load of ~50 g was applied while changing continuously, and the evaluation was made in the same manner as the pressure resistance during drying (2).

The evaluation results of pressure resistance are shown in Table 1.

From the margin table 1 below, samples 3 to 6 with high silver chloride content have excellent rapid processability, but sample 3 and sample n-5, which do not use the sensitization method of the present invention, has very low sensitivity, whereas sample-4 and sample Fl using the sensitization method of the present invention have very low sensitivity.
It can be seen that with -6, a significant increase in sensitivity has been achieved while maintaining excellent rapid processing performance. In addition, pressure resistance was also improved by the sensitization method of the present invention, and sample 6, which used an emulsion in which a small amount of high silver bromide phase was provided on the surface of silver halide grains with a high silver chloride composition, It can be seen that the resistance is also very good. On the other hand, sample Fl-7, which had a similar high silver bromide phase on the silver halide grain surface, but which used an emulsion prepared by the so-called halide conversion method, had very poor pressure resistance. It can be said that the improvement in pressure resistance is a specific effect obtained by grains having a high silver chloride composition and a high silver bromide phase.

(Example-2) Using EM-1 to EM-4 prepared in Example-1, a green-sensitive sensitizing dye (B-4) was used instead of a blue-sensitive sensitizing dye (A-3) as a sensitizing dye. Example-
Green-sensitive emulsions EMG- to EMG-7 were prepared in the same manner as EMB1 to EMB-7 in 1.
Test Fl-8 to Fl-14 were prepared using IMG-1 to IMG-7 with the following configuration.

(M-1) rcot I The obtained samples 8 to 14 (2 pairs) were evaluated for sensitivity, rapid processability, and pressure resistance by the same method as in Example 1. The results are shown in Table 2. Shown below.

14 - From Table 2, although the magnitude of the effect is slightly different from Example 1, even when the present invention is applied to green-sensitive emulsions, excellent rapid processability is maintained. At the same time, it can be seen that a silver halide photographic material with high sensitivity and excellent pressure resistance can be obtained.

(Example-3) Next, EM-2 and EM- created in Example-1
3, except that 30 mg of exemplary compound (4) was added per mol of silver halide as a silver halide solvent.
-4 and EMB-6, respectively.
8 and EMB-9 were created.

Next, using the above EMS-8 and EMB-9 and EMB-3 and EMB-5 created in Example-1,
Furthermore, as a hardening agent, bis(vinylsulfonylmethyl)ether (H-1) and exemplary hardening agent (1-2) were added in Table 3.
Silver halide photographic materials, samples 15 to 22, having the following configurations were prepared using the combinations shown below.

(Y-2) Table 3 Sensitivity and pressure resistance of the obtained samples 15 to 22 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

From Table 4, even if the silver halide solvent and hardener are changed,
It can be seen that the effects of the present invention can be obtained.

It can also be seen that from the viewpoint of improving pressure resistance, it is more preferable to use a hardening agent represented by the general formula [Ii or [Ir].

(Example-4) E except that the temperature during silver halide grain formation was 50°C.
Silver chloride emulsion EM-5 having an average grain size of 055 L1 m (in terms of spheres) was prepared in the same manner as M-2.

EM-5 was divided into two parts, and one part was treated at 50°C with sodium thiosulfate (4II 1 g per mole of silver halide) and a green-sensitive sensitizing dye (B-6, 10 g per mole of silver halide).
Chemical sensitization was performed by adding 0111 (+>) to prepare green-sensitive emulsion EMG-8.

To use EM-5, add sodium thiosulfate (
4 mQ per mole of silver halide), red-sensitive sensitizing dye (C
-9> and a polycondensate of p-methylphenol and hexamethylenetetramine (700% per mole of silver halide)
No. 2) was added to perform chemical j4 sensitivity, red-sensitive emulsion EM
R-1 was created.

Next, the above E to IR-1 were used as red-sensitive emulsions, the above E to IG-8 were carried out as edge-sensitive emulsions, and EMS-1 to EM prepared in Example-1 were used as blue-sensitive emulsions.
Using B-7, the other configurations are shown in Table 5 below.
Two samples from sample-23 were prepared.

The following margin CI (C-2) (tJV-1) (LJV-2) The obtained samples 23 to 29 were tested in the same manner as in Example 1 to determine the sensitivity, rapid processability and pressure resistance of the blue-sensitive emulsion layer. was evaluated.

The results are shown in Table-6.

From Ishi-Hohaku Table-6, it was found that the same results as in Example-1 were obtained with the halogen-arsenic photographic material having a layer structure similar to that of actual color vapor, as shown in Table-5. It can be seen that the effects of the present invention are fully exhibited.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedure? 111 official book (method) % formula % 1 Display of incident Showa era 6
1 year patent application No. 100203 2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship with the person making the amendment ￥IFF Applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Patient: 4, Agent: 102 Address: 1-1 Kudankita 4-chome, Chiyo 11-ku, Tokyo @ (Delivery date) July 1986 298 6. Pair of amendments

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is formed in the presence of a silver halide solvent and an unstable sulfur compound. 1. A silver halide photographic material comprising silver halide grains having a silver chloride content of 80 mol % or more that have been chemically sensitized. (2) Halogenation according to claim (1), wherein the silver halide grains having a silver chloride content of 80 mol % or more have a high silver chloride phase and a high silver bromide phase as different phases. Silver photosensitive material.