JPH09325449A - Silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic material suitable for quick processing and capable of obtaining a neutral black or clod black silver image by containing specific silver halide particles and a specific compound in a silver halide emulsion layer. SOLUTION: The flat plate-like silver halide particles at 50% or above of the whole projected area are contained in a silver halide emulsion layer, the average silver iodide percentage contant of the flat plate-like particles is set to 1.0mol% or below, and the aspect ratio of set to 2-20. The compound expressed by the formula is contained in the silver halide emulsion layer, where W represents -NR1 , R2 , or -OH, R1 and R2 represent alkyl group or the like, R3 represents hydrogen atom or monovalent substituent, (n) represents 1, 2, or 3, Z1 and Z2 represent nitrogen atom or =C(R3 )-respectively, X represents a group of atoms required to form five or six-membered aromatic carbon ring or aromatic heterocyclic ring together with Z1 , Z2 and the carbon atom neighboring to them, R4 represents hydrogen atom or acyl group, R represents aliphatic group or aromatic group, (p) is 1 or 2, and CP represents a specific group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a black-and-white silver halide photographic light-sensitive material which is excellent in storability with time and which produces a cold black tone silver image.

[0002]

2. Description of the Related Art In recent years, with respect to the development processing of a silver halide photographic light-sensitive material (hereinafter, also simply referred to as "light-sensitive material"), it has been strongly desired to reduce the processing time and the processing waste liquid. For example, in the medical field, the number of X-ray photographs taken is rapidly increasing due to the spread of regular medical examinations, medical checkups, etc., and the increase in diagnosis and examination in general medical care. Therefore, under the present circumstances, there is an increasing demand for further rapid development processing and further reduction of processing waste liquid.

For rapid processing of photosensitive materials, development,
It is essential to shorten the processing time such as fixing, washing and drying. However, if the conventional photosensitive material is simply shortened by the developing time, for example, the image density and the sensitivity are significantly lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing becomes defective and the image quality is deteriorated. Therefore, it is basically necessary to increase the developing speed, fixing speed, drying speed, etc. of the light-sensitive material.

Conventionally, in order to accelerate the developing speed and the fixing speed, the content of silver iodide having a low solubility is lowered, silver chlorobromide having a high solubility, the use of a silver chloride emulsion, the fine graining of silver halide grains and the flat plate are used. It is believed that shaping is advantageous. But,
It is known that the reduction of the silver iodide content and the use of silver chlorobromide and silver chloride cause a reduction in the sensitivity.

As a technique for incorporating a silver halide solvent (thiocyanic acid compound) into silver halide grains and a light-sensitive material in order to enhance sensitivity and development progress, US Pat. No. 2,222,264, 3,320, 069, JP-A-62-18538 and the like. However, it is well known that the deterioration of the storage stability with time is accompanied by the improvement of the sensitivity, which is a big problem when using a silver halide solvent.

Further, as a sensitizing method for silver chloride grains, it is known that a photosensitive material for printing can contain a metal compound of Group VIII of the Periodic Table to enhance the sensitivity, but both of them are cubic crystals. The effect on octahedral particles,
The effect with tabular grains is unknown.

Further, since it is necessary to improve developability in order to reduce the amount of processing waste liquid, silver halide grains having high covering power capable of obtaining high concentration with a small amount of silver are desirable, and sensitivity, graininess, It is known that tabular grains are suitable in terms of sharpness and color sensitization efficiency. However, on the other hand, when the grain size and grain thickness of the silver halide grains decrease, the light scattering of the blue light component of silver formed in the development process increases and the light becomes strongly yellowish, so the silver image becomes yellowish. The result is tinged.

Conventionally, as a technique for improving the color tone of image silver, many studies have been reported from a light-sensitive material and a development processing side. For example, a specific mercapto compound is well known as a typical color tone agent. There is. More recently,
For example, a technique has been proposed in which a specific dye is dissolved in a water-insoluble high-boiling point organic solvent as described in JP-A-5-165147 and dispersed in a water solvent in a minute size to be contained in a light-sensitive material. The sensitivity was changed depending on the storage conditions before exposure. Particularly, in the case of a medical X-ray photosensitive material, there is a problem that the intensifying screen brought into contact with the photosensitive material during exposure is stained. Further, this technique also has a drawback that the fog density is increased because the unexposed area contains the same amount of dye as the exposed area.

In order to solve this drawback, JP-A-3-15
No. 7645, there is proposed a technique in which a dye image corresponding to a silver image is formed by a diffusion resistant compound that releases a diffusible dye by the action of silver ions, while forming a silver image. The effect of improvement and the effect of reducing fog were insufficient.

Further, Japanese Patent Laid-Open No. 3-153234 proposes a technique using a leuco dye which gives a blue image corresponding to a silver image. Although the development of stains and stains in the developing solution is suppressed by the technique, the blue dye formed from the leuco dye has a long-wavelength color tone and has a greenish tint, so that the effect of improving the blackness of a silver image is not improved. It was insufficient. In addition, the leuco dye remaining in the unexposed portion of the processed light-sensitive material is likely to develop color over time, which causes a problem of increased fog.

[0011]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a silver halide photographic light-sensitive material capable of rapid processing and having a neutral black or cold black tone of a silver image. . A second object of the present invention is to provide a silver halide photographic light-sensitive material which is less likely to contaminate intensifying screens and developing solutions. A third object is to provide a silver halide photographic light-sensitive material in which the photographic performance of the light-sensitive material does not fluctuate with time.

[0012]

The objects of the present invention are achieved by the following.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer have a total projected area of 50 or less. % Is tabular silver halide grains, and the average silver iodide content of the tabular grains is 1.
0 mol% or less, and an aspect ratio of 2 to 20,
In addition, the silver halide emulsion layer is a silver halide photographic light-sensitive material containing a compound represented by the following general formula (1).

[0014]

[Chemical 7]

In the formula, W is --NR ₁ R ₂ , --OH or --OZ.
R ₁ and R ₂ each represent an alkyl group or an aryl group, Z represents an alkali metal atom or a quaternary ammonium salt, R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, n represents 1, 2 or 3, Z ₁ and Z ₂ each represent a nitrogen atom or = C (R ₃ )-, and X represents Z ₁ , Z ₂
And a group of atoms necessary for forming a 5- or 6-membered aromatic carbocycle or an aromatic heterocycle with the carbon atoms adjacent thereto, R ₄ is a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group or a sulfo group. A group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,
R represents an aliphatic group or an aromatic group, and p is 1 or 2
Represents CP represents the following group.

[0016]

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In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on the benzene ring. or,
R ₅ and R ₆ and R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁
Each represents an alkyl group, an aryl group or a heterocyclic group.
R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ are each R
It is synonymous with ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R
₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents 1, 2 or 3. Y represents an atomic group necessary to form a 5- or 6-membered monocyclic or condensed-ring nitrogen-containing heterocycle with two nitrogen atoms. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ have the same meaning as R ₁₉ and R ₂₀ , respectively. R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R
₂₈ represents a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ are respectively R ₂₅ , R ₂₇ and R
Synonymous with ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅
And R ₃₆ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₃ has the same meaning as R ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ are
They are synonymous with R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₇ is R ₂₆
Is synonymous with R ₄₁ , R ₄₂ and R ₄₃ are respectively R ₂₅ ,
It is synonymous with R ₂₇ and R ₂₈ . R ₄₄ has the same meaning as R ₂₆ .
* Represents a bonding point between CP and another partial structure in the general formula (1).

(2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer have a total projected area of 50. % Is tabular silver halide grains, and the average silver iodide content of the tabular grains is 1.
0 mol% or less, and an aspect ratio of 2 to 20,
In addition, the silver halide emulsion layer is a silver halide photographic light-sensitive material containing a compound represented by the following general formula (3).

[0019]

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In the formula, W is --NR ₁ R ₂ , --OH or --OZ.
R ₁ and R ₂ each represent an alkyl group or an aryl group, Z represents an alkali metal atom or a quaternary ammonium salt, R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, n represents 1, 2 or 3, Z ₁ and Z ₂ each represent a nitrogen atom or = C (R ₃ )-, and X represents Z ₁ , Z ₂
And a group of atoms necessary for forming a 5- or 6-membered aromatic carbocycle or an aromatic heterocycle with the carbon atoms adjacent thereto, R ₄ is a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group or a sulfo group. A group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,
CP represents the following group.

[0021]

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In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on the benzene ring. or,
R ₅ and R ₆ and R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁
Each represents an alkyl group, an aryl group or a heterocyclic group.
R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ are each R
It is synonymous with ₁₀ and R ₁₁ . R ₁₅ has the same meaning as R ₁₂ . R
₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents 1, 2 or 3. Y represents an atomic group necessary to form a 5- or 6-membered monocyclic or condensed-ring nitrogen-containing heterocycle with two nitrogen atoms. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ have the same meaning as R ₁₉ and R ₂₀ , respectively. R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R
₂₈ represents a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R ₂₉ , R ₃₁ and R ₃₂ are respectively R ₂₅ , R ₂₇ and R
Synonymous with ₂₈ . R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅
And R ₃₆ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₃ has the same meaning as R ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ are
They are synonymous with R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₇ is R ₂₆
Is synonymous with R ₄₁ , R ₄₂ and R ₄₃ are respectively R ₂₅ ,
It is synonymous with R ₂₇ and R ₂₈ . R ₄₄ has the same meaning as R ₂₆ .
* Represents a bonding point between CP and another partial structure in the general formula (3).

(3) The silver halide photographic light-sensitive material according to (1), wherein the compound represented by the general formula (1) is represented by the following general formula (2).

[0024]

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In the formula, R ₁ , R ₂ , R ₃ , R ₄ , CP, n and R
And p are R ₁ , R ₂ and R in the general formula (1), respectively.
It is synonymous with ₃ , R ₄ , CP, n, R and p.

(4) A silver halide photographic light-sensitive material containing at least one compound represented by the general formula (3) and at least one compound represented by RSO ₃ H. Here, R represents an aliphatic group or an aromatic group.

(5) The silver halide photographic light-sensitive material according to (4), wherein the compound represented by the general formula (3) is represented by the following general formula (4).

[0028]

[Chemical 12]

Where R ₁ , R ₂ , R ₃ , R ₄ , CP and n
Are R ₁ , R ₂ , R ₃ in the general formula (1),
It is synonymous with R ₄ , CP and n.

(6) In the compounds represented by the above general formulas (1) to (4), R ₄ , R ₉ , R ₁₂ , R ₁₅ , R ₁₇ ,
_{R 21, R 24, R 26} , R 30, R 33, R 37 and at least one of the groups represented by R _44, -COOM ¹ and -SO ₃ M ²
(M ¹ and M ² each represent a hydrogen atom or an alkali metal atom), and the silver halide photographic light-sensitive material according to any one of (1) to (5), which is substituted with at least one selected from .

(7) When the silver halide grain emulsion is prepared, the silver halide grain is 1.0% in the presence of a silver halide solvent.
The silver halide photographic light-sensitive material according to (1) or (2), which contains silver iodide in an amount of not more than mol%.

(8) 5 of the total projected area of silver halide grains
0% or more is a tabular grain having a parallel main plane of (100) planes and an aspect ratio of 1.3 or more, and a silver chloride content of 20 to 100 mol%. Group VIII metal, Group
A silver halide photographic light-sensitive material containing at least one metal selected from Group II transition metals, lead, rhenium, molybdenum and chromium, and at least one compound represented by the general formula (1).

The present invention will be described in detail below.

In the tabular silver halide grains of the present invention, silver iodobromide, silver bromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and the like can be used as the silver halide, and particularly, Silver iodobromide, silver iodochloride and silver chloroiodobromide are preferred. When silver iodobromide is used, the silver iodide content is 1.0 mol% or less, but preferably 0.5 mol% or less, as the average silver iodide content in the entire silver halide grains.

In the present invention, a method for forming silver iodide is a method in which a silver nitrate solution and a solution containing iodide ions are simultaneously added to an emulsion containing tabular grains as a base,
A method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide and the like can be applied. Of these, the method of adding fine silver halide grains is preferable. It is particularly preferable to add fine silver iodide grains.

When the tabular silver halide grain of the present invention contains silver iodide, it may be contained at any position in the grain, but it is preferably contained on the outermost surface of the grain. The outermost surface mentioned here refers to a period from the end of the grain growth portion to the end of the chemical ripening.

The silver iodide content and the average silver iodide content of each silver halide grain are determined by EPMA (Electron).
It can be determined using the Probe Micro Analyzer) method. In this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, an X-ray analysis is performed by electron beam irradiation and electron beam excitation, and elemental analysis of extremely minute portions can be performed. By this method, the silver halide composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

The tabular silver halide grains of the present invention preferably have a more uniform iodide content between grains. When the distribution of the iodide content between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

In the tabular silver halide grains used in the present invention, 50% or more of the total projected area of the silver halide grains in the light-sensitive material of the present invention has an aspect ratio (grain diameter / grain thickness).
The average value of is 2 to 20, preferably 2 to 12 or less, and more preferably 3 to 8. Here, the grain size means an average projected area diameter (hereinafter, referred to as “grain size”), which is a circle-equivalent diameter of a projected area of the tabular silver halide grain (of a circle having the same projected area as the grain). Diameter) and thickness refers to the distance between two parallel major planes forming a tabular silver halide grain.

The tabular silver halide grains are preferably monodisperse. Specifically, (standard deviation of particle size / average particle size) × 100 = when the size of the distribution is defined by the relative standard deviation (variation coefficient) that can be expressed as the size (%) of the size distribution 25
% Or less, more preferably 20% or less,
Especially preferably, it is 15% or less.

The silver halide grains of the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) = width of thickness distribution (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 20% or less. It is preferably 15% or less.

When tabular silver halide grains having twin planes are used, the tabular silver halide grains are preferably hexagonal. A hexagonal tabular grain (hereinafter sometimes referred to as “hexagonal tabular grain”) means that the main plane ((111) plane) is hexagonal and the maximum adjacency ratio is 1.0 to 2 Say that it is 0. Here, the maximum adjacent side ratio is a ratio of the length of the side having the maximum length to the length of the side having the minimum length forming the hexagon.

In the present invention, it is also preferable that the hexagonal tabular grains have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. The length of a side having a rounded corner is represented by the distance between the intersection of the straight line portion of the side and the line extending from the straight line of the adjacent side.
In addition, it is also preferred that the tabular grains have a further rounded shape and are substantially circular.

Each side forming the hexagon of the hexagonal tabular grain is
It is preferable that one-half or more of them be substantially linear. More preferably, the ratio of adjacent sides is 1.0 to 1.5.

The silver halide used in the present invention is preferably treated with a silver halide solvent, and examples of such a solvent include (a) organic thioethers, (b) thiourea derivative, (c) oxygen or A silver halide solvent having a thiocarbonyl group sandwiched between a sulfur atom and a nitrogen atom,
In addition to (d) imidazoles, (e) sulfite, (f) thiocyanate and the like, silver halide solvents described in JP-A-57-196228 and the like can be mentioned. Below, the example of these specific compounds is shown.

[0046]

Embedded image

Particularly preferred solvents are thiocyanate and tetramethylthiourea. As the thiocyanate, a water-soluble salt such as a metal thiocyanate or ammonium thiocyanate can be generally used, but in the case of a metal salt, care should be taken to use a metal element that does not adversely affect photographic performance, Potassium salts and sodium salts are preferred. Further, a sparingly soluble salt such as silver thiocyanate may be added in the form of fine particles.

The silver halide solvent may be added at any position during the emulsion preparation, but it is preferably added both before the desalting step and during the chemical sensitization.

The addition amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the total addition amount from the grain formation to the end of the chemical sensitization is silver halide 1
It is preferably 2.5 × 10 ⁻³ mol or more and less than 5 × 10 ⁻² mol per mol.

When tabular silver halide grains are used to form silver iodide in the presence of a silver halide solvent, the silver iodide content is 1.0 mol% or less, but 0.5 mol% or less. It is more preferably 0.4 mol% or less. or,
It is also preferred that 0.4 mol% or less is formed in the presence of a silver halide solvent before the desalting step, and further 0.6 mol% or less is formed during chemical ripening.

In the present invention, when a tabular silver halide grain having a (100) plane as a main plane is used, the main plane of the tabular silver halide grain has a shape of right-angled parallelogram or right-angled parallelogram. It has a rounded shape. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5,
More preferably, it is less than 2. In addition, the length of a side when the corner is rounded is represented by the distance between the intersection of the straight part of the side and the line extending the straight part of the adjacent side. The silver chloride content is 20 mol% or more, preferably 30 to 70 mol%. The content of silver iodide is preferably at most 1.0 mol%, more preferably at most 0.5 mol%.

The silver halide grains used in the present invention may have dislocations. Dislocations are described in F. Hamilt
on: Photo. Sci. Eng. , 57 (1967)
And T. Shiozawa: J. et al. Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. That is, the silver halide grains taken out with care not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope,
Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (eg, printout) due to an electron beam. This time,
The thicker the particles, the more difficult it is for an electron beam to pass. Therefore, a clearer image can be observed with a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). .

The silver halide grains may form silver nuclei during grain formation. The silver nucleation is performed by adding a reducing agent to the mixed solution for silver halide emulsion or grain growth, or the mixed solution for silver halide emulsion or grain growth is carried out under a low pAg of pAg7 or less. Alternatively, it is carried out by aging or grain growth under a high pH condition of pH 7 or higher. A method of combining these methods is a preferred embodiment of the present invention.

Reduction sensitization has long been known as a technique for forming silver nuclei. For example Journal
of Photographic Science, 2
5, 19-27 (1977) and Photograp
hic science and engineeri
ng, 32, 113-117 (1979), the silver nuclei formed by reduction sensitization have Photon
graphishe Korrespndenz, 1st
Volume, p. 20 (1957) and Photographic
Science and Engineering,
Michele in the report from 19, 49-55 (1975)
As described by ll and Lowe, it has been thought to contribute to sensitization through a reaction represented by the following formula during exposure.

AgX + hv → e ⁻ + h ⁺ ... (1) Ag ₂ + h ⁺ → Ag ⁺ + Ag ··· (2) Ag → Ag ⁺ + e ⁻ ··· (3) Here Where h ⁺ and e ⁻ are free holes and free electrons generated by exposure, hv is a photon, and Ag ₂ is a silver nucleus formed by reduction sensitization.

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and its derivatives, and stannous salt. Also, other suitable reducing agents include
Examples include borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount of these reducing agents is preferably from 10 ^-2 to 10 ^-8 mol per mol of silver halide.

A silver salt can be added for ripening with a low pAg, but a water-soluble silver salt is preferred, and silver nitrate is preferred as the water-soluble silver salt. The pAg during aging is suitably 7 or less, preferably 6 or less, more preferably 1 to 3
(Where pAg = −log [Ag ⁺ ]).

The high pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate for silver halide formation, an alkaline compound excluding ammonia is preferably used because the effect of ammonia is reduced.

As a method of adding the silver salt or the alkaline compound for forming the silver nuclei, rush addition may be performed, or addition may be performed over a certain period of time. In this case, the addition may be performed at a constant flow rate, or may be performed while changing the flow rate with respect to time. Also, the required amount may be added in several divided portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, they may be present in the reaction vessel, or they may be mixed in the soluble halide solution and added together with the halide. Furthermore,
You may add separately from a soluble silver salt and a soluble halide.

An oxidizing agent can be used in the silver halide emulsion. The following can be used as the oxidizing agent.

Hydrogen peroxide (water) and its adduct: H
₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O ₂ , Na ₄ P ₂ O ₇ -2
Such as _{H 2 O 2, 2Na 2 SO} 4 -H 2 O 2 -2H 2 O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [T
_{i (O 2) C 2 O} 4 ]-3H ₂ O or the like. Other examples include peracetic acid, ozone, iodine, bromine, and thiosulfonic acid compounds.

The amount of the oxidizing agent used depends on the type of reducing agent,
The amount depends on the conditions of silver nucleus formation, the timing of addition of the oxidizing agent, and the addition conditions, but it is 10 ^-2 per mole of the reducing agent used.
10 ^-5 mol is preferred.

The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can be added prior to the addition of the reducing agent. Also, after adding the oxidant,
It is also possible to newly add a reducing substance in order to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the above-mentioned oxidizing agents, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazine and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include endiols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The addition amount of the reducing substance is preferably 10 ^-3 to 10 ³ mol oxidizing agent per mole of using the.

Heavy metal ions usable in the present invention include metals of Group VIII of the periodic table such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt, and cadmium, zinc, mercury and the like. Examples thereof include Group II transition metals of the Periodic Table and ions of lead, rhenium, molybdenum, tungsten, chromium and the like, and among them, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable.

These heavy metal ions can be added to the silver halide emulsion in the form of salt or complex salt. Above all, it is preferable to add it in the form of a complex salt to the emulsion because it is easily incorporated into the silver halide emulsion and the effect of the present invention becomes large.

When the heavy metal ion forms a complex,
Examples of the ligand include cyanide, thiocyanic acid, isothiocyanic acid, cyanic acid, chloride, bromide, iodide, carbonyl, and ammonia.
Among them, thiocyanic acid, isothiocyanic acid and cyanate ion are preferred.

The heavy metal compounds preferably used in the present invention are shown below, but the invention is not limited thereto.

(1) FeCl ₂ , (2) FeCl ₃ ,
(3) (NH ₄ ) Fe (SO ₄ ) ₂ , (4) K ₃ [Fe (C
N) ₆ ], (5) K ₄ [Fe (CN) ₆ ], (6) K ₂ [I
rCl ₆ ], (7) K ₃ [IrCl ₆ ], (8) K ₂ [Pt
Cl ₆ ], (9) K ₂ [Pt (SCN) ₄ ], (10) K ₂
[NiCl ₄ ], (11) K ₂ [PdCl ₆ ], (12)
K ₃ [PdCl _{6], (13) CdCl 2, (} 14) Zn
Cl ₂ , (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ],
(16) K ₃ [Re (CNO) ₆ ], (17) K ₃ [Mo
(CNO) ₆ ], (18) K ₄ [Fe (CNO) ₆ ],
(19) K ₂ [W (CO) ₄ (CNO) ₂ ], (20) K ₂
[Cr (CO) ₄ (CNO) ₂ ], (21) K ₄ [Ru
(CNO) ₆ ], (22) K ₂ [Ni (CN) ₄ ], (2
3) PbCl ₂ , (24) K ₃ [Co (NH ₃ ) ₆ ], (2
5) K ₅ [Co ₂ (CNO) ₁₁ ], (26) K ₃ [Re
(CNO) ₆ ], (27) K ₄ [Os (CNO) ₆ ],
(28) K ₂ [Cd (CNO) ₄ ], (29) K ₂ [Pt
(CNO) ₄ ], (30) K ₃ [IrBr ₆ ] To allow a heavy metal ion to be contained in the silver halide emulsion, the heavy metal compound is halogenated before the formation of the silver halide grains, during the formation of the silver halide grains. It may be added at an arbitrary place in each step during physical ripening after silver particles are formed. For this purpose, for example, the heavy metal compound may be placed as an aqueous solution and added at a desired timing. Alternatively, it may be dissolved together with the silver halide and continuously added during the grain forming step.

The amount of heavy metal ions added to the silver halide emulsion is 1 × 10 ^{-9 to} 1-1 per mol of silver halide.
It is preferably from 0 to ² mol, and particularly preferably from 1 × 10 ^{−8 to} 1-10 ⁻³ mol.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.2 to 3.0 μm, more preferably 0.4 to 2.0 μm. The average thickness is preferably 0.02 to 1.0 μm, more preferably 0.05 to 0.40 μm, and further preferably 0.0.
It is 5 to 0.30 μm. Particle size and thickness can be optimized to optimize sensitivity, pressure characteristics, etc.

Gelatin is preferably used as the dispersion medium for the protective colloid of silver halide grains, and examples of the gelatin include alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000), phthalated gelatin and the like. Modified gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure magazine (Research Disclosure)
e, hereinafter referred to as RD) 176, 17643 (December 1978), item IX.

In the silver halide emulsion, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be contained. The removal of the salts can be carried out according to the method described in Item II of RD176 vol. 17643.

The tabular silver halide grains used in the present invention can be chemically sensitized.

There are no particular restrictions on the conditions of the step of chemical ripening, that is, chemical sensitization, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used.

For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound, a reduction method. A reduction sensitization method using a polar substance, gold or other, a noble metal sensitization method using a noble metal and the like can be used alone or in combination, and among them, a selenium sensitization method, a tellurium sensitization method, a reduction sensitization method and the like are preferably used. The selenium sensitization method is particularly preferable.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (allyl isoselenocyanate, etc.), selenoureas (N, N-dimethylselenourea, N, N, N′-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-
N'-heptafluoropropylcarbonylselenourea,
N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (tri-p-triselenophosphate, etc.), selenides (triphenylphosphine selenide, diethyl selenide, And diethyl diselenide). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally it is 10 ^-8 to 10 ^-4 per mol of silver halide.
Use molar amounts. The addition method is, depending on the properties of the selenium compound to be used, a method of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or a mixed solvent, or a method of adding it by mixing with a gelatin solution in advance. However, the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer is 4
A range from 0 to 90C is preferred. More preferably 45-8
0 ° C. The pH is preferably in the range of 4-9 and the pAg is preferably in the range of 6-9.5.

Examples of useful tellurium sensitizers include telluroureas (N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'- Dimethyl-N'-phenyl tellurourea, etc., phosphine tellurides (tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-di-i-propylphosphine telluride, dibutylphenylphosphine telluride, etc.) ), Telluroamides (telloacetamide, N, N-dimethyl tellurobenzamide, etc.),
Examples include telluroketones, telluroesters, and isotellurocyanates.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in an appropriate reducing atmosphere.

Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, and sulfites.

The amount of the reducing agent added is determined by the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system,
It is preferable to change it depending on environmental conditions such as pH and pAg, but in the case of thiourea dioxide, for example, as a rough guide, it is about 0.01 to 2 m per mol of silver halide.
Good results are obtained with g. In the case of ascorbic acid, about 50 mg to 2 g per mol of silver halide
Is preferred.

As conditions for reduction sensitization, the temperature is about 40 to
70 ° C., time is about 10 to 200 minutes, pH is about 5 to 11,
The pAg is preferably in the range of about 1 to 10 (the pAg value is the reciprocal of the Ag ⁺ ion concentration).

Silver nitrate is preferred as the water-soluble silver salt. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range.

As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, the following general stabilizers can be used. JP-A-57-8
2831 and / or V.I. S.
"Zeitshift fur wi" by Gahler
ssenscheftriche Photograph
hie ", Bd. 63, 133 (1969) and the thiosulfonic acids described in JP-A-54-1019 are used in combination to obtain good results. These compounds may be added at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

The silver halide emulsion layer of the present invention contains the compound represented by the general formula (1).

In the general formulas (1) to (4), the alkyl group represented by R ₁ and R ₂ is preferably a methyl, ethyl, propyl or butyl group. These may be further substituted, and preferred substituents include a hydroxyl group and a sulfonamide group. The aryl group represented by R ₁ and R ₂ is preferably a phenyl group.

Examples of the monovalent substituent represented by R ₃ include
Alkyl group (methyl, ethyl, i-propyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-
Butyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), aralkyl groups (benzyl, 2-phenethyl, etc.), aryl groups (phenyl, naphthyl, p-tolyl, p-chlorophenyl, etc.), alkoxyl groups (methoxy, ethoxy, i). -Propoxy, butoxy, etc.), aryloxy groups (phenoxy, etc.), cyano groups, acylamino groups (acetylamino, propionylamino, etc.), alkylthio groups (methylthio, ethylthio, butylthio, etc.),
Arylthio group (phenylthio, etc.), sulfonylamino group (methanesulfonylamino, benzenesulfonylamino, etc.), ureido group (3-methylureido, 3,3-dimethylureido, 1,3-dimethylureido, etc.), sulfamoylamino group (Dimethylsulfamoylamino, etc.), carbamoyl group (methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, etc.), sulfamoyl group (ethylsulfamoyl, dimethylsulfamoyl, etc.), alkoxycarbonyl group (methoxycarbonyl,
Ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), sulfonyl group (methanesulfonyl, butanesulfonyl, phenylsulfonyl, etc.), acyl group (acetyl, propanoyl, butyroyl, etc.), amino group (methylamino, ethylamino, dimethyl, etc.) Amino, etc.), hydroxyl group, nitro group, imide group (phthalimide, etc.), heterocyclic group (pyridyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, etc.)
And the like.

The acyl group represented by R ₄ is preferably an acetyl group, a trifluoroacetyl group or a benzoyl group. Preferred examples of the sulfonyl group include a methanesulfonyl group and a benzenesulfonyl group. Preferable examples of the carbamoyl group include a diethylcarbamoyl group and a phenylcarbamoyl group. Preferred examples of the sulfamoyl group include a diethylsulfamoyl group. The alkoxycarbonyl group preferably includes a methoxycarbonyloxy group and an ethoxycarbonyloxy group. Preferable examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

As the alkali metal atom represented by Z,
Examples thereof include sodium and potassium. Examples of the quaternary ammonium salt include ammonium having 8 or more carbon atoms such as trimethylbenzylammonium, tetrabutylammonium, and tetradecylammonium.

Examples of the 5- or 6-membered aromatic heterocyclic ring formed by X, Z ₁ , Z ₂ and the carbon atoms adjacent to them include pyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, pyrrole, furan and thiophene. , Thiazole, oxazole, imidazole, thiadiazole, oxadiazole ring and the like. Preferably it is a pyridine ring.

Examples of the substituent capable of substituting on the benzene ring represented by R _{5 to} R ₈ include groups having the same meanings as the monovalent substituents represented by R ₃ described above. Preferred are an alkyl group and an acylamino group.

The 5- to 7-membered ring formed by combining R ₅ and R ₆ and R ₇ and R ₈ with each other includes an aromatic carbocycle and a heterocycle, preferably a benzene ring.

Examples of the alkyl group represented by R ₁₀ and R ₁₁ include methyl, ethyl, propyl and butyl groups.
Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 5- or 6-membered aromatic heterocycle having at least one kind of O, S, and N atoms in the ring (pyridine, pyrazine, 6-membered ring azine such as pyrimidine ring and its benzerogue; pyrrole, thiophene, furan and its benzerogue; 5-membered ring azole such as imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole, oxadiazole and its benzerogue etc. Groups. R ₁₀ and R ₁₁ preferably include a phenyl group, a pyrazolyl group, a pyridyl group and the like.

Examples of the alkyl group represented by R ₁₆ include methyl, i-propyl, pentyl and t-butyl groups. Examples of the aryl group include phenyl and naphthyl groups. As the sulfonyl group, a methanesulfonyl group,
Examples thereof include a benzenesulfonyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group. Examples of the carbamoyl group include a diethylaminocarbamoyl group.

Examples of the nitrogen-containing heterocycle represented by Y include imidazole, triazole and tetrazole rings and their benzo-fused rings.

Examples of the alkyl group represented by R ₁₉ and R ₂₀ include methyl, pentyl and t-butyl groups.
Examples of the aryl group include phenyl and naphthyl groups.

Examples of the substituent represented by R ₂₅ , R ₂₇ and R ₂₈ include phenyl, methyl, benzoyl, phenoxy and ethoxy groups.

Each of the substituents represented by R _{1 to} R ₄₄ is
Further, it may be substituted with a group as described for R ₃ .

When the compound represented by the general formula (1) does not have a counter ion, that is, when p is 0 (corresponding to the general formula (3)), the compound becomes unstable. Since the compound of the present invention may not exhibit the effects of the present invention, the compound of the present invention has the above counter ion, that is, p
Is preferably 1 or 2.

The aliphatic group represented by R is preferably an alkyl group such as hexyl and dodecyl.
Examples of the aromatic group include aryl groups such as phenyl, p-tolyl, dodecylphenyl, and acylaminophenyl, but aryl groups having a substituent are preferable.

The compounds represented by formulas (1) to (4) are specifically listed below, but the compounds are not limited to these.

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[Chemical 21]

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Representative synthetic examples of the above compounds are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound 8)

[0118]

[Chemical formula 26]

(1) 3.9 g was dissolved in 50 ml of ethyl acetate, 0.5 g of 5% Pd / C was added, and normal pressure catalytic hydrogenation was carried out. The blue color of the reaction liquid disappeared and (2) was produced.

Next, 1.2 g of triethylamine and 1.5 g of acetyl chloride were added to the reaction solution, and the mixture was stirred at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 3.8 g of the desired Exemplified Compound 8 (yield: 89).
%)Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound 9)

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3.9 g of (1) of Synthesis Example 1 was mixed with 5 parts of ethyl acetate.
It was dissolved in 0 ml, 0.5 g of 5% Pd / C was added, and atmospheric pressure catalytic hydrogenation was performed. The blue color of the reaction solution disappeared and (2)
Was generated.

Next, 1.2 g of triethylamine and 4.0 g of trifluoroacetic anhydride were added to the reaction solution, and the mixture was stirred at room temperature for 2 hours. The catalyst and insolubles were separated by filtration, and the residue was recrystallized from ethyl acetate to give 4.0 g of the desired Exemplified Compound 9 (yield: 8).
5%).

The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 3 (Synthesis of Exemplified Compound 58)

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Exemplified Compound 8 was added to 30 ml of methanol 3.
5 g was dissolved, and p-toluenesulfonic acid monohydrate 2.6
g and stir.

Next, the reaction solution was poured into 300 ml of water and collected by filtration to obtain 4.1 g of the desired exemplary compound 58 (yield 87%).
Obtained.

The structure was confirmed by NMR spectrum and Mass spectrum.

Other compounds could be easily synthesized in the same manner as in the above-mentioned synthesis example.

The addition amount of the compounds represented by the general formulas (1) to (4) of the present invention is silver 1 in the medical light-sensitive material.
It is preferable that the amount is 1 × 10 ^-6 mol or more and less than 5 × 10 ^-1 mol per mol in order to realize the effect of the present patent. Addition of less than this amount has a small effect of improving the silver color tone, while addition of more than this amount The whole image is dark, which is not preferable. More preferably, it is 5 × 10 ⁻⁵ mol or more and 5 × 10 ⁵ mol / mol of silver.
^It is preferable that the content of less than ^-2 mol, more preferably 5 x 10 ^-4 mol or more and less than 1 x 10 ^-2 mol per mol of silver, in order to exhibit the effect.

As the method for adding the compounds represented by the general formulas (1) to (4), any method may be used depending on the properties of each compound. Examples thereof include a method of adding as a solid fine particle dispersion, a method of dissolving in a high boiling point solvent and performing the above dispersion, and a method of adding, and a method of dissolving in a water-miscible organic solvent (methanol, ethanol, acetone, etc.) and adding. . Among them, a preferable method is a method of adding as a solid fine particle dispersion or a method of dissolving in a water-miscible organic solvent and adding.

When added as a solid fine particle dispersion, a known method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied as the dispersion method. It can take any value, but it is preferably 0.01 to 20 μm, more preferably 0.03 to 2 μm.

The molar ratio of the compounds represented by the general formulas (3) and (4) to RSO ₃ H of the present invention is RS0 ₃ H1 per 1 mol of the compounds represented by the general formulas (3) and (4). It is preferably ˜3 mol.

The compounds represented by the general formulas (1) to (4) can be contained in any layer of the photographic constituent layers, but from the viewpoint of intensifying screen contamination, they are emulsion layers for X-ray photography. Alternatively, it is preferably contained in a layer between the emulsion layer and the support, and particularly preferably in the transverse light blocking layer.

In the present invention, the amount of the hydrophilic binder in the silver halide emulsion layer is preferably 3.0 g / m ² or less, more preferably 2.0 g, per one side of the support when the emulsion layers are provided on both sides of the support. / M ² or less. When the emulsion layer is provided on only one side of the support, the amount is preferably 6.0 g / m ² or less, more preferably 4.0 g / m ² or less.

The light-sensitive materials of the present invention include black-and-white light-sensitive materials (medical light-sensitive materials, printing light-sensitive materials, negative light-sensitive materials for general photography, etc.), color photographic light-sensitive materials (color negative light-sensitive materials, color reversal light-sensitive materials, color prints). Sensitive material), photosensitive material for diffusion transfer,
Although it is a photothermographic material or the like, it is preferably a black-and-white silver halide photographic light-sensitive material, and particularly preferably a medical light-sensitive material.

The light-sensitive material may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in a layer of the emulsion layer or other layers.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material preferably contain an inorganic or organic hardener. For example, chrome salt (chrome alum,
Chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3) , 5-Triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β- (vinylsulfonyl) propionamide), active halogen compounds (2,4-dichloro-6)
-Hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), isoxazoles, 2-chloro-6-hydroxytriazinylated gelatin, etc. can be used alone or in combination. . Among them, JP-A Nos. 53-42121 and 53-
No. 57257, No. 59-162456, No. 60-80
Active vinyl compounds described in U.S. Pat. No. 846 and US Pat.
Active halogen compounds described in No. 325,287 are preferable.

Polymeric hardeners can also be used effectively. For example, dialdehyde starch, polyacrolein, US Pat.
Polymers having aldehyde groups such as the acrolein copolymers described in 96,029, U.S. Pat. No. 3,623,87.
Polymer having an epoxy group described in US Pat.
Polymers having a dichlorotriazine group described in 362,827, RD17333 (1978) and the like,
Polymers having an active ester group described in JP-A-56-66841, JP-A-56-142524,
U.S. Pat. No. 4,161,407, JP-A-54-6503
No. 3, RD16725 (1978) and the like, and polymers having an active vinyl group or a group which is a precursor thereof are preferable. Among them, an active vinyl group or a polymer having a long spacer as described in JP-A-56-142524 is used. Particularly preferred are polymers in which the precursor group is attached to the polymer backbone.

In order to make the light-sensitive material of the present invention suitable for rapid processing, an appropriate amount of a hardener is added in advance in the step of applying the light-sensitive material to adjust the water swelling rate in the developing-fixing-washing step. By doing so, it is preferable to keep the water content in the light-sensitive material before the start of drying low.

The light-sensitive material of the present invention preferably has a water swelling ratio of 150 to 250% during the development processing, and the film thickness after expansion is preferably 70 μm or less. Water swell rate is 250
If it exceeds%, poor drying occurs, for example, automatic processor processing,
Especially in rapid processing, poor transport occurs. When the water swelling rate is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing this by the film thickness before processing, and multiplying by 100. To tell.

Examples of the support usable in the light-sensitive material of the present invention include those described on page 28 of RD17643 and page 1009 of RD308119. A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.

Various additives can be further added to the light-sensitive material according to the purpose. Examples of additives and the like used include RD17643 (December 1978)
Mon., pp. 23-28, XVIII, pp. 18716 (1)
997 Nov., page 648, upper right to page 651, left and ibid. 3
08119 (December 1989), p.996, item III to 1.
Examples thereof include those described in Section XVII, page 009.

Next, preferable development processing of the light-sensitive material of the present invention will be described.

The processing of the light-sensitive material of the present invention is carried out, for example, by the method described in R
D17643, page 29, section XX to page 30, section XXI or RD
Treatment with a treatment solution as described in 308119, pages 1011 to XX to 1012, items XXI may be performed.

Development processing using a solid processing agent is preferably used. The automatic developing machine having a mechanism for supplying the solid processing agent to the processing tank has, as a supplying means, for example, when the solid processing agent is a tablet, the above-mentioned Japanese Utility Model Publication Nos. 63-137783, 63-97522 and 1). Although there is a known method such as No. -85732, any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, it is actually
81964, 63-84151, JP-A-1-29.
Gravity drop method described in No. 2375, etc.
Nos. 05159, 63-195345 and the like are known, but are not limited to the methods using screws or screws.

The solid processing agent may be charged in any place as long as it is in the processing tank, but it is preferable that the solid processing agent is communicated with the processing section for processing the light-sensitive material and the processing solution is circulated between the processing section and the processing section. It is preferable that the structure is a place, and there is a certain amount of circulation of the treatment liquid between the treatment unit and the treatment unit, and the dissolved components move to the treatment unit. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In the developer used in the processing method of the present invention,
As the developing agent, in addition to the dihydroxybenzenes, aminophenols and pyrazolidones described in JP-A-6-138591, reductones described in JP-A-5-165161 can also be used. Among the pyrazolidones used, particularly those having a 4-position substitution (dimesone, dimesone S, etc.) are particularly preferred because they have little water-soluble property or change over time of the solid treating agent itself.

As the preservative, an organic reducing agent may be used as well as a sulfite as described in JP-A-6-138591. Besides, a chelating agent and a bisulfite adduct of a hardener described in JP-A-6-258786 can be used.

Further, as a silver sludge preventive agent, JP-A-5-
It is also preferable to add the compounds described in JP-A No. 289255 and JP-A-6-308680 (general formulas [4-a] and [4-b]). The addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A No. 1-124853 are particularly preferable.

An amine compound may be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

It is necessary to use a buffer for the developer,
As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, o -Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (5-sulfosalicylic acid) Potassium) and the like.

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazine. If necessary, compounds, mesoionic compounds, ionic compounds, imidazoles and the like can be added.

As the antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Examples thereof include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine (1-phenyl-5-mercaptotetrazole as a representative example).

In the developer composition used in the present invention, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound or the like may be used as an organic solvent for increasing the solubility of the developing agent. You can

Furthermore, various additives such as a stain inhibitor, a sludge inhibitor, and a stacking effect accelerator can be used.

A compound known as a fixing agent can be added to the fixing agent used in the present invention. In addition to the fixing agent, a chelating agent, a pH buffering agent, a hardening agent, a preservative and the like can be added. In addition, a bisulfite addition product or a known fixing accelerator can be used as a hardener.

It is also preferable to add a starter prior to the treatment, and it is also preferable to solidify the starter and add it. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as potassium bromide, organic inhibitors, and development accelerators are used.

The light-sensitive material of the present invention has a total processing time of 10 to 10.
It is preferably treated in 45 seconds, more preferably 15
~ 30 seconds. The total processing time referred to in the present invention means that the steps from development to drying are completed within 45 seconds by an automatic processor. That is, the time from when the tip of the photosensitive material starts to be dipped in the developing solution to when the tip comes out of the drying zone after the processing step (so-called Dry to Dry time).
Is within 45 seconds.

Drying time is usually 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with a far infrared ray heating means may be installed in the automatic processor. The automatic developing machine includes an automatic developing machine provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the development-fixing-rinsing steps (JP-A-3-264953). ) May be used. Further, a device capable of adjusting a developing solution or a fixing solution may be incorporated.

The light-sensitive material of the present invention can be processed by a conventional processing method using no solid processing agent.

In the present invention, the replenishment amount of the developing solution or the fixing solution can be 200 ml or less per 1 m ^{2 of the} light-sensitive material. In addition, various techniques used in the field of photography can be applied to the practice of the present invention.

[0166]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of silver iodobromide hexagonal tabular grains> (Preparation of emulsion-1) A1 ossein gelatin 75.5 g 10% aqueous solution of surfactant (A) in ethanol 6.78 ml Potassium bromide 64. 7g Finish with water to 10800ml B1 0.7N silver nitrate aqueous solution 1340ml C1 2.0N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution F1 ossein gelatin 125g water 4000ml G1 KSCN aqueous solution (2N) 60 ml H1 3 wt% gelatin and silver iodide grains (average grain size 0.05 μm) fine grain emulsion (*) 0.008 mole equivalent A: polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt * Contains 0.06 mol of potassium iodide 5.0 wt% aqueous solution of gelatin 6.64 liters, an aqueous solution containing potassium iodide 7.06 mole of silver nitrate and 7.06 mol, respectively 2 liters was added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

At 55 ° C, Japanese Patent Publications No. 58-58288 and No. 5:
400 ml of the solution (B1) and 400 ml of the solution (D1) were added to the solution (A1) using a mixing stirrer described in 8-58289.
The whole amount was added by the simultaneous mixing method over 40 seconds to form nuclei.

After the addition of the solution (B1) and the solution (D1) is completed, the solution (F1) is added and the temperature is raised to 70 ° C. to effect aging. Further, after the remaining amount of the solution (B1) is added over 25 minutes, aging is performed for 10 minutes using a 28% aqueous ammonia solution, and the pH is returned to neutral with acetic acid. Solutions (C1) and (E
While maintaining the pAg at 7.8, 1) was simultaneously added and mixed at a rate commensurate with the critical growth rate. After adding (C1) in its entirety, (G1) and (H1) were added. After stirring for 5 minutes, soluble salts were desalted and removed by a sedimentation method.

In this emulsion, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of hexagonal tabular grains was 0.20.
It was confirmed by an electron microscope that the average particle diameter was 0.80 μm. The distribution of the circle equivalent diameter is 1
5%.

(Preparation of Emulsion-2) Emulsion-2 was prepared in exactly the same manner as Emulsion-1 except that the addition amount of the solution (G1) was reduced to 6 ml.

(Preparation of Emulsion-3) Emulsion-3 was prepared in the same manner as Emulsion-1 except that the solution (G1) was not added.

(Preparation of Emulsion-4) The amount of fine silver iodide particles in the solution (H1) was equivalent to 0.16 mol, and the silver iodide content was 2.
Emulsion-4 was prepared in the same manner as Emulsion-1 except that the content was changed to 0 mol%.

(Preparation of Emulsion-5) Solutions (G1) and (H
After adding 1) and stirring for 5 minutes, emulsion-5 was prepared in exactly the same manner as emulsion-1, except that pAg was raised to 10.0 using a potassium bromide solution and stirred for 5 minutes before desalting. .

The amount of SCN in each obtained emulsion was quantified by the following method.

Ultrapure water was placed in the centrifuge tube, the emulsion was heated to 40 ° C., and then centrifuged. The supernatant after centrifugation was subjected to ultrafiltration for HPLC measurement (SCN quantification in gelatin). Further, 1% potassium bromide solution was added to the silver halide after centrifugation, the mixture was heated and stirred at 40 to 50 ° C., and the centrifuged supernatant was subjected to ultrafiltration for HPLC measurement. SCN quantification of silver halide surface).

<HPLC conditions> Equipment: Hitachi L-6200 Column: GS-220H 7.6 mm ID × 250 mm Eluent: 10 mM phosphate buffer (pH = 7) Detection: UVD UV = 210 nm Temperature: 40 ° C. Flow rate: 1.0 ml / min Injection amount: 20 μl Table 1 shows the outline of the obtained emulsion. "SCN quantitative" in the table is the sum of the quantitative value of SCN in gelatin and the quantitative value of silver halide surface.

[0178]

[Table 1]

Subsequently, the above emulsion was kept at 47 ° C., and a predetermined amount of the following spectral sensitizing dyes (SD-1, SD-2) was added as a solid fine particle dispersion, and then ammonium thiocyanate, chloroauric acid and thiol were added. Add a mixed aqueous solution of sodium sulfate and a dispersion of triphenylphosphine selenide,
Aging was performed for a total of 2 hours and 30 minutes.

At the end of the ripening, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer (ST-1).

[0181]

[Chemical 29]

Spectral sensitizing dyes and other additives and their addition amounts (per mol of AgX) are shown below.

SD-1 390 mg SD-2 4 mg Adenine 10 mg Sodium thiosulfate 3.3 mg Ammonium thiocyanate 50 mg Chloroauric acid 2.0 mg Silver iodide fine particles 5 mmol Triphenylphosphine selenide 4.0 mg ST-1 1000 mg Here The term "silver iodide fine grain" used in the description means that the grain size of 3
Weight% gelatin and silver iodide grains (average grain size 0.05μ
m) which is a fine grain emulsion.

A solid fine particle dispersion of a spectral sensitizing dye was prepared by a method similar to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye is previously set to 27
It was obtained by adding water whose temperature was adjusted to ℃ and stirring at a high speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

The dispersion liquid of the above selenium sensitizer was prepared as follows. That is, triphenylphosphine selenide 12
0 g was added to 30 kg of ethyl acetate at 50 ° C. and stirred,
It was completely dissolved. Separately, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.

Then, these two liquids were mixed to obtain a diameter of 10
5 by a high speed stirring type disperser with a cm dissolver
Dispersion was performed at 0 ° C. for 30 minutes at a dispersing blade peripheral speed of 40 m / sec.

Immediately after dispersion, stirring was performed under reduced pressure until the residual concentration of ethyl acetate was 0.3 wt% or less.
The ethyl acetate was removed. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used for experiments.

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a transverse light shielding layer coating solution and a protective layer coating solution described below were also prepared.

As the support, an undercoat layer comprising a layer containing glycidyl methacrylate-methyl acrylate-butyl methacrylate copolymer (50:10:40 wt%) as a main component and a layer containing cross-linked gelatin as a main component was applied. A 175 μm thick polyethylene terephthalate (PET) film base for X-rays, which was colored blue with a concentration of 0.15, was used.

The following transverse light-shielding layer was coated on both sides of this support, and the emulsion layer coating solution and the protective layer coating solution described above were added in that order from the side closer to the support to the emulsion layer and the protective layer. Simultaneous multi-layer coating and drying were carried out so as to obtain a predetermined amount, and X-ray photosensitive materials (Samples 1-1 to 1-30) were obtained. The addition amount is shown as an amount per 1 m ^{2 on} one side of the light-sensitive material.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (D-1) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg Latex (L) 0.2 g Hardener (H -1) 5 mg Compound of the present invention or comparative compound Described in Table 2 Colloidal silica (average particle size 0.014 μm) 10 mg Hardener (H-2) 2 mg Second layer (emulsion layer) In each emulsion obtained above The following various additives were added.

Compound (G) 0.5 mg Compound (T) 5 mg t-butyl-catechol 130 mg Polyvinylpyrrolidone (molecular weight 10,000) 35 mg Styrene-maleic anhydride copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl / triphenylphosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 500 mg 2-Mercaptobenzimidazole-5-sulfonic acid sodium 5 mg Compound (H) 0.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg Compound (M) 5 mg Compound (N) 5 mg Compound (R) 2 mg Colloidal silica 0.5 g Latex (L) 0.2 g Dextran (average molecular weight 1000) 0.2 g Compound (P) 0.2 g Compound of the present invention or comparative compound described in Table 2 Compound (Q) 0.2 g However, the amount of gelatin is 0.8 g / m ² . Was adjusted.

Third layer (protective layer) Gelatin 0.6 g Matting agent (polymethyl methacrylate having an area average particle size of 7.0 μm) 50 mg Hardener (formaldehyde) 20 mg Hardener (H-1) 10 mg Hardener (bis (Vinylsulfonylmethyl ether) 36 mg Latex (L) 0.2 g Polyacrylamide (average molecular weight 10000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Surfactant ( B) 7 mg Compound (K) 15 mg Compound (O) 50 mg Surfactant (C) 5 mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH _{2 CH 2 O) 15 H 2mg} C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 O ₃ Na 1 mg compound of this invention or comparative compound in Table 2 described hardener (H-3) 2mg coated silver amount was adjusted to be 1.5 g / m ² as a one-sided min.

H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: 1,3,5-triacryloyl-hexahydro-s-triazine T: 2,6-bis (hydroxyamino) ) -4-Diethylamino-1,3,5-triazine J: 12-mol ethylene oxide adduct of p-nonylphenol B: sulfosuccinic acid (i-amyl decyl) sodium salt C: sulfosuccinate bis (2,2,3) , 3, 4, 4, 5,
5,6,6,7,7-dodecylfluoroheptyl) sodium salt

[0195]

Embedded image

[0196]

[Chemical 31]

[0197]

Embedded image

Table 2 shows the constitution of each of the obtained samples.

[0199]

[Table 2]

[0200]

[Chemical 33]

Each sample was sandwiched between fluorescent intensifying screens KO-250,
After irradiation with X-rays through Penetrometer-B type (manufactured by Konica Medical Co., Ltd.), processing was performed with the following developer formulation for a total processing time of 25 seconds.

Next, the developing process will be described.

First, a developing tablet was prepared according to the following procedure.

Procedure (A) 13,000 g of sodium erythorbate as a developing agent is ground in a commercial Bantam mill until the average particle size becomes 10 μm. To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone, and 1635 g of DTPA were added, mixed in a mill for 30 minutes, and mixed at room temperature in a commercial stirring granulator at room temperature.
After granulating for 30 minutes by adding 30 ml of water,
The granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated product.

2167 g of polyethylene glycol 6000 was uniformly mixed with the prepared granules for 10 minutes in a room where the humidity was controlled to 25 ° C. and 40% RH or less, and then the mixture was toughened by Kikusui Seisakusho. Presto collect 15
The tableting machine modified from 27HU was used for compression and tableting at a filling amount of 8.715 g per tablet to prepare 2500 tablets E for development replenishment.

DTPA: diethylenetriaminepentaacetic acid
5. Sodium operation (B) 19,500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, sodium hydrogen carbonate
25 g, 650 g of glutaraldehyde sulfite adduct, and 1354 g of polyethylene glycol 6000 are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 3
After granulating to 0.0 ml, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product. The resulting mixture was compressed and tableted using a tableting machine modified from Tough Press Collect 1527HU (described above) with a filling amount per tablet of 9.90 g, and 2,500 tablets F for development replenishment were prepared. Created.

Next, a fixing tablet was prepared by the following procedure.

Procedure (C) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide and 2.32 g of ethylenediaminetetraacetic acid disodium salt are pulverized and granulated in the same manner as in the procedure (A). The amount of water added is 500 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. The obtained mixture was subjected to a tableting machine modified from Tough Presto Collect 1527HU (described above),
Compression and tableting were performed at a filling amount of 8.214 g per tablet to prepare 2500 fixing supplement replenishing tablets G.

Operation (D) Boric acid 1860 g, aluminum sulfate.18 hydrate 6500
g, glacial acetic acid 1860 g, sulfuric acid (50 wt%) 928 g
Are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granules are dried for 30 minutes to almost completely remove the water content. The obtained mixture was filled with 4.459 g of tablet per tablet using a tableting machine modified from Tough Press Collect 1527HU (described above).
Then, compression and tableting were performed to prepare 2500 fixing replenishing tablets H.

Developer starter Glacial acetic acid 2.98 g Potassium bromide 4.00 g Water was added to make 1 liter.

At the start of processing of the developing solution (start of running), developing solution 16.5 prepared by diluting the developing tablet with diluting water
The processing was started by filling the developing tank with a liquid obtained by adding 330 ml of a starter per liter as a starting liquid.
The pH of the developer to which the starter was added was 10.45.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running was carried out. For running, Konica's automatic processor SRX-
A solid processing agent charging member is attached to 502, and the processing speed is 25
The one modified so that it can be processed in seconds was used.

During running, the photosensitive material 1.
1 ² per the A agent 00m, two and water B agent 20
ml. When each of A and B was dissolved in 20 ml of water, the pH was 10.70.

To the fixing solution, 4 parts of the above-mentioned C agent, ² parts of the D agent and 50 ml of water were added per 1.00 m ² of the light-sensitive material.
For each treatment agent, the rate of water addition starts at about the same time as the addition of the treatment agent and is approximately 10 in proportion to the dissolution rate of the treatment agent.
Minutes at a constant speed.

(Processing conditions) Current image 35 ° C. 8.2 sec Settling 33 ° C. 5.0 sec Water washing Normal temperature 4.5 sec Squeeze 1.6 sec Dry 40 ° C. 5.7 sec (total 25 sec) Treatment The liquid composition is as follows.

Developer composition (per liter of water) Potassium carbonate 120.0 g Sodium erythorbate 40.0 g DTPA 5.0 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium hydrogencarbonate 20.0 g 1-phenyl-3- Pyrazolidone 3.0 g Sodium sulfite 15.0 g Polyethylene glycol 15.0 g Glutaraldecit sulfite adduct 4.0 g Fixer composition (per liter of water) Ammonium thiosulfate 160.0 g Sodium sulfite 12.0 g Boric acid 10.0 g Sodium hydroxide 5. 0 g Glacial acetic acid 10.0 g Aluminum sulfate-18 hydrate 35.0 g Sulfuric acid (50 wt%) 5.0 g Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g Sensitivity, storability, intensifying screen contamination, and development of treated samples Silver They were evaluated for fog and the like in accordance with the following.

<< Sensitivity >> Sample 1-1 was shown as a relative value with the reciprocal of the X-ray exposure amount required to obtain the minimum density + 1.0 as 100.

As a surrogate evaluation of storability, the sample was placed at 23 ° C.
After leaving it under 48% RH for 4 hours, it was sealed in a moisture-proof bag and left at 55 ° C. for 4 days, and then the same exposure / development treatment was performed.

<< Staining of intensifying screen >> The sample and the intensifying screen were rubbed 500 times back and forth, and the surface was visually observed and evaluated.

<< Color tone of silver image >> Density of processed sample
The color tone of part 5 was visually observed and evaluated.

<Fog> As a substitute evaluation of the preservability of the treated sample, the sample was left at 23 ° C. and 48% RH for 4 hours, then sealed in a moisture-proof bag and left at 55 ° C. for 4 days, and then the visible density was measured. The difference between the measured values of Samples 1-3 was shown.

The results are shown in Table 3.

[0223]

[Table 3]

From Table 3, it can be seen that the samples of the present invention have a good silver image color tone even after the passage of time, and there is no transfer as intensifying screen contamination.
It can be seen that this is a light-sensitive material with less fog and less fluctuation in photographic performance.

Example 2 <Preparation of silver chloroiodide tabular grains> (Preparation of emulsion-6) A5 ossein gelatin 75.0 g potassium iodide 1.25 g sodium chloride 33.0 g distilled water to make 15000 ml B5 silver nitrate 410 g Distilled water to 684 ml C5 Silver nitrate 11590 g Distilled water to 19316 ml D5 Potassium iodide 4 g Sodium chloride 140 g Distilled water to 684 ml E5 Sodium chloride 3980 g Distilled water to 19274 ml At 40 ° C, JP-B-58-58288 , 58-
Solution in mixing stirrer as shown in No. 58289 (A5)
To the above, the total amount of the solutions (B5) and (D5) was added over 1 minute. After adjusting the EAg to 149 mV and aging Ostwald for 20 minutes, the total amount of the solutions (C5) and (E5) was 32.
Added over 0 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the completion of addition, desalting and washing with water were performed.
Emulsion 6 thus prepared had tabular grains in which 65% of the total projected area of silver halide grains were (100) planes as main planes, and had an average thickness of 0.14 μm and an average diameter of 1.0.
μm, the coefficient of variation was found to be 25% by electron microscope observation.

(Preparation of Emulsion-7) Emulsion-7 was prepared in the same manner as Emulsion-6 except that 8 × 10 ^-6 mol of potassium hexachloroiridium (IV) was added to the above solution (E5).

Subsequently, sensitization was performed by the following method.

Emulsion-6 and Emulsion-7 were kept at 55 ° C., and predetermined amounts of the spectral sensitizing dyes (SD-3, SD-4) were added as a solid fine particle dispersion. After that, a sulfur sensitizer, a selenium sensitizer, a gold sensitizer and the compound (R) were further added, and the mixture was aged for a total of 90 minutes.
-1) was added in an appropriate amount, and then the same additives as in the emulsion coating solution of Example 1 were added except for the compound of the present invention or the comparative compound to prepare an emulsion coating solution.

(Compound added in ripening step and amount thereof) Silver iodide fine grain emulsion 5 mmol equivalent SD-3 280 mg SD-4 40 mg Sulfur sensitizer 20 mg Gold sensitizer 1.0 mg Selenium sensitizer (triphenylphosphine Selenide) 4.0 mg Compound (R) 5.0 mg ST-1 50 mg

[0231]

Embedded image

Further, a transverse light-shielding layer coating solution was prepared in the same manner as in Example 1 except that the compound of the present invention or the comparative compound was changed.
A protective layer coating solution was also prepared. The obtained coating solution was coated on both sides in the same manner using the same support as in Example 1 and dried to prepare photosensitive material samples shown in Table 4. The samples obtained are shown in Table 4.

[0233]

[Table 4]

Each sample was sandwiched between the fluorescent intensifying screens used in Example 1, exposed and developed in the same manner as in Example 1, and evaluated in the same manner.

The results are shown in Table 5.

[0236]

[Table 5]

As is clear from the table, according to the present invention, even when a high silver chloride emulsion is used, the color tone of the silver image is good,
In addition, it is difficult to transfer the intensifying screen, and it is possible to obtain a light-sensitive material with less fluctuation in photographic performance and fogging.

[0238]

According to the present invention, a neutral black or cold black tone silver image can be obtained even when a high silver chloride emulsion suitable for rapid processing is used, and the transfer of the intensifying screen and the increase of fog over time are suppressed. A silver halide photographic light-sensitive material could be provided.

Claims (8)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
In the silver halide grains contained in the silver halide emulsion layer, 50% or more of the total projected area thereof are tabular silver halide grains, and the average silver iodide content of the tabular grains is 1.0.
A silver halide photographic light-sensitive material, characterized in that it has a mol% or less and an aspect ratio of 2 to 20, and the silver halide emulsion layer contains a compound represented by the following general formula (1). Embedded image [Wherein W represents -NR ₁ R ₂ , -OH or -OZ;
₁ and R ₂ each represent an alkyl group or an aryl group, and Z
Represents an alkali metal atom or a quaternary ammonium salt,
R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, n represents 1, 2 or 3, Z ₁ and Z ₂ each represent a nitrogen atom or = C (R ₃ )-, and X represents Represents a group of atoms necessary for forming a 5- or 6-membered aromatic carbocycle or an aromatic heterocycle with Z ₁ , Z ₂ and the carbon atom adjacent to them;
₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R represents an aliphatic group or an aromatic group, and p represents 1 or 2. Represent
CP represents the following group. Embedded image In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent capable of substituting on the benzene ring. R ₅ and R ₆ and R ₇ and R ₈ may be bonded to each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meanings as R ₁₀ and R ₁₁ , respectively. R ₁₅ has the same meaning as R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents 1, 2 or 3. Y represents an atomic group necessary to form a 5- or 6-membered monocyclic or condensed-ring nitrogen-containing heterocycle with two nitrogen atoms. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ have the same meaning as R ₁₉ and R ₂₀ , respectively. R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R
₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅ and R
₃₆ has the same meaning as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₃
Is synonymous with R ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₇ has the same meaning as R ₂₆ . R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₄₄ has the same meaning as R ₂₆ . * Represents a bonding point between CP and another partial structure in the general formula (1). ] 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide grains contained in the silver halide emulsion layer have tabular silver halide grains of which the total projected area is 50% or more, and the average silver iodide content of the tabular grains is 1.0.
A silver halide photographic light-sensitive material, characterized in that it has a mol% or less and an aspect ratio of 2 to 20, and the silver halide emulsion layer contains a compound represented by the following general formula (3). Embedded image [Wherein W represents -NR ₁ R ₂ , -OH or -OZ;
₁ and R ₂ each represent an alkyl group or an aryl group, and Z
Represents an alkali metal atom or a quaternary ammonium salt,
R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, n represents 1, 2 or 3, Z ₁ and Z ₂ each represent a nitrogen atom or = C (R ₃ )-, and X represents Represents a group of atoms necessary for forming a 5- or 6-membered aromatic carbocycle or an aromatic heterocycle with Z ₁ , Z ₂ and the carbon atom adjacent to them;
₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and CP represents the following groups. Embedded image In the formula, R _{5 to} R ₈ each represent a hydrogen atom, a halogen atom, or a substituent capable of substituting on the benzene ring. R ₅ and R ₆ and R ₇ and R ₈ may be bonded to each other to form a 5- to 7-membered ring. R ₉ has the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₂ has the same meaning as R ₄ . R ₁₃ and R ₁₄ have the same meanings as R ₁₀ and R ₁₁ , respectively. R ₁₅ has the same meaning as R ₁₂ . R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ . R ₁₈ has the same meaning as R ₃ , and m represents 1, 2 or 3. Y represents an atomic group necessary to form a 5- or 6-membered monocyclic or condensed-ring nitrogen-containing heterocycle with two nitrogen atoms. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ has the same meaning as R ₄ . R ₂₂ and R ₂₃ have the same meaning as R ₁₉ and R ₂₀ , respectively. R ₂₄ has the same meaning as R ₂₁ . R ₂₅ , R ₂₇ and R ₂₈ represent a hydrogen atom or a substituent. R ₂₆ has the same meaning as R ₄ . R
₂₉ , R ₃₁ and R ₃₂ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₀ has the same meaning as R ₂₆ . R ₃₄ , R ₃₅ and R
₃₆ has the same meaning as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₃
Is synonymous with R ₂₆ . R ₃₈ , R ₃₉ and R ₄₀ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₃₇ has the same meaning as R ₂₆ . R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as R ₂₅ , R ₂₇ and R ₂₈ , respectively. R ₄₄ has the same meaning as R ₂₆ . * Represents a bonding point between CP and another partial structure in the general formula (3). ] 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (2). Embedded image [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , CP, n, R and p are
R ₁ , R ₂ , R ₃ , R ₄ and C in the general formula (1) respectively.
It is synonymous with P, n, R, and p. ] 4. A silver halide photographic light-sensitive material containing at least one compound represented by the general formula (3) and at least one compound represented by RSO ₃ H. Here, R has the same meaning as R in the general formula (1). 5. The silver halide photographic light-sensitive material according to claim 4, wherein the compound represented by the general formula (3) is represented by the following general formula (4). [Chemical 6] _{Wherein, R 1, R 2, R} 3, R 4, CP and n, R ₁ in the general formula (1), _{respectively, R 2, R 3, R} 4, CP and n
Is synonymous with ] 6. In the compounds represented by the general formulas (1) to (4), R ₄ , R ₉ , R ₁₂ , R ₁₅ , R ₁₇ , R ₂₁ and R
_At least one of the groups represented by ₂₄ , R ₂₆ , R ₃₀ , R ₃₃ , R ₃₇ and R ₄₄ is —COOM ¹ and —SO ₃ M ² (M ¹ and M ² are each a hydrogen atom or an alkali metal atom; Is substituted with at least one selected from the group consisting of (1) to (6), and the silver halide photographic light-sensitive material according to claim 1. 7. A silver halide grain emulsion is prepared, wherein the silver halide grain contains 1.0 mol% or less of silver iodide in the presence of a silver halide solvent.
Or the silver halide photographic light-sensitive material of 2. 8. 50% of the total projected area of silver halide grains
The above are tabular grains whose parallel principal planes are (100) planes and have an aspect ratio of 1.3 or more and a silver chloride content of 20 or more.
% To 100 mol%, and at least one metal selected from Group VIII metals, Group II transition metals, lead, rhenium, molybdenum and chromium of the Periodic Table in at least one of the inside and the surface of the silver halide grains. A silver halide photographic light-sensitive material containing the compound and containing at least one compound represented by the general formula (1).