JPH103140A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce fluctuation and deterioration of photographic performance and to neutralize a silver image tone after development by incorporating a specified dye in a silver halide emulsion layer. SOLUTION: The silver halide emulsion layer contains flat silver halide grains having principal (111) faces and occupying >=50% of the projection areas of the total silver halide grains and each of these flat grains has an aspect ratio of 2-20 and an average silver iodide content of 0-1.0mol% and has its grain grown in the presence of a silver halide solvent, and the silver halide emulsion layer or a nonphotosensitive hydrophilic colloidal layer contains a dye represented by formula I and a polymer dye comprising monomer units each represented by the formula: (Dye)-Q and at least one kind of dye represented by formula III, and in formula I, Dye is a dye skeleton; and Ball is a ballasting group; and X is COOW<1> or SO3 W<2> , and in formula II, A is an atomic group necessary to form an azomethine dye, and R1 is a group replaceable with benzene ring.

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 silver halide photographic light-sensitive material having a good storage stability with time and obtaining a pure black color tone of a silver image.

[0002]

2. Description of the Related Art In recent years, with regard to development processing of silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials), it has been increasingly desired to shorten processing time and reduce processing waste liquid. For example, in the medical field, the number of X-ray photography is rapidly increasing due to the spread of periodic medical examinations, medical checkups and the like and the increase in diagnosis and examinations in general medical care. For this reason, at present, further speeding up of development processing and further reduction of processing waste liquid are increasing.

In order to speed up the processing of a photosensitive material, it is essential to shorten the processing time for development, 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 greatly reduced and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing becomes defective, which causes deterioration of the image quality. Therefore, it is basically necessary to increase the developing speed, the fixing speed, the drying speed, and the like of the photosensitive material.

Conventionally, to increase the developing speed and the fixing speed, it is necessary to reduce the content of silver iodide having low solubility, to use silver chlorobromide and silver chloride emulsions having high solubility, and to make silver halide grains fine. Flattening is believed to be advantageous.
However, it is known that a decrease in the silver iodide content and the use of silver chlorobromide and silver chloride cause a decrease in sensitivity.

Techniques for incorporating a silver halide solvent (thiocyanate compound) into silver halide grains and a light-sensitive material to enhance sensitivity and development progress are disclosed in US Pat. No. 320,069,
It is described in JP-A-62-18538. However, it is well known that storage stability with time is deteriorated with an increase in sensitivity, which is a major problem when using a silver halide solvent.

Further, as a method of sensitizing silver chloride particles, it is known that the sensitivity of a photosensitive material for printing can be increased by including a metal compound of Group VIII in the periodic table. The effect is for octahedral grains, and the effect for tabular grains is not known.

In order to reduce the amount of processing waste liquid, it is necessary to improve developability. Therefore, silver halide grains having a high covering power and a high density can be obtained with a small amount of silver. It is known that tabular grains are suitable in terms of properties, sharpness, color sensitization efficiency and the like.

However, when the grain size or grain thickness of the silver halide grains is reduced, the light scattering of the blue light component by the silver formed by the development process is increased and the light becomes strongly yellowish, so that the silver image becomes yellowish. Gives an unpleasant impression. Such a phenomenon occurs particularly when a fine grain emulsion (for example, an average grain size of 0.4 μm or less) or a tabular grain having a small grain thickness (for example, a grain thickness of 0.4 μm or less) is used as a silver halide emulsion. It is well known in the art that when the content of silver chloride is reduced or when the content of silver chloride is increased, the problem becomes significant and becomes a problem. To solve this problem, there has been proposed a technique disclosed in, for example, JP-A-5-165147 in which a specific dye is dissolved in a water-insoluble high-boiling organic solvent, dispersed in a fine size in an aqueous solvent, and contained in a photosensitive material. However, the sensitivity changed depending on the storage conditions before exposure. In particular, in the case of a medical X-ray photosensitive material, there has been a problem that the intensifying screen which is brought into contact with the photosensitive material at the time of exposure is stained.

[0009]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a pure silver image in which the photographic performance of the photosensitive material is less likely to fluctuate with time and the color tone of the silver image after development processing is neutral. An object of the present invention is to provide a photosensitive material capable of obtaining black color. Another object of the present invention is to provide a photosensitive material that does not contaminate the surface of the fluorescent intensifying screen in X-ray photography.

[0010]

The above object of the present invention is achieved by the following means.

In a silver halide photographic material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, 50% of the total projected area of the silver halide grains contained in the silver halide emulsion The above are the tabular silver halide grains having the (111) plane as the main plane, the aspect ratio is from 2 to 20, and the average silver iodide content of the tabular silver halide grains is from 0 to 1.0 mol. %, Wherein the tabular grains are grains formed in the presence of a silver halide solvent, and are represented by the following general formula (1) in the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising at least one of a dye, a dye comprising a polymer containing a monomer component represented by the general formula (2), and a dye represented by the general formula (3).

[0012]

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[In the formula, Dye has an absorption maximum of 520 nm or more.
Represents a dye skeleton is 750 nm, Ball represents an immobilization group, X represents a COOW ¹ or SO ₃ W ^2. W ¹ and W
² represents a hydrogen atom, an alkali metal, or an alkaline earth metal. n ₁ represents an integer of ₁ to 3, and m ₁ represents an integer of 1 to 6. General formula (2) (Dye) -Q wherein Dye represents a dye skeleton having an absorption maximum of 520 nm to 750 nm, and Q represents a group having an ethylenically unsaturated group. ]

[0014]

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[Wherein, A and N atoms together have an absorption maximum of 5
It represents an atomic group necessary for forming an azomethine dye having a thickness of 20 nm to 750 nm. R ₁ represents a group that can be substituted on a benzene ring, and n ₃ represents an integer of 0 to 4. When n ₃ is 2 or more,
A plurality of R _{1 s} may be the same or different, and may combine with each other to form a ring. R ₂ , R ₃ , R ₄ and R ₅ each independently represent an alkyl group, an aryl group or a polymer residue. ] In a silver halide photographic material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support,
At least 50% of the total projected area of the silver halide grains contained in the emulsion of the silver halide photographic light-sensitive material has parallel (100) planes and an aspect ratio of 2.0 or more.
0 or less tabular grains having a silver chloride content of 20 mol%
Not less than 100 mol%, and the silver halide grains contain at least one of Group VIII metals, Group II transition metals, lead, rhenium, molybdenum and chromium in the inside and / or on the surface of the silver halide grains. Tabular grains are formed in the presence of a silver halide solvent, and the dye represented by the formula (1) and the dye represented by the formula (2) are added to the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer. A silver halide photographic material comprising at least one of a dye comprising a polymer containing a monomer component and a dye represented by formula (3).

In a silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, total projection of silver halide grains contained in the emulsion of the silver halide photographic light-sensitive material 50% or more of the area is tabular silver halide grains having a (111) plane as a main plane, and the tabular silver halide grains have an average silver iodide content of 0%.
1.0 to 1.0 mol%, the aspect ratio is 2 to 20 and the tabular grains are grains formed in the presence of a silver halide solvent. Absorption maximum in the hydrophilic hydrophilic colloid layer is 520 nm
A silver halide photographic material comprising at least one metal chelate dye having a wavelength of from 750 to 750 nm.

The silver halide photographic light-sensitive material as described in any one of the above items, wherein the total content of the dye is from 1 × 10 ^-7 mol to 1 × 10 ^-1 mol per mol of silver.

Hereinafter, the present invention will be described in detail.

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 silver halide. Silver iodobromide, silver iodochloride and silver chloroiodobromide are preferred. When silver iodobromide or silver chloroiodobromide is used, the silver iodide content is from 0 to 1.0 mol% as an average silver iodide content of the whole silver halide grains, but from 0 to 0 mol%. 0.5 mol% is preferred.

In the present invention, silver iodide can be formed by simultaneously adding a silver nitrate solution and a solution containing iodide ion to an emulsion containing tabular grains as a base, silver iodide, silver iodobromide, and the like. Alternatively, a method of adding silver halide fine particles such as 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. Particularly preferred is the addition of silver iodide fine grains.

When the tabular silver halide grains of the present invention contain silver iodide, the silver iodide may be located anywhere in the grains, but is preferably located on the outermost surface of the grains. Here, the outermost surface means a period from the end of the grain growth portion to the end of chemical ripening.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (E
Electron Probe Micro Analysis
zer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared, an electron beam is irradiated, and X-ray analysis is performed by electron beam excitation. Elemental analysis of an extremely small portion can be performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. 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 iodine content between grains.
When the distribution of iodine 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, an average value of grain diameter / grain thickness (hereinafter referred to as aspect ratio) of at least 50% of the total projected area of the photographic material of the present invention is 2 or more. 20 or less. It is preferably 2 or more and 12 or less, and more preferably 3 or more and 8 or less. Here, the grain size means an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). (Diameter), and thickness refers to the distance between two parallel major planes forming tabular silver halide grains.

The tabular silver halide grains of the present invention are preferably monodisperse. Specifically, (standard deviation of particle size / average particle size) × 100 = 25% or less when the width of the distribution is defined by the relative standard deviation (coefficient of variation) expressed by the width (%) of the particle size distribution Is preferably 20% or less, more preferably 15% or less.

The silver halide grains of the present invention preferably have a small thickness distribution. Specifically, when the width of 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 1
5% or less.

In the present invention, when tabular silver halide grains having twin planes are used, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter sometimes abbreviated as hexagonal tabular grains) are those whose main plane (111) plane is hexagonal and whose maximum adjacency ratio is 1.0 to 2.0. Say something. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grains preferably have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. If the corner is rounded, the length of the side is
It is represented by the distance between the intersection of the straight line portion of the side and the line obtained by extending the straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.0
More preferably, it is 1.5.

As the silver halide solvent used in the present invention, US Pat. Nos. 3,271,157 and 3,53
Nos. 1,289 and 3,574,628;
(A) Organic thioethers described in JP-A Nos. 10-1919 and 54-158917, and JP-A-53-82408.
(B) thiourea derivatives described in JP-A Nos. 55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group interposed between an oxygen or sulfur atom and a nitrogen atom described in JP-A-19, (d) imidazoles described in JP-A-54-100717, e) Sulfite, (f) thiocyanate and the like, and silver halide solvents described in JP-A-57-196228 and the like can be mentioned.

The following are specific examples of these compounds.

[0031]

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Particularly preferred solvents include thiocyanate and tetramethylthiourea. As the thiocyanate, a water-soluble salt such as a metal salt of thiocyanate or NH ₄ SCN can be generally used. In the case of a metal salt, care must be taken to use a metal element which does not adversely affect photographic performance. Are preferred. Further, a sparingly soluble salt such as AgSCN may be added in the form of fine particles. The silver halide solvent may be added at any position during the preparation of the emulsion, but is preferably added both before the desalting step and during 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 time of grain formation to the end of chemical sensitization is 2.5 × 10 ^-3 mol or more per mol of silver halide.
Less than × 10 ^-2 mol is preferred.

In the tabular silver halide grains of the present invention, when silver iodide is formed in the presence of a silver halide solvent, the silver iodide content is 0 to 1.0 mol%. It is preferably 5 mol%, more preferably 0 to 0.4 mol%. It is also preferred that 0 to 0.4 mol% is formed in the presence of a silver halide solvent before the desalting step, and further 0 to 0.6 mol% is formed during chemical ripening.

In the present invention, silver chloride containing (10
In the case of using tabular silver halide grains having the 0) plane as the main plane, the shape of the main plane of the tabular silver halide grains is a shape of a rectangular parallelogram or a rectangular parallelogram with rounded corners. The adjacent side ratio of the right-angled parallelogram is less than 10,
Preferably it is less than 5, more preferably less than 2. In addition, the length of a side when the corner is rounded is represented by a distance between an intersection of a line extending the straight part of the side and the straight part of the adjacent side. The silver chloride content is 20 mol% or more, but preferably 30 mol% or more and 70 mol% or less. The content of silver iodide is preferably at most 1.0 mol%, more preferably at most 0.5 mol%.

The silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilton,
Photo. Sci. Eng., 57 (1967);
Shiozawa, J .; Soc. Photo. Sci. J
Apan, 35, 213 (1972), which can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to pass through. Therefore, a high-pressure type (200 KV or more for a 0.25 μm-thick particle)
Can be observed more clearly using an electron microscope.

The silver halide grains of the present invention may form silver nuclei during grain formation. Silver nucleation is carried out by adding a reducing agent to the silver halide emulsion or the mixed solution for grain growth, or the silver halide emulsion or the mixed solution for grain growth is prepared under a low pAg of pAg7 or less. Or by ripening or growing particles under high pH conditions of pH 7 or higher. A method performed by 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 o
f Photographic Science No. 25
Vol. 19-27 (1977) and Photogra.
phic scienceand engineeri
ng, Vol. 32, pp. 113-117 (1979), the silver nuclei formed by reduction sensitization are Ph
autographfish Korrespndenz
Volume 1, 20 (1957) and Photograph
ic Science and Engineerine
g In the 19th volume, 49-55 (1975)
As described by icell and Lowe, it has been considered that the compound contributes to sensitization through a reaction represented by the following formula at the time of exposure.

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

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and its derivatives,
And tin salts. 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.

In order to perform low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferable and silver nitrate is preferable as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3 (where pAg = -log [Ag ⁺ ]).

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 to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

As a method of adding a silver salt and an alkaline compound for forming silver nuclei, rush addition or addition over a certain period of time may be used. 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.

The required amount may be added in several portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Furthermore,
The addition may be performed separately from the soluble silver salt and the soluble halide.

An oxidizing agent can be used in the silver halide emulsion of the present invention. The following oxidizing agents can be used.

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 _{[Ti (O 2) C 2 O} 4 ]-3H ₂ O and the like.

In addition, peracetic acid, ozone, iodine, bromine,
And thiosulfonic acid compounds.

The amount of the oxidizing agent used in the present invention is influenced by the type of the reducing agent, the conditions for forming silver nuclei, the timing of adding the oxidizing agent, and the adding conditions. ^-2 to ^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. Further, after the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives.
The amount of the reducing substance is preferably an amount per mole ^10-3 to ³ moles of the oxidizing agent to be used is.

The heavy metal ions usable in the present invention include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and other Group VIII metals of the periodic table, and cadmium, zinc and mercury. Examples thereof include transition metals of Group II of the periodic table, and ions of lead, rhenium, molybdenum, tungsten, chromium, and the like. 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 a salt or a complex salt. Among them, those added to the emulsion in the form of a complex salt are preferable because they can be easily incorporated into the silver halide emulsion and the effect of the present invention is increased.

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 are not limited thereto.

(1) FeCl ₂ , (2) FeCl ₃ , (3) (NH ₄ ) Fe (SO ₄ ) ₂ , (4) K ₃ [Fe (CN) ₆ ], (5) K ₄ [Fe ( CN) _6], (6) K ₂ [IrCl _6], (7) K ₃ [IrCl _6], (8) K ₂ [PtCl _6], (9) K ₂ [Pt (SCN) _4], (10 ) K ₂ [PdCl ₆ ], (11) K ₃ [PdCl ₆ ], (12) CdCl ₂ , (13) ZnCl ₂ , (14) K ₂ [Mo (CO) ₄ (CNO) ₂ ], (15) K ₃ [Re (CNO) ₆ ], (16) K ₃ [Mo (CNO) ₆ ], (17) K ₄ [Fe (CNO) ₆ ], (18) K ₂ [W (CO) ₄ (CNO) ₂ ], (19) K ₂ [Cr (CO) ₄ (CNO) ₂ ], (20) K ₄ [Ru (CNO) ₆ ], (21) K ₂ [Ni (CN) ₄ ], (22) ) PbCl ₂ , (23) K ₃ [Co (NH ₃ ) ₆ ], (24) K ₅ [Co ₂ (CNO) ₁₁ ], (25) K ₃ [Re (CNO) ₆ ], (26) K ₄ [Os (CNO) ₆ ], (27) K ₂ [Cd (CNO) ₄ ], (28) K ₂ [Pt (CNO) ₄ ], (29) K ₃ [IrBr ₆ ], Heavy metal in silver halide emulsion In order to contain ions, the heavy metal compound may be added at any place in each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. For this purpose, for example, a heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, they may be dissolved together with the silver halide and added continuously during the grain formation step.

The amount of heavy metal ions added to the silver halide emulsion is from 1 × 10 ^{-9 to} 1-1 per mole 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 from 0.2 to 3.0 μm, more preferably from 0.4 to 2.0 μm. The average thickness of the tabular silver halide grains of the present invention is preferably from 0.02 to 1.0 μm, more preferably from 0.05 to 0.40.
μm, and more preferably 0.05 to 0.30 μm.
Particle size and thickness can be optimized to optimize sensitivity, pressure characteristics, etc.

In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of silver halide grains. As gelatin, alkali-treated gelatin, acid-treated gelatin, low-molecular-weight gelatin (molecular weight of 20,000 to 10
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Resea
rch Disclosure, hereinafter abbreviated as RD. ) Vol. 17643 (December 1978), section IX.

The silver halide emulsion of the present invention may remove unnecessary soluble salts during the growth of silver halide grains,
Alternatively, it may be kept contained. When removing the salts, see RD Vol. It can be carried out based on the method described in 17643, Section II.

The tabular silver halide grains of the present invention can be subjected to chemical sensitization. Chemical ripening, that is, the conditions of the step of chemical sensitization, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be carried out under conditions generally used in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, a reducing substance The reduction sensitization method used, gold or the like, a noble metal sensitization method using a noble metal or the like can be used alone or in combination, and among them, selenium sensitization method, tellurium sensitization method, reduction sensitization method, etc. are preferably used. In particular, a selenium sensitization method is preferably used.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. For example, US Pat. Nos. 1,574,944 and 1,60.
No. 2,592, No. 1,623,499;
150046, JP-A-4-25832, 4-10
No. 9240 and No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N '
-Trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids And selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide) , Diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles. Depending on the nature of the selenium compound to be used, the addition method may be a method of adding the compound by dissolving it in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or by adding a mixture with a gelatin solution in advance. The method may also be a method disclosed in JP-A-4-140739, that is, a method of adding the compound in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The temperature of chemical ripening using a selenium sensitizer is as follows:
A range from 40 to 90C is preferred. More preferably, 45
It is not less than 80 ° C and not less than 80 ° C. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

The tellurium sensitizers and sensitization methods are disclosed in JP-A-4-204640 and JP-A-4-330430. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N ').
Dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (e.g., tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, Dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

It is also preferable to perform so-called reduction sensitization on the surface of the grains by placing the grains in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system,
It is preferable to change the pH depending on environmental conditions such as pH and pAg. For example, in the case of thiourea dioxide, as a rough guide, about 0.01 to 2 per mole of silver halide is used.
Use of mg gives favorable results. In the case of ascorbic acid, about 50 mg to 2 mg / mol of silver halide is used.
The range of g is preferred. The conditions for reduction sensitization are as follows: temperature is about 40 to 70 ° C., time is about 10 to 200 minutes, and pH is about 5
-11 and pAg are preferably in the range of about 1-10 (where the pAg value is the reciprocal of Ag + ion concentration).

As the water-soluble silver salt, silver nitrate is preferable.
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 from 1 to 6, and preferably from 2 to 4. Conditions such as temperature, pH, and time are preferably in the above-described reduction sensitization condition range. As a stabilizer for a silver halide emulsion containing silver halide grains subjected to reduction sensitization, the following general stabilizers can be used, but the stabilizers disclosed in JP-A-57-82831 can be used. Inhibitors and / or V.I. S. Ga
hler's paper [Zeithshift fur w
issenschaftliche Photogra
phi Bd. 63, 133 (1969)] and the use of thiosulfonic acids described in JP-A-54-1019 can often give good results. still,
These compounds may be added in any step of the emulsion production process from crystal growth to the preparation process immediately before coating.

The dye skeleton in the present invention specifically refers to a dye skeleton of anthraquinone, azo, azomethine, triarylmethane, methine, phenazine, oxazine, arylidene or the like.

In formula (1), the dye skeleton is preferably anthraquinone, azo, azomethine, or triarylmethane. The immobilizing group represented by Ball is a stable group having a molecular size and shape that makes the dye represented by the general formula (1) resistant to diffusion, and the dye represented by the general formula (1) Is not limited except that the non-diffusion-resistant is, but preferably an immobilization group represented by Ball,
An alkoxy group having an alkyl group and / or an aryl group having 8 to 32 carbon atoms, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an arylazo group, an acyloxy group, an alkylsulfonyl group An arylsulfonyl group, an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, an alkylsulfonyloxy group, an arylsulfonyloxy group, or a nitrogen-containing heterocycle (for example, pyrrole, pyrazole, imidazole, triazole, tetrazole, indole, indazole, Benzimidazole, benztriazole, phthalimide, succinimide, 2,4-imidazolidinedione, 2,4-oxazolidinedione, 2,4-thiazolidinedione, triazolidine-3,5-di It can be exemplified each group of radicals derived from emissions, etc.).

The dyes represented by formula (1) will be specifically described below, but the invention is not limited thereto.

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In formula (2), the dye skeleton is preferably anthraquinone, azo or azomethine. Q
The group having an ethylenically unsaturated bond represented by is preferably represented by the general formula (3). In the formula (3), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group (preferably a lower alkyl group having 1 to 4 carbon atoms), and the alkyl group may have a substituent. A represents a divalent group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) or a phenylene group, and the alkylene group may be linear or branched, and specifically, methylene, methylmethylene,
It represents each group such as dimethylene and decamethylene. Further, the alkylene group and the phenylene group may have a substituent. n ₃ represents the 0-4. Examples of the substituent which R ₁ and A may have include a halogen atom (a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t -Butyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.),
Aralkyl groups (eg, benzyl group, 2-phenethyl group, etc.), aryl groups (eg, phenyl group, naphthyl group,
p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino group (eg, Acetylamino group, propionylamino group, etc., alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group) Ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.),
Carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ,
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (for example, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group,
Nitroso group, amine oxide group (for example, pyridine-oxide group), imide group (for example, phthalimido group), disulfide group (for example, benzene disulfide group, benzothiazolyl-2-disulfide group, etc.), heterocyclic group (for example, pyridyl group, benz) Imidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.). R ₁
And A may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent.

Specific examples of the dye monomer represented by the general formula (2) will be given below, but it should not be construed that the invention is limited thereto.

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The polymer dye derived from the monomer represented by the general formula (2) of the present invention may be a so-called homopolymer of a repeating unit composed of only one kind of the monomer represented by the general formula (2). The copolymer may be a copolymer obtained by combining two or more monomers represented by the general formula (2), and may be a copolymer comprising at least one other copolymerizable comonomer having an ethylenically unsaturated group. Is also good. Preferably, it is a copolymer comprising at least one other copolymerizable comonomer having an ethylenically unsaturated group.

Examples of the comonomer having an ethylenically unsaturated group capable of forming a copolymer with the monomer represented by the general formula (2) of the present invention include acrylates, methacrylates, vinyl esters, olefins, and styrene. , Crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, many Functional monomers and various unsaturated acids can be exemplified. Further examples of other comonomers include U.S. Pat. No. 3,459,790,
No. 3,438,708 and No. 3,554,987
No. 4,215,195 and No. 4,247,67
No. 3,247,673, JP-A-57-205
No. 735, etc. can be used.

When a copolymer is formed from the monomer represented by the general formula (2) of the present invention and the comonomer, preferably, the repeating unit composed of the monomer represented by the general formula (2) is contained in a weight ratio of the whole. 10-90 of the polymer
% By weight, more preferably 30 to
70% by weight. Generally, a polymer is produced by an emulsion polymerization method or a solution polymerization method, and a polymer dye containing at least one of the dye monomers represented by the general formula (2) according to the present invention as a comonomer is also produced by the same method. Can be.

The emulsion polymerization method is described in US Pat.
0,211 and 3,370,952, and the method described in US Pat. No. 3,451,820 for producing a lipophilic polymer by latex polymerization in an aqueous gelatin solution. it can. Further, a polymerization method other than the above polymerization methods, for example, a suspension polymerization method and a bulk polymerization method can also be applied. General formula (2) of the present invention
The weight average molecular weight of the polymer dye containing at least one dye monomer represented by
00000000, more preferably 5000
0 to 2,000,000. In the present invention, the weight average molecular weight is measured by a GPC method (gel permeation chromatography method).

To disperse a polymer dye containing at least one of the dye monomers represented by the general formula (2) of the present invention as a comonomer in the form of a latex in an aqueous gelatin solution,
First, after dissolving the lipophilic polymer in an organic solvent, this is dispersed in an aqueous gelatin solution in the form of a latex using an ultrasonic wave, a colloid mill or the like with the aid of a dispersant. A method of dispersing a lipophilic polymer in latex form in an aqueous gelatin solution is described in U.S. Pat. No. 3,451,820. As the organic solvent for dissolving the lipophilic polymer, esters such as ethyl acetate and propyl acetate, alcohols, ketones, halogenated hydrocarbons, ethers and the like can be used.

Specific examples of the polymer dye containing at least one of the dye monomers represented by the formula (2) as a comonomer are listed below, but the invention is not limited thereto.

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In the compound represented by formula (3) of the present invention, the atomic group represented by A includes a benzene ring, a naphthalene ring, a heterocyclic ring, an active methylene group, and an arylamino group forming an azo bond. And derivatives such as a heterocyclic amino group. The benzene ring and naphthalene ring may have a substituent, and as the substituent,
Acyl group, urethane group, ureido group, carbamoyl group,
Examples include a hydroxyl group, a halogen atom, and an alkyl group. Examples of the heterocycle include a 5-membered or 6-membered monocyclic or fused ring. As a single ring, pyridine, imidazole, pyrazolone and the like are preferably used, and as a condensed ring, pyrazolotriazole, pyrazolobenzimidazole,
Quinoline and isoquinoline rings are preferably used. Examples of the compound having an active methylene group include compounds having an electron-withdrawing group such as a carbonyl group, an ester group, and a cyano group at both ends of methylene, and specifically, β-ketoamide, β-ketoester, and β-ketoester. Diketone, malononitrile, and the like. The arylamino group forming the azo bond includes an anilino group and a naphthylamino group. Examples of the heterocyclic amino group forming the azo bond include a pyridylamino group, a quinolylamino group, and a benzothiazolylamino group.

The group which can be substituted on the benzene ring represented by R ₁ is preferably a halogen atom or an alkyl group. The alkyl group represented by R _{2 to} R ₅ may be linear, branched or cyclo ring, and preferably has a total carbon number of 15 or more. Preferred examples of the aryl group represented by R _{2 to} R ₅ include phenyl, naphthyl, and pyridyl groups.

The polymer residue represented by R _{2 to} R ₅ is preferably a polymer residue derived from a group having a comonomer component represented by the following general formula (4).

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In the general formula (4), R ₆ represents a hydrogen atom, a halogen atom or an alkyl group (preferably a lower alkyl group having 1 to 4 carbon atoms), and this alkyl group has a substituent. Is also good. L is -CONH-, -NHCONH-
Or a divalent group -NH-, B ₂ represents -CONH- or -COO- divalent group. D represents a divalent group such as an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) or a phenylene group, and the alkylene group may be linear or branched, and specifically, methylene, methylmethylene,
It represents each group such as dimethylene and decamethylene. Further, the alkylene group and the phenylene group may have a substituent. p and q each represent 0 or 1.

The polymer residue represented by R _{2 to} R ₅ may be a so-called homopolymer of a repeating unit consisting of only a group having a comonomer component represented by the aforementioned general formula (4), It may be a copolymer comprising at least one comonomer having an ethylenically unsaturated group to be obtained. Preferably, it is a copolymer comprising at least one other copolymerizable comonomer having an ethylenically unsaturated group.

Examples of the comonomer having an ethylenically unsaturated group capable of forming a copolymer with the comonomer represented by the general formula (4) of the present invention include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins,
Styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, Examples thereof include polyfunctional monomers and various unsaturated acids. Further examples of other comonomers include U.S. Pat. No. 3,459,790,
No. 3,438,708 and No. 3,554,987
No. 4,215,195 and No. 4,247,67
No. 3,247,673, JP-A-57-205
No. 735, etc. can be used. In the case where a copolymer is formed from the monomer represented by the general formula (4) and the comonomer of the present invention, the repeating unit composed of the monomer represented by the general formula (4) preferably has a weight ratio of 10% to the total polymer. ~ 90
% By weight, more preferably 30 to
70% by weight.

In the present invention, R _{2 to} R ₅ of the general formula (3)
Preferably, at least one of them is a polymer residue. In this case, the weight average molecular weight of the dye represented by formula (3) of the present invention is preferably 10,000 to 100,000,000, and more preferably 50,000 to 2,000,000. In the present invention, the weight average molecular weight is measured by a GPC method (gel permeation chromatography method).

The dyes represented by formula (3) will be specifically described below, but the invention is not limited thereto.

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The dye in the metal chelate dye of the present invention specifically refers to dyes such as anthraquinone, azo, azomethine, triarylmethane, methine, phenazine, oxazine, arylidene, and formazan. Preferably, they are azo, azomethine, methine, and formazan.
The central metal of the chelate dye is not particularly limited as long as it is a chelatable metal, but is preferably nickel,
Copper, zinc, chromium, cobalt, iron and the like can be mentioned. Particularly preferred are nickel, copper and cobalt.

The metal chelate dyes of the present invention will be specifically described below, but it should not be construed that the invention is limited thereto.

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The amount of the dye to be added in the present invention is preferably 1 × 10 ⁻⁷ mol or more and less than 1 × 10 ⁻¹ mol per 1 mol of silver in a medical light-sensitive material. Below, the effect of improving the silver tone is small, and above this, the whole image is dark, which is not preferable. In particular, when the content is 1 × 10 ⁻⁶ mol or more and less than 1 × 10 ⁻² mol, the effect of the present patent is remarkable and preferable.

In the present invention, any method can be used for adding the above-mentioned dyes depending on the properties of each compound. For example, a method of adding as a solid fine particle dispersion, a method of dissolving in a high boiling point solvent and then adding after dispersing, a method of dissolving in a water-miscible organic solvent (for example, methanol, ethanol, acetone, etc.) and adding the same may be mentioned. . As a preferable method, a method of adding as a solid fine particle dispersion or a method of dissolving in a water-miscible organic solvent (for example, methanol, ethanol, acetone or the like) and adding the same is used. When added as a solid fine particle dispersion, the dispersion method is an acid precipitation method,
A known method such as a ball mill, a jet mill or an impeller dispersion method can be applied, and the average particle diameter of these solid-dispersed dye fine particles can take any value, but is preferably 0.01 to 20 μm, more preferably Is 0.03 ~
2 μm.

In the present invention, the amount of the hydrophilic binder in the silver halide emulsion layer is preferably not more than 3.0 g / m ^2, more preferably 2.0 g / m ² per one side of the support when the emulsion layer is on both sides of the support. m ² or less. When it is on one side of the support, it is preferably at most 6.0 g / m ^2, more preferably at most 4.0 g / m ² .

The light-sensitive material of the present invention includes black-and-white light-sensitive materials (for example, medical light-sensitive materials, printing light-sensitive materials, negative films for general photography), color light-sensitive materials (for example, color negative light-sensitive materials, color reversal light-sensitive materials). Photosensitive materials for color printing, etc.), photosensitive materials for diffusion transfer, and heat-developable photosensitive materials, but are preferably black-and-white photosensitive materials, and particularly preferably medical photosensitive materials.

The silver halide emulsion of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in an emulsion layer or a layer having another layer.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contain an inorganic or organic hardener. For example, chromium salts (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)
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine) such as methyl ether, N, N'-methylenebis (β- (vinylsulfonyl) propionamide), and mucohalic acids (mucochloric acid, mucophenoxy) Chloric acid, etc.), isoxazoles, 2-
Chlor-6-hydroxytriazinylated gelatin or the like can be used alone or in combination. Among them, JP-A-53-41221 and JP-A-53-57257.
Nos. 59-162456, 60-80846 and US Pat. No. 3,325,2.
No. 87 is preferred.

As the hardener used in the present invention, a polymer hardener can also be effectively used. For example, dialdehyde starch, polyacrolein, US Patent 3,396,029
Polymers having an aldehyde group, such as the acrolein copolymer described in US Pat. No. 3,623,878, polymers having an epoxy group described in US Pat.
No. 827, Research Disclosure Magazine 17333
(1978), a polymer having an active ester group described in JP-A-56-66841, and a polymer having an active ester group described in JP-A-56-66841.
No. 6,142,524, U.S. Pat. No. 4,161,407
And polymers having an active vinyl group or a group which is a precursor thereof described in JP-A-54-65033, Research Disclosure Magazine 16725 (1978), etc. Particularly preferred are polymers in which the active vinyl group, or a precursor group thereof, is attached to the polymer backbone by a long spacer as described.

In the light-sensitive material of the present invention, an appropriate amount of a hardening agent is added in advance in the coating step of the light-sensitive material so as to be suitable for rapid processing, and the water swelling ratio in the development-fixing-washing step is adjusted. By doing so, it is preferable to reduce the water content in the light-sensitive material before the start of drying.

The swelling ratio of the light-sensitive material of the present invention is preferably 150 to 250% during the development processing, and the film thickness after expansion is 7%.
It is preferably 0 μm or less. When the water swelling ratio exceeds 250%, poor drying occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing. Further, the water swelling ratio is 150
%, Development unevenness and residual color tend to be deteriorated when developed. 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 the difference by the film thickness before processing and multiplying by 100. .

Examples of the support that can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer.

In the light-sensitive material of the present invention, various additives can be further added to the silver halide emulsion depending on the purpose. Examples of additives and others used include, for example, Research Disclosure (RD) No. 17643 (1
No. 978), pp. 23-29. 18716
(November 1979) pp. 638 to 651 and the same No. 3
08119 (December 1989), pp. 996-1009. Next, preferred development processing of the photosensitive material of the present invention will be described.

The processing of the light-sensitive material of the present invention is carried out, for example, in the manner described in RD-17643, pages XX to XXI, pp. 29 to 30 or 3 above.
Treatment with a processing solution as described in 08119, XX to XXI, pp. 1011 to 1012 may be performed.

In the present invention, a development treatment using a solid processing agent is preferably used. An automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank may be provided, for example, when the solid processing agent is a tablet, when the solid processing agent is a tablet.
No. 37783, No. 63-97522, No. 1-85
No. 732, etc., but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is granules or powder, the gravity drop method described in Japanese Utility Model Application Laid-Open Nos. 62-81964 and 63-84151, and JP-A-1-292375, and Japanese Utility Model Application Laid-Open Nos. Although there is a known method using a screw or a screw described in -195345 or the like, the method is not limited thereto.

The place where the solid processing agent used in the present invention is charged may be in a processing tank, but is preferably in communication with a processing section for processing a photosensitive material, and a processing liquid is supplied between the processing section and the processing section. It is preferable to have a structure in which the components are circulated, and furthermore, a certain amount of the processing solution circulates between the processing unit and the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In the developer used in the developing method used in the present invention, JP-A-6-1385 is used as a developing agent.
In addition to dihydroxybenzenes, aminophenols and pyrazolidones described in JP-A-91, reductones described in JP-A-5-165161 are also used. Of the pyrazolidones used, those in which the 4-position is particularly substituted (dimesone, dimesone S, etc.) are particularly preferred because they are less soluble in water and have less change with time of the solid treating agent itself.

As a preservative, an organic reducing agent can be used as a preservative in addition to the sulfite described in JP-A-6-138591. In addition, a chelating agent described in JP-A-6-138591 or a bisulfite adduct of a hardening agent described in the same publication can be used.

Further, a silver sludge inhibitor is disclosed in JP-A-5-252.
89255, JP-A-6-308680 (general formula [4
-A] [4-b]) is also preferred. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

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

It is necessary to use a buffer for the developer. Examples of the buffer include sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, o-hydroxybenzoic acid Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. Can be mentioned.

Examples of the development accelerator include JP-B-37-160.
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; No. 50-15554
Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429. US Patent 2,61
P-aminophenols described in U.S. Pat. Nos. 0,122 and 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253. No. 919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like. 42-25201
No. 3,128,183, JP-B-41-11
Nos. 431 and 42-23883 and U.S. Pat.
2,501 or the like, a polyalkylene oxide,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

As 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, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, the developer composition used in the present invention may contain, if necessary, methylcellosolve, methanol,
Acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378, 44-9
No. 509 can be used as an organic solvent for increasing the solubility of a developing agent.

Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

The fixing agent used in the present invention may contain a compound known as a fixing agent. Fixing agent, chelating agent, p
An H buffer, a hardener, a preservative, and the like can be added. These are described in, for example, JP-A-4-242246 (p. 4) and JP-A-5-15-1.
No. 13632 (pages 2 to 4) can be used. In addition, as a hardening agent, a chelating agent described in JP-A-6-138593, a bisulfite adduct of a hardening agent described in JP-A-6-13891, and a known fixing accelerator can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The light-sensitive material of the present invention has a total processing time of 1 hour.
Processing is preferably performed in 0 to 45 seconds. More preferably, it is 15 seconds to 30 seconds. The term "total processing time" as used in the present invention means that the steps from development to drying are completed within 45 seconds by an automatic developing machine. That is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through a processing step (so-called Dry t)
o Dry) is within 45 seconds.

The drying time may be generally 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with a heating means using far infrared rays may be provided in the automatic developing machine. An automatic developing machine equipped 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 developing, fixing and washing steps (Japanese Patent Laid-Open No. 3-264953). May be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

The light-sensitive material of the present invention can be processed by a conventional processing method without using a solid processing agent.

In the present invention, the replenishing amount of the developing solution and the fixing solution is 200 ml / m ^{2 of the} silver halide photographic light-sensitive material.
It can be processed as follows.

In addition, in carrying out the present invention, various techniques used in photographic techniques can be applied.

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

Example 1 <Preparation of Hexagonal Tabular Grains of Silver Iodobromide> (Preparation of Emulsion-1) A1 Ossein Gelatin 75.5 g Sodium salt of polypropyleneoxy-polyethyleneoxy-disuccinate (10% aqueous ethanol) 6.78 ml Odor 64.7 g Potassium bromide Make up to 10800 ml with water B1 0.7 N silver nitrate aqueous solution 1340 ml C1 2.0 N silver nitrate aqueous solution 1500 ml D1 1.3 N potassium bromide aqueous solution 410 ml E1 2.0 N potassium bromide aqueous solution F1 ossein gelatin 125g Water 4000ml G1 KSCN aqueous solution (2N) 60ml H1 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average particle size 0.05μ) (*) 0.008 mol equivalent * 0.06 mol iodide 5.0% by weight zera containing potassium To 6.64 l of the aqueous tin solution, 2 l of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

At 55 ° C., JP-B-58-58288, 5
Solution A using a mixing stirrer described in JP-A-8-58289.
400 ml of the solution B1 and the entire amount of the solution D1 were added to 1 by a simultaneous mixing method over 40 seconds to form nuclei.

After the addition of the solution B1 and the solution D1, the solution F1 is added, and the temperature is raised to 70 ° C. for aging. After the remaining amount of the solution B1 was further added over 25 minutes, the mixture was aged for 10 minutes using a 28% aqueous ammonia solution, and the pH was adjusted with acetic acid.
To neutral. Simultaneous addition and mixing of solutions C1 and E1 at a rate commensurate with the critical growth rate while maintaining pAg = 7.8,
After the total amount of C1 was added, G1 and H1 were added. After stirring for 5 minutes, soluble salts were desalted and removed by sedimentation. In this emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0,
It was confirmed by an electron microscope that the average thickness of the hexagonal tabular grains was 0.20 μm and the average particle diameter (in terms of circular diameter) was 0.80 μm. The distribution of the circle equivalent diameter was 15%.

(Preparation of Emulsion-2) G1 was added in an amount of 6 ml.
Emulsion-2 was prepared in the same manner as Emulsion-1 except that the weight was reduced.

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

(Preparation of Emulsion-4) Emulsion was performed in exactly the same manner as Emulsion-1, except that the amount of the silver iodide fine particles of H1 was equivalent to 0.16 mol and the silver iodide content was 2.0 mol%. -4 was prepared.

Table 1 shows the obtained emulsion. Emulsion-1
The aspect ratio of ４4 was 4.1.

[0150]

[Table 1]

Subsequently, this emulsion was heated to 47 ° C.
After adding predetermined amounts of the spectral sensitizing dyes A and B as a dispersion in the form of solid fine particles, a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide are added, and a total of 2 hours Aged for 30 minutes. At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The spectral sensitizing dyes and other additives, and their amounts (per mole of AgX) are shown below.

Spectral sensitizing dye (A) 390 mg Spectral sensitizing dye (B) 4 mg Adenine 10 mg Sodium thiosulfate 3.3 mg Ammonium thiocyanate 50 mg Chloroauric acid 2.0 mg Fine silver iodide 5 mmol Triphenylphosphine selenide 4. 0mg Stabilizer (TAI) 1000mg

[0154]

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The term "silver iodide fine grains" used herein refers to a fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) used during emulsion growth.

A dispersion of the solid fine particles of the spectral sensitizing dye was prepared by a method according to the method described in JP-A-5-297496.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been previously adjusted to 27 ° C., and the mixture was subjected to 3.5 with a high-speed stirrer (dissolver).
Obtained by stirring at 00 rpm for 30-120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used for experiments.

Additives described below were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a transverse light-shielding layer and a coating solution for a protective layer described later were prepared. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10
a base layer composed of a copolymer composed mainly of three types of monomers consisting of 3% by weight of butyl methacrylate and 40% by weight of butyl methacrylate; X-ray polyethylene terephthalate film base (thickness: 175 μm) was used.

The following transverse light-shielding layers are coated on both sides of the support, and the emulsion layer coating solution and the protective layer are coated on both sides of the support in the order of the emulsion layer and the protective layer from the side closer to the support. The coating solution was simultaneously coated in multiple layers so as to have the following predetermined amount and dried. The amount of addition was shown per 1 m ² on one side of the silver halide photosensitive material.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AD-2) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² Latex (L) 0.2 g / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² Compound of the present invention or comparative compound Colloidal silica (average particle size) shown in Table 2 (0.04 μm) 10 mg / m ² Hardener (A) 2 mg / m ² Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3 ammonium dihydroxybenzene-4-sulfonic acid 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² compound ^{(H) 0.5mg / m 2 n} -C 4 H 9 OCH ₂ CH (OH) CH ₂ N ( (CH ₂ COOH) ₂ 350 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Compound (R) 2 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² Dextran (average molecular weight 1000) 0.2 g / m ² Compound (P) 0.2 g / m ² Compound of the present invention or comparative compound Compound (Q) shown in Table 2 0.2 g / m ² However, gelatin is 0 It was adjusted to be 0.8 g / m ² .

Third layer (protective layer) Gelatin 0.6 g / m ² Matt agent composed of polymethyl methacrylate 50 mg / m ² (area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-dichloro-6 Hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonyl methyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² polyacryl Sodium acid 30 mg / m ² Polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50mg / m ² compound (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2 O) 11 -H 3mg / m 2 _{8 F 17 SO 2 NH- [CH} 2 C (C 3 H 7) HO] 15 -H 2mg / m 2 C 8 F 17 SO 2 NH- [CH 2 C (C 3 H 7) HO] 4 - (CH ₂ ) ₄ SO ₃ Na 1 mg / m ² Hardener (B) 2 mg / m ² Compound of the present invention or comparative compound

[0164]

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[0165]

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[0166]

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[0167]

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The amount of silver applied was adjusted to 1.5 g / m ² on one side.

Table 2 shows the obtained samples.

[0170]

[Table 2]

[0171]

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The obtained sample was sandwiched between fluorescent intensifying screens KO-250, irradiated with X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.), and then treated for a total processing time of 25 seconds with the following developer formulation Was done.

A developing tablet was prepared according to the following operations (A, B).

[Operation (A)] 13,000 g of sodium erythorbate as a developing agent is pulverized in a commercially available bandam mill until the average particle diameter becomes 10 μm. To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone, DTPA
After adding 1635 g and mixing in a mill for 30 minutes and granulating by adding 30 ml of water for about 10 minutes at room temperature in a commercially available stirred granulator, the granulated product is subjected to 40 minutes by a fluidized bed drier.
After drying at 2 ° C. for 2 hours, the water content of the granules is almost completely removed. After 2167 g of polyethylene glycol 6000 was uniformly mixed with the thus-prepared granules for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less, the obtained mixture was mixed with Kikusui A tableting machine modified from Tough Presto Collect 1527HU manufactured by Seisakusho Co., Ltd.
The tablet was compressed at a filling amount of 8.715 g per tablet, and 2500 tablets E for development replenishment were prepared.

[Operation (B)] Potassium carbonate 19500
g, 1-phenyl-5-mercaptotetrazole 8.1
5 g, sodium hydrogen carbonate 3.25 g, glutaraldehyde sulfite adduct 650 g, polyethylene glycol 6
1354 g of 000 is crushed and granulated in the same manner as in the operation (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material.
The mixture thus obtained was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 9.90 g, and 2,500 development replenishers were used. Tablet F was prepared.

Next, a fixing tablet was prepared in the following manner.

[Operation (C)] Ammonium thiosulfate 18
560 g, 1392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate are pulverized and granulated as in (A). The amount of water to be added is 500 ml, and after granulation, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture thus obtained was subjected to compression tableting with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount per tablet of 8.214 g, and
2500 fixing replenishing tablets G were prepared.

[Operation (D)] 1860 g of boric acid, 6500 g of aluminum sulfate / 18-hydrate, 1860 g of glacial acetic acid,
928 g of sulfuric acid (50 wt%) is pulverized and granulated in the same manner as in the operation (A). The amount of water added was 100 ml, and after granulation,
After drying at 50 ° C. for 30 minutes, the water content of the granules is almost completely removed. The mixture thus obtained was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 4.459 g. Tablet H was prepared.

(Developer Starter) Glacial acetic acid 2.98 g KBr 4.00 g Water was added to make 1 liter.

At the start of processing of the developer (start of running), 16.5 l of the developer prepared by diluting the developing tablet with dilution water was used.
The processing was started by filling the developing tank with a liquid having 330 ml of a starter added thereto as a starting liquid. The pH of the developer to which the starter was added was 10.45.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 equipped with a charging member of a solid processing agent and modified so as to be able to process at a processing speed of 25 seconds was used.

During the running, the photosensitive material contains 1.0 photosensitive material.
One agent A, two agents B and 20 m of water per 0 m ²
1 was performed. When each of A and B was dissolved in 20 ml of water, the pH was 10.70. To the fixing solution, four of the above-mentioned C agent, two of the D agent and 50 ml of water were added per 1.00 m ² of the photosensitive material. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent.

[0183] In addition, if the said solid processing agent formulation is shown by a liquid formulation, it is as follows.

(Developer composition) Potassium carbonate 120 g Sodium erythorbate 40 g Diethylene triamine pentaacetic acid / 5Na 5 g (DTPA) 1-phenyl-5-mercaptotetrazole 0.05 g Sodium hydrogen carbonate 20 g Phenidone 3 g Sodium sulfite 15 g Polyethylene per 1000 ml of water Glycol 15 g Glutaraldehyde amino sulfite adduct 4 g (Fixing solution composition) Ammonium thiosulfate 160 g Sodium sulfite 12 g Boric acid 10 g Sodium hydroxide 5 g Glacial acetic acid 10 g Aluminum sulfate / 18-hydrate 35 g Sulfuric acid (50 wt%) 5 g Ethylene diamine 4 disodium acetate 2 per 1000 ml of water Water salt 0.02 g The sensitivity was evaluated by the reciprocal of the X-ray exposure required for Sample 1-1 to obtain a density of minimum density + 1.0. Is shown as a relative value with respect to 100.

As a substitute evaluation of storage stability, a sample was placed at 23 ° C. for 48 hours.
After leaving for 4 hours at% RH, it was sealed with a moisture-proof bag, left at 55 ° C. for 4 days, and then subjected to the same exposure treatment.

The intensifying screen contamination was evaluated by rubbing the sample and the intensifying screen 500 times and observing the surface by visual observation.

The color tone of the silver image was evaluated by visually observing the color tone of the processed photographic material having a density of 1.5.

The results are shown in Table 3.

[0189]

[Table 3]

From Table 3, it can be seen that the present invention is a silver halide photographic light-sensitive material having a good silver image color tone even after lapse of time, no transfer as intensifying screen contamination, and little change in photographic performance.

Example 2 <Preparation of silver iodochloride tabular grains> (Preparation of emulsion-5) A5 Ossein gelatin 75 g KI 1.25 g NaCl 33 g Distilled water to 15000 ml B5 Silver nitrate 410 g Distilled water to 684 ml C5 11590 g of silver nitrate Make 19316 ml with distilled water D4 KI 4 g NaCl 140 g Make 684 ml with distilled water E5 NaCl 3980 g Make 19274 ml with distilled water At 40 ° C., JP-B-58-58288, 58-58
No. 58289, a solution A5 in a mixing stirrer was added to B
5 and D5 were added over 1 minute. 14 EAg
After adjusting to 9mV and aging Ostwald for 20 minutes, C
5 and E5 were added over 320 minutes. Meanwhile, E
Ag was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed.
Em-5 thus prepared is a tabular grain having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane, and has an average thickness of 0.14 μm and an average diameter of 1.
It was found by electron microscope observation that the coefficient of variation was 0 μm and the coefficient of variation was 25%.

(Preparation of Emulsion-6) Emulsion-6 was prepared in the same manner as Emulsion-5, except that 8 × 10 ^-6 mol of potassium hexachloroiridate (IV) was added to the above solution E5.

Emulsions 5 to 6 had an aspect ratio of 7.2.

Subsequently, sensitization was performed by the following method. After the temperature of the emulsion-5 to the emulsion-6 was 55 ° C., predetermined amounts of the spectral sensitizing dyes (C) and (D) were added as a dispersion in the form of solid fine particles. Thereafter, a sulfur sensitizer, a selenium sensitizer, a gold sensitizer and a compound (R) are further added, and ripening is performed for a total of 90 minutes. When ripening is completed, 4-hydroxy-6-methyl-1,3 is used as a stabilizer. After adding an appropriate amount of 3,3,7-tetrazaindene (TAI), 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 Spectral sensitizing dye (C) 280 mg Spectral sensitizing dye (D) 40 mg Sulfur sensitizer 20 mg Gold sensitizer 1.0 mg Selenium Sensitizer (triphenylphosphine selenide) 4.0 mg Compound (R) 5.0 mg Stabilizer (TAI) 50 mg

[0197]

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Further, a coating solution for a transverse light-shielding layer and a coating solution for a protective layer were prepared in the same manner as in Example 1 except for the compound of the present invention or the comparative compound. 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 samples shown in Table 4.

[0199]

[Table 4]

[0200]

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The samples shown in Table 4 were sandwiched between the fluorescent intensifying screens used in Example 1 and evaluated in the same manner as in Example 1.

Table 5 shows the results.

[0203]

[Table 5]

As is clear from Table 5, according to the present invention, even when a high silver chloride emulsion was used, the color tone of the silver image was good,
Further, it can be seen that a silver halide photographic light-sensitive material is obtained in which the intensifying screen is not easily transferred and the photographic performance is less changed.

[0205]

According to the present invention, it is possible to obtain a pure black in which the silver image after development processing has little fluctuation in photographic performance due to the aging of the photosensitive material and the color tone of the developed silver image is neutral. Thus, a photosensitive material that does not contaminate the image was provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Reference number in the agency FI Technical display location G03C 1/09 G03C 1/09 1/835 1/835 7/00 510 7/00 510 520 520 520 530 530

Claims (4)

[Claims] In a silver halide photographic material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, the total projected area of silver halide grains contained in the silver halide emulsion is determined. 50% or more are tabular silver halide grains having a (111) plane as a main plane and having an aspect ratio of 2
20 or less, the tabular silver halide grains have an average silver iodide content of 0 to 1.0 mol%, and the tabular grains are grains formed in the presence of a silver halide solvent. And a dye comprising a polymer containing a monomer component represented by the following general formula (1), a monomer component represented by the following general formula (2) in the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer, and a general formula: A silver halide photographic material comprising at least one of the dyes represented by (3). Embedded image Wherein, Dye represents a dye skeleton absorption maximum is 520nm~750nm, Ball represents an immobilization group, X represents a COOW ¹ or SO ₃ W ^2. W ¹ and W ² represent a hydrogen atom, an alkali metal, or an alkaline earth metal. n ₁ is 1
Represents an integer of 1 to 3, and m ₁ represents an integer of 1 to 6. General formula (2) (Dye) -Q wherein Dye represents a dye skeleton having an absorption maximum of 520 nm to 750 nm, and Q represents a group having an ethylenically unsaturated group. [Chemical formula 2] [In the formula, A has an absorption maximum of 520 nm to 7 together with an N atom.
It represents an atomic group necessary for forming a 50 nm azomethine dye. R ₁ represents a group that can be substituted on a benzene ring, and n ₃ represents an integer of 0 to 4. When n ₃ is 2 or more, plural R ₁ may be the same or different, or may be bonded to each other to form a ring. R ₂ , R ₃ , R ₄ and R ₅ each independently represent an alkyl group, an aryl group or a polymer residue. ] 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support, wherein silver halide grains contained in the emulsion of the silver halide photographic light-sensitive material are removed. 50% or more of the total projected area is tabular grains having a parallel principal plane consisting of (100) planes and an aspect ratio of 2.0 or more and 20 or less, and a silver chloride content of 20 mol% or more and 100 mol% or less. Wherein at least one of a Group VIII metal, a Group II transition metal, lead, rhenium, molybdenum, and chromium of the periodic table is contained inside and / or on the surface of the silver halide grain; The grains are formed in the presence of a silver halide solvent, and the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer contains the dye represented by the general formula (1) and the monomer component represented by the general formula (2) Polymer A silver halide photographic light-sensitive material comprising at least one of a dye represented by formula (1) and a dye represented by formula (3): 3. A silver halide photographic material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, wherein the silver halide grains contained in the emulsion of the silver halide photographic material are More than 50% of the total projected area is (1
11) Tabular silver halide grains having a plane as a main plane, wherein the average silver iodide content of the tabular silver halide grains is from 0 to 1: 1.
0 mol%, the aspect ratio is 2 or more and 20 or less, the tabular grains are grains formed in the presence of a silver halide solvent, and the silver halide emulsion layer or the non-photosensitive hydrophilic The absorption maximum is 520 nm to 7 in the colloid layer.
A silver halide photographic material comprising at least one metal chelate dye having a thickness of 50 nm. 4. The total content of the above dye is 1 to 1 mol per silver.
The silver halide photographic material according to any one of claims 1 to 3, characterized in that × 10 ^-7 mol to 1 × 10 ^-1 molar content.