JPH10339925A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material high in maximum density and free from dye stains and improved in storage stability with the lapse of time and low in fog and high in sensitivity by specifying an iodide content of the total silver halide amount on the outermost surfaces to the subsurface of the silver halide gains and incorporating at least one kind of specified compound in the photosensitive material. SOLUTION: The photosensitive material has at least one photosensitive silver halide emulsion layer and the outermost surfaces to the subsurface of the silver halide grains have a silver iodide content of 0.01-2 mol.% of that of the total grains and the photosensitive material contains at least one of the compounds represented by the formula R-S-(M)y in which R is an aliphatic or aromatic or heterocyclic or alicyclic group each substituted by a water-soluble group; (y) is 1 or 0; M is an H or alkali metal atom or a cation; when (y) is 0, the compound of the formula is R=S, thus permitting the obtained photosensitive material to be high in sensitivity and maximum density and low in fog and superior in resistance to a safe-light and small in residual dye stains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity silver halide photographic material having a high maximum density, a small amount of dye contamination, and excellent storage stability over time, and more particularly to a silver halide photographic light-sensitive material for medical use and its processing method. It is about.

[0002]

2. Description of the Related Art In recent years, the demand for rapid processing of silver halide photographic light-sensitive materials has been increasing more and more. In the field of medical X-ray films, for example, the spread of health examinations and the increase of examination items have led to a decrease in the number of photographed images. Because of the increase or the need to grasp the diagnosis results sooner, there is a strong demand for ultra-rapid development processing.

[0003] However, for the purpose of rapid processing, it is necessary to shorten the processing time of each processing step such as development, fixing, washing, and drying, but the load of each processing increases. For example, if the development time is simply shortened, the conventional photosensitive material is accompanied by a reduction in sensitivity and image density and a deterioration in gradation. Further, when the fixing time is shortened, the fixing of silver halide becomes incomplete and causes deterioration of image quality. Further, shortening the time of each processing step causes insufficient elution of the dye or the like, which causes dye contamination by the residual dye.

In order to solve such a problem, for example, means for increasing the developing speed and fixing speed of the photosensitive material itself, reduction of the amount of dye, acceleration of detachment and decolorization of dye, and the like can be considered.

[0005] It is well known that reducing the amount of binder is effective in eliminating dye contamination. However, when the amount of binder is reduced, the pressure resistance is significantly deteriorated,
This causes problems such as abrasion caused by the roller of the automatic developing machine in rapid processing and pressure fog and pressure desensitization during bending.

Although silver saving techniques have been well studied for ultra-rapid processing and environmental protection, conventional photosensitive materials are accompanied by a reduction in sensitivity and image density and a deterioration in gradation.

On the other hand, it is essential to reduce development processing waste liquid for environmental protection. To this end, it is necessary to reduce the amount of processing solution and replenisher or to reduce the fatigue of the processing solution itself. As well as various problems.

As techniques for improving such a problem, for example, Japanese Patent Publication No. 43-4931, Japanese Patent Publication No. 44-16589,
EP-0,506,584, JP-A-5-88293
And JP-A-5-93975 disclose a technique using benzimidazolocarbocyanines having good decoloring performance as spectral sensitizing dyes. JP-A-5-61148 discloses that oxacarbocyanines and benzimidazolocarbocyanines are used in a specific ratio as a spectral sensitizer in a silver halide emulsion having a silver iodide content of 1 mol% or less. Further, a technique for performing chemical sensitization with a selenium compound and / or a tellurium compound has been disclosed.

[0009] However, these disclosed techniques, although improving the residual color and the rapid processing to some extent, are still insufficient to meet other desired levels. In particular, since the absorption maximum of the photosensitive material is on the long wavelength side and the sensitivity to red light is too high, the fog increase by safelight is large. Further, when the photographic material is stored for a long time under high humidity and high temperature, there is a disadvantage that the sensitivity is greatly reduced.

[0010] Many basic studies have been carried out on the adsorption of sensitizing dyes on the surface of silver halide grains for a long time. For example, Photogr. Sci. Eng, (18)
215 to 225 (1974) describe that when a sensitizing dye is adsorbed on an emulsion having a (100) plane, the desensitization of the intrinsic sensitivity of silver halide is small. When the chemical sensitization method is performed in the presence of a sensitizing dye, the chemical sensitization is controlled,
It also states that the desensitization of the intrinsic sensitivity can be reduced. However, these techniques do not suggest any pressure tolerance.

Further, silver halide photographic light-sensitive materials have characteristics of failure in illuminance, and the characteristics may vary depending on the processing solution. Especially low light failure is easily affected by the developing agent,
There is a problem that the long exposure sensitivity is greatly reduced, and improvement thereof is desired.

Meanwhile, in the field of medical light-sensitive materials, simplification and safety over the entire processing work are being promoted in order to improve workability. Conventionally, a liquid processing agent system in which a commercially available concentrated solution is diluted to a certain amount and then supplied to a processing tank of an automatic developing machine to replenish the processing agent has been usual. Therefore, since it is heavy and has a large volume, it has a drawback that work efficiency and safety are difficult to achieve. As an alternative to this, in recent years, a solid processing agent system supplied with a solid component and dilution water has been proposed. According to this method, it is possible to improve the working efficiency in addition to the reduction of the transportation cost of the processing agent, the reduction of the storage space, and the like, and also to reduce the amount of the plastic packaging material used conventionally in large quantities. It has favorable environmental benefits.

However, this method is not without its problems. For example, since the processing agent is a solid component, solubility (dissolution rate) is involved, and when the processing time is very short, the processing is stable. There is a problem that running performance cannot be obtained.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a low fog and high sensitivity silver halide photographic light-sensitive material having a high maximum density, no dye contamination, and improved storage stability over time.

[0015]

The above problems have been solved by the following. (1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the iodine content of the sub-surface to the outermost surface of the silver halide grains is adjusted to the whole grain. A silver halide photographic light-sensitive material, which is 0.01 mol% to 2 mol%, and contains at least one compound represented by the following general formula (1) in the light-sensitive material.

In the formula (1), RS- (M) _Y , R represents an aliphatic group, an aromatic heterocyclic group or an alicyclic group substituted with a water-soluble group. Y is 1 or 0.
M represents a hydrogen atom, an alkali metal, or a cation. When Y is 0, the general formula (1) represents R = S.

(2) The silver halide photographic material as described in (1) above, which contains at least one of benzimidazolocarbocyanines represented by the following general formula (2):

[0018]

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[0019] In the formula, each R ₁ and R ₃ represents a substituted or unsubstituted lower alkyl or alkenyl group, R ₂
And R ₄ represents an alkyl group, and at least one of R ₂ and R ₄ represents an alkyl group substituted with a hydrophilic group. Z ₁ , Z ₂ ,
Z ₃ and Z ₄ may be the same or different and each represents a hydrogen atom or a substituent. X ₁ represents an ion necessary for neutralizing an intramolecular charge, and n represents 1 or 2. However, when an inner salt is formed, n is 1.

(3) The silver halide photographic material as described in the above item (1) or (2), comprising silver halide grains chemically sensitized in the presence of a selenium compound or a tellurium compound.

(4) The silver halide photograph as described in (1), (2) or (3) above, which contains silver halide grains chemically sensitized in the presence of a compound represented by the following general formula (3): Photosensitive material.

Formula (3) A- (W) _m -Z In the formula, A is an atom group containing a group capable of adsorbing to silver halide, Z is an atom group containing an unstable selenium site, and W is 2 M represents 0 or 1;

(5) A method for continuously processing the silver halide photographic light-sensitive material according to any one of the above items (1) to (4) by an automatic processor, wherein each processing solution is continuously processed with a solid processing agent. A method for processing a silver halide photographic light-sensitive material, characterized in that the material is supplied while being supplied.

Hereinafter, the present invention will be described in detail.

One form of the silver halide photographic light-sensitive material of the present invention has at least one light-sensitive silver halide emulsion layer on at least one side of a support, and the amount of silver on one side is 0.5 g. well / m ² ~1.60g / m ^2, and preferably from ^{1.0g / m 2 ~1.50g / m 2} . Further, the photosensitive silver halide emulsion layer may be on only one side of the support,
Both sides may be used.

In the silver halide photographic light-sensitive material of the present invention, silver chloride, silver bromide, silver iodochloride, silver chloroiodobromide, silver chlorobromide, silver iodobromide, etc. are used as the base silver halide. Can be. Preferred is pure silver chloride, silver chlorobromide or pure silver bromide.

The silver chlorobromide grains used in the silver halide photographic light-sensitive material of the present invention preferably contain 50 mol% or more of silver chloride, more preferably 70 mol% or more, and more preferably 90 mol%. It is more preferable to contain the above.

It is necessary that the silver halide grains used in the present invention contain silver iodide in a localized manner from the subsurface to the outermost surface. Here, the outermost surface refers to a layer formed between the time when the grain growth is completed and the time when the chemical ripening is completed, and the subsurface is a layer having a depth of 20% of the thickness of the grain from the outermost surface. Point to.

The silver halide grains according to the present invention preferably have a silver iodide content of not more than 5.0 mol% as an average silver iodide content in the whole silver halide grains. The silver iodide content from the subsurface to the outermost surface needs to be 0.01 mol% to 2 mol% based on the whole grains. The content is preferably 0.01 mol% or more and 1.5 mol% or less, and 0.3 mol% or less.
More preferably, it is at least 1 mol% and at most 1 mol%.

In the present invention, silver iodide can be formed by simultaneously adding a silver nitrate solution and a solution containing iodide ions to an emulsion containing base grains, silver iodide, silver iodobromide or a salt. A method of adding silver halide fine particles such as silver iodobromide, 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.

The silver iodide content of the subsurface to the outermost surface of the silver halide grains of the present invention is 2.0 mol% or less based on the whole grains. Is preferably 1 mol% or less based on the whole particles. More preferably, it is 0.5 mol%. When the silver iodide-containing layer is formed during chemical ripening, the amount is preferably at most 0.6 mol%, more preferably at most 0.3 mol%.

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 silver halide grains used in 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.

The silver halide grains used in the present invention are:
Tabular silver halide grains having 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 light-sensitive material of the present invention are preferably 2 or more and 20 or less. It is more preferably 2 or more and 12 or less, and particularly 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 used in 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 referred to as hexagonal tabular grains) are those whose main plane ((111) plane) is hexagonal and whose maximum adjacency ratio is 1.0 to 2; 2.0.
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. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended 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.

When a silver halide solvent is used in the present invention, examples of the silver halide solvent include those described in US Pat.
No. 1,157, No. 3,531,289, No. 3,5
74,628, JP-A-54-1019, JP-A-54-1
(A) Organic thioethers described in JP-A-58917 and the like, JP-A-53-82408 and JP-A-55-77737.
(B) thiourea derivatives described in JP-A Nos. 55-2982 and 55-2982, and (c) a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent
(D) imidazoles described in -100717,
(E) Sulfite, (f) thiocyanate and the like, and silver halide solvents described in JP-A-57-196228 and the like can be mentioned. 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 of silver halide from the time of grain formation to the end of chemical sensitization is 1
It is preferably at least 2.5 × 10 ⁻³ mol and less than 5 × 10 ⁻² mol per mol.

In the present invention, when a tabular silver halide grain having a (100) plane as a main plane is used, the shape of the main plane of the tabular silver halide grain is a right-angled parallelogram or an angle of a 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, and 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 halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilton,
Photo. Sci. Eng, 57 (1967),
T. Shiozawa, J .; Soc. Photo. Sc
i. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. That is, silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, 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 penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

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.

As a technique for forming silver nuclei, reduction sensitization has been known for a long time. For example, Journal o
f Photographic Science No. 25
Vol. 19-27 (1977) and Photogra.
phi Scienceand Engineerine
g, Vol. 32, pp. 113-117 (1979) shows that silver nuclei formed by reduction sensitization are Pho.
togphile Korespndends, Vol. 1, 20 (1957) and Photographi.
c Science and Engineering
Mi in the 19th volume, 49-55 (1975)
As described by cell and Lowe, it has been considered that this contributes to sensitization through a reaction represented by the following formula at the time of exposure.

AgX + hv → 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, hv 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.

For 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 [T
_{i (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 affected by the type of the reducing agent, the conditions for forming silver nuclei, the timing of the addition of the oxidizing agent, and the addition 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. As these reducing substances,
A substance capable of reducing the oxidizing agent, sulfinic acids,
Di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, enediols, oximes, reducing sugars, phenidones, sulfites, ascorbic acid derivatives, etc. is there. These reducing substances are added in an amount of 10 ^-3 to 10 ³ per mole of the oxidizing agent used.
Molar is preferred.

The average grain size of the tabular silver halide grains used in 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 0.02 to 1.0 μm, more preferably 0.05 to 0.40 μm, and still more preferably 0.05 to 0.30 μm. It is. 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 the silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 10%) is used.
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.

Next, the compound represented by formula (1) will be described.

[0062] Formula (1) R-S- (M ) in which _Y formulas, R represents an aliphatic group substituted with a water-soluble group, an aromatic group,
Represents a heterocyclic group or an alicyclic group. Y represents 1 or 0. M represents a hydrogen atom, an alkali metal atom or a cation. When Y is 0, the general formula (1) represents R = S.

As the water-soluble substituent of R, -SO ₃ M,-
COOM ₁ , —OH and —NHR ₅ can be mentioned. Among the water-soluble substituents, -COOM ₁ is preferable (M ₁
Represents a hydrogen atom, an alkali metal atom or a cation. ). One or more water-soluble substituents may be substituted. R ₅ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -C
Represents OR ₆ , —COOR ₆ or —SO ₂ R ₆ , wherein R ₆ represents a hydrogen atom, an aliphatic group or an aromatic group. Further, it is particularly preferable that an electron-withdrawing group is contained as a substituent of R. For example, halogen atom (especially F, Cl), trifluoromethyl, cyano, carboxy, carbamoyl, ethynyl, acetyl, ethoxycarbanyl, trifluoromethoxy, sulfamoyl, methanesulfonyl, benzenesulfonyl, trifluoromethylthio, isothiocyanate, 1-pyrroline , 2-pyridyl and the like.

The aliphatic group represented by R has 1 to 1 carbon atoms.
30, preferably 1 to 20 linear or branched alkyl, alkenyl, alkynyl or cycloalkyl groups. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl , Cyclohexyl, cyclododecyl and the like. Examples of the aromatic group represented by R include those having 6 to 20 carbon atoms,
Specific examples include groups such as phenyl, naphthyl, and anthranyl.

The heterocyclic group represented by R may be a single ring or a condensed ring, and may have at least one of O, S, and N atoms.
5- to 6-membered heterocyclic groups having a species in the ring are included.
Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole,
Examples include isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and groups derived from these benzerogues.

The alicyclic group represented by R includes a carbon ring having 4 to 7 members or a condensed ring thereof. For example, cyclopentene, cyclopentadiene, cyclohexane, cyclohexadiene, terpene, steroid and the like can be mentioned.

The aliphatic group, aromatic group, heterocyclic group or alicyclic group represented by R may be further substituted, such as a halogen atom (for example, chlorine atom, bromine atom, etc.), Alkyl groups (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl groups (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl groups (eg, Benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.) An aryloxy group (for example, a phenoxy group, a 4-methoxyphenoxy group, etc.), a cyano group,
Acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (eg, phenylthio group, p-methylphenylthio group, etc.), sulfonylamino group (eg, Methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoyl) Amino group, diethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbo (For example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, p-chlorophenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.) , An acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), an amino group (methylamino group, ethylamino group, dimethylamino group, etc.), a hydroxy group, a nitro group, a nitroso group, an amine oxide group (eg, pyridine-oxide Group), an imide group (eg, a phthalimido group), a disulfide group (eg, a benzenedisulfide group, a benzthiazolyl-2-disulfide group, etc.), a heterocyclic group (eg, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxy group) Zoriru group). R may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. m is 2-6
And preferably 2 to 3. Among them, it is particularly preferable to contain an electron-withdrawing group.

Hereinafter, specific examples of the compound represented by formula (1) used in the present invention will be shown, but the present invention is not limited thereto.

[0069]

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[0070]

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[0071]

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[0072]

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The compound represented by the general formula (1) is characterized in that it is added to an emulsion layer and / or a non-emulsion layer before, during or after chemical sensitization. A preferable addition amount is 0.1 to 500 mg / m ² , more preferably 1 to 300 mg / m ² .
mg / m ² . The compound of the general formula (1) is dissolved in water or an organic solvent (eg, methanol) miscible with water,
Alternatively, it can be added in a finely dispersed form in a gelatin solution or the like. In the emulsion and the light-sensitive material, the compound of the general formula (1) may exist as a silver salt compound.

When the silver halide grains of the present invention are chemically sensitized, a silver halide emulsion having high sensitivity and good developability is obtained, but the fogging and the fogging during storage tend to increase. When the compound of the general formula (1) of the present invention is added,
The storage stability is good while maintaining high sensitivity, and an effect more than expected can be obtained.

Next, the spectral sensitizing dye represented by formula (2) used in the present invention will be described.

Spectral sensitizing dyes are those which adsorb to silver halide grains and contribute to sensitization.

The spectral sensitizing dye used in the present invention is not particularly limited as long as it has a spectral sensitizing function. The sensitizing dye represented by the above general formula (2) is adsorbed on silver halide emulsion grains and reflected. When the spectrum is measured, the maximum absorption wavelength of the J cohesion band is preferably 555 nm or less.
In the application to X-ray medical light-sensitive materials utilizing a phosphor emitting green light, the spectral sensitizing dye of the present invention is adsorbed on silver halide emulsion grains, and the fluorescence spectrum is measured when its reflection spectrum is measured. J- in the same wavelength range as green light emitted from
Preferably, a band is formed. That is,
It is preferable to select and combine spectral sensitizing dyes such that the J-band having the maximum absorption is preferably formed in the range of 520 nm to 555 nm. More preferably, it is 530-553 nm, most preferably 540-550 nm.

Preferred spectral sensitizing dyes of benzimidazolocarbocyanines are represented by the above formula (2).

In the general formula (2), R ₁ and R ₃ each represent a substituted or unsubstituted alkyl group or alkenyl group.
Examples of the alkyl group include linear or branched groups such as ethyl, propyl, and 3-methylbutyl groups. Examples of the substituted alkyl group include 2-hydroxyethyl and 2-
Examples include methoxyethyl, 2-ethoxyethyl, ethoxycarbonylethyl, allyl, phenethyl, methanesulfonylethyl, and 3-oxobutyl groups.

The alkyl groups represented by R ₂ and R ₄ include, for example, straight-chain and branched groups such as methyl, ethyl, butyl, and isobutyl groups. , Carboxy, methanesulfonylaminocarbonyl, methanesulfonylaminosulfonyl,
There are dissociable groups such as acetylaminosulfonyl, sulfoamino, trifluoroacetylaminosulfonyl, acetylaminocarbonyl, and N-methylsulfamoyl, and specific examples include, for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 5-sulfopentyl,
2-N-ethyl-N-sulfoaminoethyl, carboxymethyl, carboxyethyl, 3-sulfoaminopropyl, 6-sulfo-3-oxahexyl, 10-sulfo-
Examples include 3,6-dioxadecyl, 6-sulfo-3-thiahexyl, o-sulfobenzyl, p-carboxybenzyl, methanesulfonylaminocarbonylmethyl, and acetylaminosulfonylmethyl groups.

Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different, and each has a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine atom, etc.) and an alkyl group (eg, methyl , Ethyl, propyl and other lower alkyl groups), alkoxy groups (for example, methoxy, ethoxy, propoxy and the like), and halogen-substituted alkoxy groups (for example, fluoromethoxy, trifluoromethyl,
2,2,2-trifluoroethyl group, etc.), aryloxy group (eg, phenoxy, p-bromophenoxy group, etc.), acyl group (eg, acetyl, benzoyl group, etc.),
Acyloxy groups (eg, acetyloxy, propionyloxy groups, etc.), alkylthio groups (eg, methylthio, ethylthio groups, etc.), halogen-substituted alkylthio groups (eg, trifluoromethylthio, difluoromethylthio groups, etc.), and alkoxycarbonyl groups (eg, methoxycarbonylmethyl) , Ethoxycarbonyl group, etc.), carbamoyl group (for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-3-oxa-pentamethylenecarbamoyl, N-phenylcarbamoyl group, etc.) ), Sulfamoyl groups (eg, N-methylsulfamoyl, N, N
-Tetramethylenesulfamoyl, N, N-3-oxapentamethylenesulfamoyl, N-phenylsulfamoyl, N, N-diethylsulfamoyl group, etc.), haloalkyl group (for example, monofluoromethyl, difluoromethyl, Trifluoromethyl, monochloromethyl group, etc.),
A sulfonyl group (eg, methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, fluorosulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.), an acylamino group (eg, N-acetylamino, N
-Trifluoroacetylamino group, etc.), substituted or unsubstituted aryl groups (eg, phenyl, o-fluorophenyl, p-cyanophenyl, m-chlorophenyl group, etc.),
Examples of the heterocyclic group include substituted or unsubstituted ones (for example, 1-pyrrolyl, 2-furyl, 2-benzoxazolyl group, etc.).

The ion required to neutralize the charge in the dye molecule represented by X ₁ may be either an anion or a cation. Examples of the anion include a halogen ion (an ion such as chloro, bromo or iodine). ), Perchlorate, ethyl sulfate, thiocyanate, p-
There are toluene sulfonate, perfluoroborate, etc.
Examples of the cation include a hydrogen ion, an alkali metal ion (an ion such as lithium, sodium, and potassium), an alkaline earth metal ion (an ion such as magnesium and calcium), an ammonium ion, and an organic ammonium ion (triethylammonium, triethanolammonium, and tetraethylammonium). Ions such as methylammonium).

Next, specific examples of the spectral sensitizing dye represented by the general formula (2) according to the present invention will be described, but the present invention is not limited thereto.

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The spectral sensitizing dye of the present invention may be used in combination with another spectral sensitizing dye. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobora cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
These dyes can be applied to any of the nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., these nuclei are fused with an alicyclic hydrocarbon ring, that is, indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These patents are described, for example, in German patent 92
9,080; U.S. Pat. Nos. 2,231,658;
493,748, 2,503,776, 2,5
19,001, 2,912,329, 3,65
5,394, 3,656,959 and 3,67
2,897, 3,649,217, British Patent 1,
242,588 and JP-B-44-14030.

In addition to these spectral sensitizing dyes, a dye which does not itself have spectral sensitization or a substance which does not substantially absorb visible light and exhibits supersensitizing effect is added to the emulsion layer. Is preferred.

In the present invention, the amount of the spectral sensitizing dye added is
Type of dye and structure, composition, ripening condition of silver halide,
Although it depends on the purpose and application, it is preferable to add the spectral sensitizing dye as solid dispersed fine particles or an acidic solution. To obtain the object of the present invention should be silver amount of the substrate side is ^{0.1g / m 2 ~1.6g / m 2} . Further, the amount of gelatin is from 0.1 g / m ² to 2.
It is preferable that the sensitizing dye is added in an amount of ² g / m ² and the weight ratio of the amount of sensitizing dye to the amount of silver per fixed area is 0.0001 to 0.004.

The technique of using two or more spectral sensitizing dyes according to the present invention is useful for photosensitive materials requiring sensitivity to green light.

It is necessary to contain at least one of the spectral sensitizing dyes of the general formula (2) according to the present invention. In addition,
The light-sensitive material of the present invention has a maximum absorption wavelength of 530 nm to 560.
If it is nm, the spectral sensitizing dye represented by the general formula (2) of the present invention may be used alone or in combination of two or more. Further, other spectral sensitizing dyes may be used in combination. Dyes used include cyanine, merocyanine,
Holopolar cyanine may be used in combination.

In addition to these spectral sensitizing dyes, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits supersensitizing effect is added to the emulsion layer. May be.

In the present invention, the amount of the spectral sensitizing dye added is
Type of dye and structure, composition, ripening condition of silver halide,
Although it depends on the purpose and application, it is preferable that the coverage of the monomolecular layer on the surface of each photosensitive particle in the silver halide emulsion be less than 75%. Further, less than 65% is particularly preferred.

In the present invention, the monolayer coverage is 5%.
The saturated adsorption amount when the adsorption isotherm is created at 0 ° C. is relatively determined as an amount corresponding to a coverage of 100%. The appropriate amount of the spectral sensitizing dye per mole of silver halide varies depending on the total surface area of the silver halide grains in the emulsion, but is preferably less than 500 mg. Further, it is preferably 400 mg or less.

In the present invention, forming the development start point at or near the apex means that the surface of the silver halide grains is coated with a silver halide-adsorbing compound such as a spectral sensitizing dye or a stabilizer in the chemical sensitization step. And by controlling the chemical sensitization nucleation site or / and by using a reaction site selective chemical sensitizer.

As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols and the like have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol,
There are 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like.

However, in the present invention, the effect is increased by adding the spectral sensitizing dye as an acidic solution or a dispersion in the form of solid fine particles, as compared with the case where the spectral sensitizing dye is added as a solution of an organic solvent. Preferably, at least one of the spectral sensitizing dyes is added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant. .

In the present invention, an organic solvent and / or
Alternatively, the aqueous system free of a surfactant is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably refers to ion-exchanged water and distilled water.

The spectral sensitizing dye of the present invention can be added at the time of chemical ripening, particularly preferably at the start of chemical ripening. By adding it by the end of the process, a high-sensitivity silver halide emulsion having excellent spectral sensitizing efficiency can be obtained. (From the nucleation step to the end of the desalting step), the same or a different kind of spectral sensitizing dye of the present invention may be additionally added.

In the present invention, the conditions of the step of chemical sensitization,
For example, the pH, pAg, temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art.

In the present invention, it is more preferable that the chemical sensitization is performed using a selenium compound or a tellurium compound. A sulfur sensitization method using a compound containing sulfur or a reactive gelatin capable of reacting with silver ions for chemical sensitization, a reduction sensitization method using a reducing substance, gold or the like, a noble metal sensitization method using a noble metal alone or the like They can be used in combination.

For the chemical sensitization method used for chemical sensitization, the sensitization method described in JP-A-7-114131 can be referred to.

Selenium sensitizers used for chemical sensitization include a wide variety of selenium compounds. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, 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, selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides ( For example, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) And selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones. However, in the present invention, the effect is increased by adding the selenium sensitizer as a dispersion of solid fine particles as compared with the case where the selenium sensitizer is added as a solution of an organic solvent.

For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, British Patent No. 235211
No., No. 1121496, No. 1295462, No. 13
No. 96696, Canadian Patent No. 800958,
Nos. -2064040 and 4-333430. 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), telluramides (e.g., , Telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates and the like.

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

In the present invention, reduction sensitization is preferably used in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. It also includes a method of growing the perceived silver halide grains.

The reduction sensitization performed in the present invention is performed during the growth of silver halide grains of the silver halide emulsion.
A reducing agent and / or a water-soluble silver salt are added to the silver halide emulsion.

The gold sensitizer includes chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds. The amounts of the sulfur sensitizer and the gold sensitizer used are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like, but are usually 1 × per mol of silver halide.
It is preferably from 10 ^-4 mol to 1 × 10 ^-9 mol. Further, the amount is preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

It is preferable to use a selenium sensitizer as a chemical sensitizer for the silver halide emulsion used in the present invention.
As the selenium sensitizer, a compound having an adsorptive group to silver halide and an unstable selenium site is more preferably used, and specific examples include a compound represented by the following general formula (3).

Formula (3) A- (W) _m -Z In the formula, A represents an atom group containing a group capable of adsorbing to silver halide, Z represents an atom group containing an unstable selenium site, and W represents 2 M represents 0 or 1;

Next, the general formula (3) will be described in detail. In the general formula (3), as an atom group including a group adsorbable to silver halide represented by A, specifically, an atom group having a mercapto group (a mercaptotetrazole group, a mercaptotriazole group, a mercaptoimidazole group, Mercaptothiadiazole group, mercaptooxathiazole group, mercaptobenzthiazole group, mercaptobenzoxazole group, mercaptobenzimidazole group, mercaptotetrazaindene group, mercaptopyridyl group,
An atom group having a thione group (such as a mercaptoalkyl group or a mercaptophenyl group) (thiazoline-2-thione group, imidasolin-2-thione group, benzimidazoline-2-thione group, benzothiazoline-2-thione group, etc.) And atoms forming imino silver (benzotriazole group, tetrazole group, hydroxyazaindene group, benzimidazole group, benztriazole group, etc.). Preferably, it is a group of atoms having a mercapto group or a thione group.

In the general formula (3), examples of the atomic group containing an unstable selenium site represented by Z include (1) selenoureas (for example, N, N-dimethylselenourea, selenoureas, N-acetyl-N, N ', N'-trimethylselenourea, N-trifluoroacetyl-N,
N ', N'-trimethylselenourea), (2) selenoamides (eg, N, N-dimethylselenobenzamide, N, N-diethyleneselenobenzamide, etc.), (3) phosphine selenides (eg, triphenyl Phosphine selenide, diphenyl (pentafluorophenyl) phosphine selenide, tris (m-fluorophenyl) phosphine selenide, etc., (4) selenophosphates (tri-p-tolyl selenophosphate,
Selenophosphoric acid o, o, o-tris (hydroxyethyl) ester and the like, (5) selenoesters (for example, p-methoxyselenobenzoic acid o-isopropyl ester, selenobenzoic acid Se- (3'- Oxobutyl) ester, p-
Methoxyselenobenzoic acid Se- (3'-
(6) diacyl selenides (eg, bis (2,6-dimethoxybenzoyl) selenide), (7) bis (alkoxycarbonyl) selenides (eg, bis (n-butoxycarbonyl) selenide, Bis (benzyloxycarbonyl)
(8) dicarbamoyl selenides (e.g., bis (N, N-dimethylcarbamoyl) selenide), (9) triselenanes (e.g., 2,4,6-
Tris (p-methoxyphenyl) triselenane, etc.),
(10) selenoketones (for example, 4,4'-methoxyselenobenzophenone and the like), (11) diselenides,
Polyselenides (12) selenocarboxylic acids (13) isoselenocyanates (p-tolyl isoselenocyanate, cyclohexyl isoselenocyanate, etc.), (14) selenourethanes, selenocarbonates, selenohitrazines, ( 15) Selenols and the like. Preferably, selenoureas, selenoamides, phosphine selenides, bis (alkoxycarbonyl) selenides, triselenanes, isoselenocyanates, selenourethanes, selenocarbonates, selenohydrazides, selenoesters are preferred. Can be More preferred are selenoureas, selenamides, phosphine selenides, bis (alkoxycarbonyl) selenides, and selenoesters. General formula (3)
Wherein the divalent linking group represented by W is a carbon atom, a hydrogen atom,
Represents a divalent linking group composed of an oxygen atom, a nitrogen atom, and a sulfur atom, and specifically, an alkylene group having 1 to 20 carbon atoms (methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, etc. ), An arylene group having 6 to 20 carbon atoms (phenylene group, naphthylene group, etc.), -CO
_{NR 11 -, - SO 2 NR} 12 -, - O -, - S -, - NR
_{13 -, - NR 14 CO -} , - NR 15 SO 2 -, - NR 16 C
_{ONR 17 -, - COO -,} - OCO- , and the like.
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ or R ₁₇ represent a hydrogen atom, an aliphatic group or an aromatic group.

In the general formula (3), R ₁₁ , R ₁₂ ,
The aliphatic group represented by R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ or R ₁₇ is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms. Group, alkenyl group, alkynyl group and aralkyl group. Examples of the alkyl group, alkenyl group, alkynyl group, aralkyl group include, for example, methyl group, ethyl group, isopropyl group,
t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group,
Examples thereof include a cyclohexyl group, an allyl group, a 2-butenyl group, a 3-benthenyl group, a propargyl group, a 3-pentynyl group, and a pendyl group.

In the general formula (3), R ₁₁ , R ₁₂ ,
The aromatic group represented by R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ or R ₁₇ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. An aryl group,
For example, a phenyl group, a naphthyl group, etc. The above groups may be combined with each other to form a divalent linking group.

Hereinafter, specific examples of the compound represented by formula (3) will be shown, but the present invention is not limited thereto.

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The silver halide photographic light-sensitive material of the present invention includes
When at least one of the layer containing the photosensitive silver halide emulsion or at least one of the constituent layers other than the emulsion layer contains a dye capable of decoloring and / or flowing out during the development processing, high sensitivity and high sharpness are obtained. A light-sensitive material having a low dye stain can be obtained. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.
When the emulsion layer contains a suitable amount of a cyan dye which exhibits an absorption maximum at 580 to 700 nm and does not flow out during development, a photosensitive material having excellent silver tone and residual color is obtained.

The silver halide light-sensitive material according to the present invention includes:
Various photographic additives can be used. Known additives include, for example, Research Disclosure (R
D) No. No. 17643 (December 1978);
No. 18716 (November 1979) and the same No. 3081
19 (Dec. 1989). The compound types and locations described in these three RDs are described below.

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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 one of the emulsion layers and other layers. .

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 polyethylene terephthalate film or the like, and the surface of these supports 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.

When the silver halide photographic light-sensitive material of the present invention is provided with a silver halide emulsion layer and a crossover cut layer on both sides of a support, a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained.

In the photographic light-sensitive material of the present invention, the total amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is preferably in the range of 1.5 to 2.2 g / m ² on one side of the support. . If the amount of gelatin is too large, dyes and dyes are adsorbed, resulting in color contamination of the photographic element. In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of the silver halide grains. Examples of the gelatin include alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000), and phthalated gelatin. And the like. Other hydrophilic colloids can also be used. Specifically, RD-No. 17643 (19
(December 1978).

The silver halide photographic light-sensitive material of the present invention can be processed using a solid processing agent. The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as a tablet, a pill, a granule, or the like, which is subjected to moisture proof processing as required.

The powder as used in the present invention refers to an aggregate of fine crystals. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

The silver halide photographic light-sensitive material of the present invention can be supplied while continuously processing a solid processing agent. The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as a tablet, a pill, a granule, and the like. The powder refers to an aggregate of fine particle crystals. Granules are obtained by adding a granulation process to powder.
A tablet refers to a granular material having a particle size of 50 to 5000 μm, and a tablet refers to a product obtained by compression molding a powder or a granule into a predetermined shape.

To solidify the processing agent, a concentrated liquid or a fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded processing agent is sprayed with the water-soluble binder. Or any other means such as forming a coating layer (see JP-A-4-29136 and JP-A-4-85533).
Nos. 4-85534, 4-85535, 4-
No. 85536, 4-172341).

A preferred tablet production method is a method in which a powdered solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet. As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm, because when mixing the granules and compressing and compressing, the components become non-uniform, so-called segregation hardly occurs. Is preferably used, and more preferably 200 to 750 μm.
Further, the particle size distribution is such that 60% or more of
Those with a deviation of 150 μm are preferred. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handling, or dust when used on the user side, a cylindrical type, so-called tablet, is preferable. .

Preferably, at the time of granulation, the above effect is further remarkable by separating and granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

A method for producing a tablet processing agent is described in, for example,
Nos. 1-61837, 54-155038 and 52-
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-109043.
And JP-A-3-39735, JP-A-3-39939, and the like. Further, powder processing agents are described, for example, in JP-A-54-133332 and British Patent 72.
5,892, 729,862 and German Patent 3,
It can be produced by a general method as described in the specification such as 733,861.

The bulk density of the above-mentioned solid processing agent is 1.0 g / cm ³ in the case of a tablet from the viewpoint of solubility and effect.
To 2.5 g / cm ³ is in terms of the strength of preferably 1.0 g / cm ³ greater than the resulting solid, and more preferred in view of solubility of the solid product obtained as 2.5 g / cm ³ less than. When the solid processing agent is granules or powder, the bulk density is 0.
Those having 40 to 0.95 g / cm ³ are preferred.

The solid processing agent used in the present invention is a developer,
Although used for photographic processing agents such as fixing agents and rinsing agents, it is the developer that has a great effect of the present invention, especially an effect of stabilizing photographic performance.

The solid processing agent used in the present invention may be such that only one part of a certain processing agent is solidified, but it is preferable that all the components of the processing agent be solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

In the case of solidifying the developer, it is preferable that all of the alkali agent and the reducing agent be solid processing agents, and in the case of tablets, at least three agents are used and most preferably one agent is used. It is a preferred embodiment of the agent. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63-97
There are known methods such as Japanese Patent Application Laid-Open No. 522 and Japanese Utility Model Application Laid-Open No. 1-85732, 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 in the form of granules or powder, it is disclosed in Japanese Utility Model Application Laid-Open No. 62-8196.
4, JP-A-63-84151, JP-A-1-292375
No., the gravity drop method described and the actual opening 63-105159
And a method using a screw or a screw described in JP-A-63-195345 are known methods, but are not limited thereto.

However, in a preferred method, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened according to the processing amount of the photosensitive material. There is a way to take it out. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials. The part is opened so that it can be removed. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall. Since a predetermined amount of the solid processing agent is stored in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off, the moisture proof is guaranteed unless opened.

As an embodiment, it is conceivable that a package made of at least two packaging materials is tightly adhered or adhered to each other so as to sandwich the solid processing agent so as to be able to separate the periphery of the solid processing agent. . By pulling each packaging material sandwiching the solid processing agent in a different direction, the contact surfaces adhered or adhered are separated, and the solid processing agent can be taken out.

As another embodiment, a configuration is conceivable in which at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or the package is opened. It is conceivable that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting information on the processing amount. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. Also, when the processing agent is packaged and needs to be opened, the driving means for separating or opening operates based on the obtained supply start signal, and the driving means for separating or opening based on the supply stop signal stops. Can be controlled.

The solid processing agent supply means may have a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material. That is, in an automatic developing machine, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance.

The processing amount information of the photographic material is the processing amount of the silver halide photographic material processed with the processing solution or
It is a value proportional to the processing amount of the processed silver halide photographic light-sensitive material or the processing amount of the silver halide photographic light-sensitive material being processed, and indicates indirectly or directly the reduction amount of the processing agent in the processing solution. Before the photosensitive material is carried into the processing solution,
It may be detected at any time after or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution, a change in the concentration, pH, and specific gravity may be used. Alternatively, the amount of the treatment liquid that has come out after drying may be used.

The place where the solid processing agent of the present invention is charged may be in a processing tank, but is preferably in communication with a processing section for processing a photographic material, and a processing liquid flows between the processing section and the processing section. And a structure in which there is a constant processing solution circulation amount with 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.

It is preferable that the developer in the processing method of the present invention does not substantially contain a dihydroxybenzene-based developing agent.

In the developing solution in the processing method of the present invention, an organic reducing agent can be used as a preservative in addition to the sulfite described in Japanese Patent Application No. 4-286232 as a preservative. In addition, a chelating agent described in Japanese Patent Application No. 4-586323 (p. 20) or a bisulfite adduct of a hardener described in the same (p. 21) can be used. It is also preferable to add compounds described in JP-A-5-289255 and JP-A-6-308680 (general formulas [4-a] and [4-b]) as silver sludge inhibitors. 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. Further, it is necessary to use a buffer, and examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, and potassium borate. Sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) , 5-sulfo-2
Potassium-hydroxybenzoate (potassium 5-sulfosalicylate);

As development accelerators, for example, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, ionic compounds, Mesoionic compounds, imidazoles and the like can be added as needed.

As an antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
Examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine, and typical organic antifoggants include 1-phenyl-5-mercaptotetrazole.

Further, if necessary, methyl cellosolve,
Methanol, acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378
And the compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the starter after solidifying it. 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 processing temperature of the developer is preferably from 25 to 5
At 0 ° C, more preferably 30 to 40 ° C. The development time is 3 to 15 seconds, more preferably 3 to 10 seconds. The total processing time in the present invention is Dry to Dry
For 30 seconds or less, and preferably 25 seconds or less. The term "total processing time" as used herein refers to the total processing time including the steps of developing, fixing, washing and drying the photosensitive material.

The replenishment of the treating agent replenishes the amount corresponding to the treating agent fatigue and oxidative fatigue. The replenishment method is disclosed in
No. 43, replenishment by width and feed speed.
No. 104946, refilling area, JP-A-1-149915
Area replenishment controlled by the number of sheets continuously processed described in No. 6 may be used, and a preferable (development) replenishment amount is 14 ml / quarter or less. More preferably, it is 7 ml / quarter or less.

The fixing temperature and time are more preferably from 20 ° C. to 50 ° C. for 2 seconds to 8 seconds. Preferred fixing solutions include fixing materials generally used in the art, and the iodine content is preferably 0.3 g / liter or less, more preferably 0.1 g / liter or less. Fixer pH is 3.8
As mentioned above, it is preferably 4.2 to 5.5. A preferred replenishing rate of the fixing solution is 14 ml / quarter or less, more preferably 7 ml / quarter or less. The fixing solution may be one that forms an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

The fixing solution may optionally contain a preservative such as sulfite or bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid, oxalic acid, malic acid, etc.). PH adjusting agents such as various acids such as hydrochloric acid, metal hydroxides (potassium hydroxide and sodium), and chelating agents having a water softening ability.

Examples of the fixing accelerator include, for example, JP-B-45-3
No. 5754, No. 58-122535, No. 58-122
No. 536, US Pat. No. 4,126,
And the thioethers described in JP-A No. 459.

The silver halide photographic light-sensitive material of the present invention is interposed between high sensitivity intensifying screens and X-ray photographed.

The filling rate of the phosphor in the phosphor layer of the high-sensitivity intensifying screen used in the present invention is 68% or more, preferably 70% or more, more preferably 72% or more.

The thickness of the phosphor layer is 150 μm or more,
It is 50 μm or less. When the thickness of the phosphor layer is less than 150 μm, sharpness is sharply deteriorated. It is preferable that the radiation intensifying screen is filled with a phosphor in a gradient particle size structure.

In particular, it is preferable to coat large-sized phosphor particles on the surface protective layer side and small-sized phosphor particles on the support side. And those having a large particle diameter are preferably in the range of 10 to 30 μm. In the high-sensitivity fluorescent intensifying screen used in the present invention, the filling rate of the phosphor particles is increased so that the X-ray absorption of each intensifying screen is 30% or more per 100 μm of the thickness of the phosphor layer. Is preferred. The amount of X-ray absorption was determined as follows.

That is, an X-ray generated from a tungsten target operated at 80 kVp from an X-ray generator whose intrinsic filtration is equivalent to 2.2 mm of aluminum with three-phase power supply is used to convert an aluminum plate having a thickness of 3 mm and a purity of 99% or more to an aluminum plate. 200c from the tungsten anode of the target tube
to the radiation intensifying screen fixed at position m,
Next, 50c from the phosphor layer of the radiographic intensifying screen.
The position after m was measured using an ionizing dosimeter to determine the amount of X-ray absorption. As a reference, the X-ray dose at the measurement position without passing through the intensifying screen was used.

Preferred binders used in the radiographic intensifying screen according to the present invention include thermoplastic elastomers. Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene,
Examples include at least one thermoplastic elastomer selected from the group consisting of ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber, and silicone rubber.

Preferred phosphors of the intensifying screen used in the present invention include the following.

Tungstate phosphors (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S:
Tb, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂ S: Tb,
Tm etc.), terbium-activated rare earth phosphate-based phosphor (YP
O ₄ : Tb, GdPO ₄ : Tb, LaPO ₄ : Tb, etc.),
Terbium-activated rare earth oxyhalide phosphor (L
aOBr: Tb, LaOBr: Tb. Tm, LaOC
l: Tb, LaOCl: Tb. TmGdOBr: Tb,
GdOCr: Tb), thulium-activated rare earth oxyhalide phosphor (LaOBr: Tm, LaOCl: T)
m, etc.), barium sulfate-based phosphor [BaSO ₄ : P
b, BaSO ₄ : Eu ²⁺ , (Ba.Sr) SO ₄ : Eu ²⁺
Etc.] divalent eurobium-activated alkaline earth metal phosphate-based phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ , (Ba, S
r) ₃ , (PO ₄ ) ₂ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor [Ba
FCl: Eu ²⁺ , BaFBr: Eu ²⁺ , BaFCl: E
u ²⁺ . Tb, BaFBr: Eu ²⁺ . Tb, BaF ₂ . B
aCl ₂ . XBaSO ₄ . KCl: Eu ²⁺ , (Ba.M
g) F ₂ . BaCl ₂ . KCl: Eu ²⁺ etc.], iodide-based phosphors (CSI: Na, CSI: Tl, NaI.KI: T
l), a sulfide-based phosphor [ZnS: Ag, (Zn.C
d) S: Ag, (Zn. Cd) S: Cu, (Zn. C)
d) S: Cu. Al etc.), hafnium phosphate phosphor (H
fP ₂ O ₇ : Cu, etc.) However, the phosphor used in the present invention is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

[0169]

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 silver iodobromide hexagonal tabular grains> Preparation of Em-1 A1 Ossein gelatin 75.5 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous solution of ethanol) 6.78 ml 64.7g Potassium bromide Make up to 10800ml with water.

B1 0.7N aqueous silver nitrate solution 1340ml C1 2.0N aqueous silver nitrate solution 1500ml D1 1.3N aqueous potassium bromide solution 410ml E1 2.0N aqueous potassium bromide solution Silver potential control amount F1 ossein gelatin 125g water 4000ml G1 KSCN aqueous solution 2N) 60 cc H1 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μ) (*) Equivalent to 0.008 mol * 5.0 weight containing 0.06 mol of potassium iodide 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 6.64 liters of a 6% aqueous gelatin solution over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, p is added using an aqueous sodium carbonate solution.
H was adjusted to 6.0.

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. to ripen. 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, the silver iodide content of the silver halide grains was 0.03 mol%, and 90% or more of the total projected area was 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 Em-2 It was prepared in the same manner as in Em-1. However, C1 and E1
When adding 95% of the total amount of C1,
At the same time, H1 was added. Em-2 without adding G1
Was prepared.

Preparation of Comparative Emulsion Em-3 (Preparation of Seed Emulsion-1) Seed Emulsion-1 was prepared as follows.

A1 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxydisuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 odor Potassium iodide 824 g Potassium iodide 70.5 g Water 2825 ml D1 1.75 N Potassium bromide aqueous solution The following silver potential control amount: 42 ° C, JP-B-58-58288, 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. for 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again added. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.06 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.59 μm.
The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Em-3) Using Seed Emulsion-1 and the following solution, a tabular silver halide emulsion Em-3 having a surface silver iodide content of 0 mol% was prepared.

A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxydisuccinate sodium salt (10% ethanol aqueous solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3150 ml with water.

B2 1967 g Potassium bromide Make up to 4151 ml with water.

C2 Silver nitrate 2468 g Make up to 4151 ml with water.

In the reaction vessel, the solution A1 was vigorously stirred while maintaining it at 60 ° C., and a part of the solution B2 and a part of the solution C2 were added thereto over 46 minutes by the simultaneous mixing method. The remaining amount of the solution C2 was added by a double jet method over 24 minutes. During this time, the pH was 5.8 and the pAg was
It was kept at 9.0 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate. That is, they were added at an appropriate addition rate so as to prevent generation of small particles other than the growing seed particles and to prevent polydispersion by Ostwald ripening.

After the addition was completed, the emulsion was cooled to 40 ° C.
1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate 90%) was added as an aggregating polymer agent, and the mixture was stirred for 3 minutes. afterwards,
A 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.6. After stirring for 3 minutes, the emulsion was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Thereafter, 9.0 l of distilled water at 40 ° C. was added, and after stirring and standing, the supernatant was drained. Further, 11.25 l of distilled water was added, and after stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% (by weight) aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes and redispersion. After redispersion, the pH was 5.80 at 40 ° C.,
The pAg was adjusted to 8.06.

When the obtained silver halide emulsion having a surface iodine of 0 mol% was observed with an electron microscope, the average grain size was 0.98.
μ, average thickness 0.22μ, average aspect ratio (AR) about 4.5, the ratio of particles with AR> = 2 is 93%, b / a>
= 5 = 79%, (111) faces accounted for 85%, and the grain size distribution was 20.9% in tabular silver halide grains. The average of the twin plane distance is 0.0
18μ. The particles having a thickness / twin plane distance ratio of 10 or more contain 50% or more of all the particles.

Subsequently, the emulsions Em-1 and Em-
2 was divided into predetermined amounts, the temperature was set to 55 ° C., and 0.2 mol% of silver iodide fine particles were added. 6,6'-dithiodinicotinic acid was added in an amount of 9 × 10 ^-6 mol, and 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene (TA
25 mg of I) and a spectral sensitizing dye (shown in Table 2) were added as a dispersion of solid fine particles. Continue with sulfur sensitizer 1
After adding 0 mg, a solid particulate dispersion of 95 mg of potassium thiocyanate, 12.5 mg of chloroauric acid, and 2 mg of triphenylphosphine selenide was added, and aging was performed for a total of 2 hours. At the end of ripening, 3 TAI as stabilizer
00 mg and the compound of the general formula (1) (addition amounts and addition layers are shown in Table 2) were added. The amount of addition was per mole of AgX.

Emulsion Em-3 was chemically sensitized in the same manner as Em-1 and Em-2 without adding silver iodide fine grains.

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 adjusted to 27 ° C. in advance, and 3,5,
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.

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using both coating solutions, two slide hopper coaters were used to coat both sides of the support at a speed of 80 m / min so that the amount of silver applied to one side of the support was 1.6 g / m ^2. Simultaneous application was performed, and drying was performed for 2 minutes and 20 seconds to obtain a sample.

As the support, a film obtained by biaxially stretching a film-forming polyester containing a naphthalenedicarboxylic acid-containing dicarboxylic acid component and a diol component as main components was used, and an undercoat layer was coated thereon. An X-ray film base colored blue at a concentration of 0.15 was used. Also, when a tin oxide compound is contained in the undercoat layer, it is effective for preventing the photosensitive material from being charged.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4- Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) Various additives were added.

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 of formula (1) (shown in Table 2) mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² gelatin Third layer (protective layer) Solid fine particle dispersion dye 50 mg / m ² gelatin 0.8 g / m ² 4-hydroxy- 6-methyl-1,3,3a, 7-tetrazaindene 200 mg / m ² Polymethyl methacrylate mat agent (area average particle size 7.0 μm) 50 mg / m ² 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 Sodium polyacrylate 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 formula (1) compound (shown in Table 2) mg / m ² compound (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 (CH ₂ O) ₁₁ -H 3 mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ -H 2 mg / m ² C ₈ F ₁₇ SO ₂ N- (C _{3 H 7) (CH 2 CH 2} O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

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[0198]

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[0200]

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[0201]

[Table 2]

Next, each sample was stored for three days under the following two conditions.

Condition A: 23 ° C., 40% RH Condition B: 55 ° C., 40% RH The photographic characteristics were evaluated using the obtained sample. First, the sample is sandwiched between two fluorescent intensifying screens (high-sensitivity intensifying screens described below), a tube voltage of 80 kVp, and a tube current of 100 m via an aluminum wedge.
A, Exposure was performed by irradiating X-rays for 0.05 seconds.

(Production of High Sensitive Intensifying Screen) Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Binder Polyurethane-based thermoplastic elastomer Demolac TPKL-5-262 5 <solid content: 40% > (Manufactured by Sumitomo Bayer Urethane Co., Ltd.) 20 g of nitrocellulose (digestibility: 11.5%) was added to 2 g of methyl ethyl ketone solvent and dispersed with a propeller mixer to obtain a coating solution for forming a phosphor layer having a viscosity of 25 PS (25 ° C.). Prepared (binder / phosphor ratio = 1/22).

Separately, 90 g of a soft acrylic resin solid and 50 g of nitrocellulose were added to methyl ethyl ketone as a coating liquid for forming an undercoat layer, and dispersed and mixed to obtain a viscosity of 3-6.
A dispersion of PS (25 ° C.) was prepared.

A thickness of 250 μm into which titanium dioxide has been kneaded.
Of polyethylene terephthalate (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly applied on the support using a doctor blade, and then gradually raised from 25 ° C to 100 ° C. The coating film was dried by drying to form an undercoat layer on the support (thickness of the coating film: 15 μm).

The above-mentioned coating solution for forming a phosphor layer was uniformly coated with a doctor blade to a thickness of 240 μm, dried, and then compressed. Compression was performed using a calender roll at a pressure of 300 kgw / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of JP-A-6-75097. The characteristics of the obtained intensifying screen were that the phosphor thickness was 160 μm, the phosphor filling rate was 68%, and the sharpness (CTF) was 48%.

Next, an automatic developing machine (SRX manufactured by Konica Corporation)
-502) and processed with a developing solution and a fixing solution having the following formulation. Note that tablets were prepared according to the following operations (A to D).

Procedure (A) 3000 g of hydroquinone as a developing agent is ground in a commercially available bantam mill until the average particle diameter becomes 10 μm. 3000 g of sodium sulfite and 2 parts of potassium sulfite were added to the fine powder.
000 g and 1000 g of Dimaison S were added and mixed in a mill for 30 minutes, and then at room temperature for about 10 minutes in a commercially available stirring granulator.
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material. 25 g of 100 g of polyethylene glycol 6000 was added to the granules thus prepared.
After mixing uniformly for 10 minutes using a mixer in a room humidified at 40 ° C. and below 40% RH, one tablet of the obtained mixture was obtained using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compression tableting was performed with the filling amount per unit being 3.84 g to prepare 2500 tablets A for development replenishment.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, and 200 g of N-acetyl-D, L-penicillamine Grind and granulate as in (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 similar to the above, with the filling amount per tablet being 1.73 g, and compression tableting was carried out.
00 development replenishing tablets B were prepared.

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

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
and perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was subjected to compression tableting using a tableting machine similar to that described above with a filling amount per tablet of 6.202 g to prepare 2500 fixing supplementary tablets C.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18-hydrate 150
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, the mixture is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product. After adding 4 g of sodium N-lauroylalanine to the thus-prepared product and mixing for 3 minutes, the mixture obtained was adjusted to a filling amount of 4.562 g per tablet using the same tableting machine as described above. By compression tableting, 1250 fixing replenishing tablets D were prepared.

Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make up to 1 liter.

At the start of processing of the developing solution (start of running), 16.5 liters of developing solution prepared by diluting a developing tablet with diluting 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 the development processing became 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 (manufactured by Konica Corporation) equipped with a solid processing agent charging member and modified so as to be able to process at a processing speed of 15 seconds was used. During the running, the above-mentioned ^two agents A and B and 0.6 ml of water were added to the developer per 0.62 m ² of the photosensitive material.
The pH of each of Agents A and B when dissolved in 38 ml of water was 10.70. 0.62m ² of photosensitive material in fixing solution
Two C agents, one D agent and 74 ml of water were added per unit. 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.

[0219] Photographic properties (fogging, sensitivity, maximum density) were measured for each sample, and sample No. Based on the result of 1 (1
00). Regarding the residual color contamination, the spectral absorption density at 500 nm of the sample after the development processing was measured and defined as the residual color degree. In addition, evaluation of safelight resistance was performed by irradiating each sample through a red filter having the transmittance shown in FIG. 1 with a white light bulb light from 1.2 m above the sample for 30 minutes, developing as described above, and increasing fog. The value was measured and regarded as safelight resistance. Regarding the residual color degree and safelight fog, Sample No. It is represented by a relative value with the value of 1 being 100, and the smaller the value, the better.

Table 3 shows the evaluation results.

[0219]

[Table 3]

Example 2 A sample of Example 2 was prepared in the same manner as in the chemical sensitization method of Example 1. However, a compound of the general formula (3) was added as shown in Table 4 in place of the solid particulate dispersion of triphenylphosphine selenide. Sample No. Based on 12 results (10
0). Other evaluation methods were the same as in Example 1.

[0221]

[Table 4]

[0222]

[Table 5]

As is clear from the results, when the emulsion of the present invention and the compound of the formula (1) are used in combination, Dmax is high and
Good storage stability. Further, when the dye of the present invention is used,
Further, it is excellent in high sensitivity, excellent in safelight resistance, and with little residual color contamination. In addition, it was confirmed that the sensitivity was hardly impaired even in ultra-rapid processing such as 15 seconds using a solid processing agent, and that even after storage at a high temperature, sensitivity and Dmax maintained high image quality and no fog increase.

[0224]

As described above, a silver halide photographic material having high sensitivity, low fog, high maximum density, excellent safelight resistance and little residual color contamination was obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a spectral transmittance of a red filter for evaluating safelight resistance.

Claims (5)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein the iodine content of the sub-surface to the outermost surface of the silver halide grains is equal to the whole of the grains. A silver halide photographic light-sensitive material, which is 0.01 mol% to 2 mol%, and contains at least one compound represented by the following general formula (1) in the light-sensitive material. Formula (1) R-S- (M) _Y [wherein, R represents an aliphatic group substituted with a water-soluble group, an aromatic group, a heterocyclic group or an alicyclic group. Y represents 1 or 0. M represents a hydrogen atom, an alkali metal atom or a cation. When Y is 0, the general formula (1) represents R = S. ] 2. A silver halide photographic light-sensitive material according to claim 1, comprising at least one of benzimidazolocarbocyanines represented by the following general formula (2): Embedded image [Wherein, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group or alkenyl group, R ₂ and R ₄ each represent an alkyl group, and at least one of R ₂ and R ₄ is a hydrophilic group. Represents an alkyl group substituted with Z ₁ , Z ₂ , Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom or a substituent. X ₁ represents an ion necessary for neutralizing an intramolecular charge, and n represents 1 or 2. However, when an inner salt is formed, n is 1. ] 3. The silver halide photographic material according to claim 1, which contains silver halide grains chemically sensitized in the presence of a selenium compound or a tellurium compound. 4. The silver halide photographic light-sensitive material according to claim 1, which contains silver halide grains chemically sensitized in the presence of a compound represented by the following general formula (3). material. Formula (3) A- (W) _m -Z wherein A is an atom group containing a group that can be adsorbed to silver halide, Z is an atom group containing an unstable selenium site, and W is a divalent atom. In the linking group, m represents 0 or 1. ] 5. A method for continuously processing a silver halide photographic material according to claim 1, 2, 3, or 4 using an automatic processor, wherein each processing solution is continuously processed with a solid processing agent. A method for processing a silver halide photographic light-sensitive material, characterized in that the material is supplied while being supplied.