JPH09274273A - Silver halide photographic material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic material having low fog and high sensitivity by incorporating a specified amido compd. into hydrophilic colloidal layers. SOLUTION: This sensitive material has hydrophilic colloidal layers including a silver halide emulsion layer on the substrate and the colloidal layers contain an N-halosulfonamido compd. and a polysulfide compd. These compds. are preferably added to a silver halide emulsion at the time from the beginning of chemical sensitization to just before application of a sensitive material to the substrate. The N-halosulfonamido compd. is preferably a compd. represented by the formula R5 -SO2 -NXM and releasing active halogen. In the formula, X is halogen, M is a metal and R5 is an aliphatic, arom. or heterocyclic group. Low fog and superior color leaving property are ensured, and even in the case of processing with a developing soln. not contg. hydroquinone, low fog, high sensitivity and superior color leaving property are ensured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having low fog and high sensitivity, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, it has been strongly desired to shorten the processing time and reduce the processing waste liquid in the development processing of silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials). For example, in the medical field, as the number of X-ray photographs taken increases with the increasing number of examinations in general medical care and the establishment of regular medical examinations as the aging society advances, there is a demand for rapid processing after radiography. Furthermore, in recent years, when the problem of global environmental pollution has been widely taken up, the regulations on treatment wastes have become strict, and reduction of the amount of treatment waste liquid has become an urgent issue.

For rapid processing, it is necessary to shorten the processing time such as developing, fixing, washing with water, and drying. However, in the conventional light-sensitive material, if the developing time is simply shortened, the sensitivity and gradation deteriorate. If the fixing time is shortened, the fixing of silver halide becomes incomplete and causes deterioration of image quality. Further, the shortening of the processing time results in insufficient elution of the sensitizing dye, resulting in color contamination by the residual dye. In order to solve these problems, a silver halide photographic light-sensitive material which is excellent in development progress and fixing property, does not deteriorate photographic performance, and elutes a sensitizing dye in a short time and does not cause residual color contamination is required. Is desired.

On the other hand, in order to reduce the processing waste liquid, it is necessary to reduce the fatigue of the processing liquid and to reduce the amount of the replenishing liquid, but this is accompanied by the common problems with the speeding up. As a technique for improving these problems, a technique using benzimidazolocarbocyanines having good decolorizing performance as a spectral sensitizing dye is known. Further, in JP-A-5-61148, a combination of oxacarbocyanine and benzimidazolocarbocyanine as a spectral sensitizing dye in a specific ratio is used in a silver halide emulsion having an iodine content of 1 mol% or less. Alternatively, a technique of performing chemical sensitization with a tellurium compound is disclosed.

However, although these disclosed techniques improve the residual color property, they have the drawbacks that fog tends to occur and high sensitivity cannot be obtained, and the sensitivity to safelight light increases, which causes troubles during work. , Was insufficient to meet the recent demand levels.

On the other hand, it is well known that the iodine contained in silver halide grains affects various photographic performances. For example, in order to shorten the development time, a method of reducing the iodide content, particularly the surface iodide content is known.
However, if the iodine content on the surface of silver halide grains is lowered, the adsorption of the spectral sensitizing dye is deteriorated, and the sensitivity is lowered during the production or storage of the light-sensitive material. On the other hand, when the iodide content on the surface of the silver halide grain is increased, the pressure resistance is improved and the adsorption of the spectral sensitizing dye is enhanced, but the development speed is slowed down, and the sensitivity during development processing within a certain period However, there is an unfavorable problem that the gradation is not excellent and the residual color contamination is increased. In addition, development processing using dihydroxybenzenes as a developing agent is not preferable in terms of work environment management.

When silver chloride having excellent developability is used as the silver halide, the influence of Cl ⁻ ions on the developing solution is Br.
^Since it is very small as compared with ⁻ ions and I ⁻ ions, and accumulation fatigue of the developing solution can be avoided, it is effective, but there is a problem that sufficient sensitivity cannot be obtained with silver chloride grains.

Further, a technique in which flattened silver halide grains are sensitized with selenium to improve sensitivity and image quality is disclosed in, for example, JP-A-4-291252. However, when this technique is subjected to a treatment with a low replenishment of the treatment liquid, there is a drawback that the image quality is deteriorated due to contamination due to the residual sensitizing dye and fog.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having low fog and high sensitivity. Still another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which can obtain the above-mentioned performance even when processed with a developer containing no dihydroxybenzenes and has excellent residual color. is there.

[0010]

The above-mentioned problems of the present invention are as follows. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains an N-halosulfonamide compound. material,

2. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains an N-halosulfonamide compound and a polysulfide compound. Silver photographic material,

3. 3. The silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto contains a compound represented by the following general formula (1).

[0013]

Embedded image In the formula, R ₆ and R ₈ each represent a substituted or unsubstituted alkyl group or alkenyl group, R ₇ and R ₉ represent a lower alkyl group, and at least one of R ₇ and R ₉ represents a hydrophilic group. Represents a substituted alkyl group. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1. Z ₁ , Z
₂ , Z ₃ and Z ₄ are halogen atom, alkyl group, alkoxy group, alkylthio group, trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group, acyl group, sulfonyl group, carbamoyl group, sulfamoyl group, acetylamino group Represents an acetyloxy group and an aryl group.

4. 4. The silver halide photographic light-sensitive material as described in any one of 1 to 3, wherein the silver halide grains contained in the silver halide emulsion layer are selenium-sensitized and / or tellurium-sensitized. ,

5. 5. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to any one of 1 to 4 above in a processing step including a development step (fixing step and drying step if necessary). ,

6. 6. A method for processing a silver halide photographic light-sensitive material as described in 5 above, which comprises processing with a developer containing at least one compound represented by the following general formula (2) in the developer.

[0017]

Embedded image In the formula, R ₁₀ and R ₁₁ are a hydroxy group and —O, respectively.
M represents an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group, and M represents an alkali metal atom or an ammonium group. P and Q represent a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a mercapto group, an alkyl group or an aryl group,
Alternatively, P and Q represent an atomic group necessary for forming a 5- to 8-membered ring by bonding. Y represents = O or = _{N-R 12,.} R ₁₂ is a hydrogen atom, a hydroxyl group, an alkyl group,
Acyl group, hydroxyalkyl group, sulfoalkyl group,
Represents a carboxyalkyl group. Is achieved by each of

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The N-halosulfonamide compound that achieves low fog and high sensitivity for the purpose of the present invention is preferably a compound that releases an active halogen represented by the following general formula (3).

General formula (3) R ₅ —SO ₂ —NXM In the formula, X represents a halogen atom, M represents a metal atom,
R ₅ represents an aliphatic group, an aromatic group or a heterocyclic group.

M is a metal atom, more preferably an alkali metal atom. Examples of the aromatic group represented by R ₅ include those having 6 to 20 carbon atoms, and specific examples thereof include phenyl, naphthyl and anthranyl groups. The aromatic heterocyclic group represented by R ₅ may be a single ring or a condensed ring, and examples thereof include a 5- or 6-membered heteroaromatic ring having at least one kind of O, S, and N atoms in the ring. Specifically, pyrrole, pyridine, pyrimidine, triazine, furan,
Examples thereof include thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and benzerogues thereof. R
₅ is most preferably a benzene ring. The aromatic group or aromatic heterocyclic group represented by R ₅ may be further substituted, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (for example, a methyl group, an 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 (for example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.),
Alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, n-butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino group etc.), alkylthio group (Eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group) 3,
3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl Group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group) Group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), hydroxy group, nitro group, D Roso group, amine oxide group (eg pyridine-oxide group), imide group (eg phthalimido group etc.), disulfide group (eg benzene disulfide group, benzothiazolyl-2-disulfide group etc.), heterocyclic group (eg pyridyl group, benzine group) Imidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.), carboxyl group, sulfo group and the like. The substituent is preferably a methyl group, an ethyl group or a methoxy group, and particularly preferably a methyl group. R ₅ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent.

Specific examples of the N-halosulfonamide compound used in the present invention are listed below, but the present invention is not limited thereto.

[0022]

Embedded image

The N-halosulfonamide compound of the present invention is used in an amount of 1 × 10 ⁻⁸ to 5 mol per mol of silver halide.
It is preferable to contain ^{x10 -1} mol, particularly 1 x 10
^It is preferably ^-7 mol to 2 × 10 ^-1 mol.

Next, the polysulfide compound of the present invention will be described. The polysulfide compound of the present invention is a compound represented by the following general formula (4). In formula (4) R _1- (S) nR ₂ , R ₁ and R ₂ represent an aliphatic group, an aromatic group or a heterocyclic group, and R ₁ and R ₂ are bonded to each other to form a ring. And R ₁ and R ₂ may be the same or different,
n represents an integer of 2 or more and 6 or less.

In the general formula (4), R₁And R₂Represented by
The aliphatic group to be produced has 1 to 30 carbon atoms, preferably 1 to
20 straight chain, branched alkyl, alkenyl, alkynyl
And a cycloalkyl group. In particular,
Methyl, ethyl, propyl, butyl, hexyl, deci
Ru, dodecyl, isopropyl, t-butyl, 2-ethyl
Hexyl, allyl, 2-butenyl, 7-octenyl, pr
Lopargyl, 2-butynyl, cyclopropyl, cyclope
Include cyclohexyl, cyclohexyl and cyclododecyl.
You. R₁And R₂The aromatic group represented by has 6 carbon atoms.
~ 20, specifically phenyl and naphthi
And anthranyl group. R₁And R₂Represented by
The heterocyclic group may be a monocyclic ring or a condensed ring, and O,
5-6 member having at least one of S and N atoms in the ring
And the heterocycle of. Specifically, pyrrolidine, pipette
Lysine, tetrahydrofuran, tetrahydropyran, o
Xylan, morpholine, thiomorpholine, full free
, Thiopyran, tetrahydrothiophene, pyrrole,
Pyridine, furan, thiophene, imidazole, pyrazo
, Oxazole, thiazole, isoxazole, a
Sothiazole, triazole, tetrazole, thiasia
Zole, oxadiazole and their benzerogues
Is mentioned. R₁And R₂To form a ring with
Can be a 4- to 7-membered ring. This is 5
~ 7-membered ring. R₁And R₂And a preferable group is
A telocyclic group, more preferably a heteroaromatic ring group.
You. R₁And R ₂An aliphatic group represented by, an aromatic group, or
The heterocyclic group may be further substituted, and may have a substituent atom or a substituent.
As a substituent, a halogen atom (chlorine atom, bromine atom, etc.),
Alkyl group (eg methyl group, ethyl group, isopropyl
Group, hydroxyethyl group, methoxymethyl group, trifluor
Methyl group, t-butyl group, etc.), cycloalkyl group (eg
For example, cyclopentyl group, cyclohexyl group, etc.), aral
Kill group (for example, benzyl group, 2-phenethyl group, etc.),
Reel group (eg, phenyl group, naphthyl group, p-tolyl group)
Group, p-chlorophenyl group, etc.), alkoxy group (for example,
Methoxy group, ethoxy group, isopropoxy group, n-but
Oxy group, etc., aryloxy group (eg phenoxy group)
Etc.), cyano groups, acylamino groups (eg acetylamido)
Group, propionylamino group, etc.), alkylthio group (eg
For example, methylthio group, ethylthio group, n-butylthio group
Etc.), arylthio groups (eg phenylthio groups, etc.),
Rufonylamino group (for example, methanesulfonylamino group,
Benzenesulfonylamino group, etc., ureido group (eg
3-methylureido group, 3,3-dimethylureido group,
1,3-dimethylureido group, etc.), sulfamoylami
Group (dimethylsulfamoylamino group, etc.), carbamo
Group (eg methylcarbamoyl group, ethylcarbamoyl group
Group, dimethylcarbamoyl group, etc.), sulfamoyl
Groups (eg ethylsulfamoyl group, dimethylsulfamoyl group
Moyl group, etc., alkoxycarbonyl group (eg methoxy group)
Sicarbonyl group, ethoxycarbonyl group, etc.), aryl
Oxycarbonyl group (eg phenoxycarbonyl group
Etc.), sulfonyl group (eg methanesulfonyl group, pig
Sulfonyl group, phenylsulfonyl group, etc.), acyl group
(For example, acetyl group, propanoyl group, butyroyl group
Etc.), amino groups (methylamino group, ethylamino group, di
Methylamino group, etc.), hydroxy group, nitro group, nitro
So group, amine oxide group (eg pyridine-oxide
Group), imide group (eg, phthalimido group, etc.), disulfate
Group (eg benzenedisulfide group, benzothiazo group
Ryl-2-disulfide group, etc., a heterocyclic group (eg,
Pyridyl group, benzimidazolyl group, benzthiazolyl
Group, a benzoxazolyl group, etc.). n is 2 or more
It is an integer of 6 or less, preferably 2 to 5, and more preferably
n = 2.

Specific examples of the compound represented by formula (4) of the present invention are listed below, but the present invention is not limited thereto.

[0027]

[Chemical 6]

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

The polysulfide compound of the present invention contains 1 × 10 ⁻⁸ to 5 × 10 ⁻² mol per mol of silver halide.
It is preferably contained in a molar amount, and particularly preferably 1 × 10 ⁻⁷ to 2 × 10 ⁻² mol. The above N-halosulfonamide compound and polysulfide compound can be used by dissolving them in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide and methylcellosolve. It can also be added as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or an ultrasonic disperser by a method known as a solid dispersion method.

In the present invention, the N-halosulfonamide compound and the polysulfide compound are contained in the hydrophilic colloid layer containing the silver halide emulsion layer. These compounds may be added at any step during the preparation of the silver halide photographic light-sensitive material, but preferably from the start of chemical sensitization of the silver halide emulsion to immediately before coating the silver halide emulsion on the support of the light-sensitive material. It is preferable to add them by no more.

Next, the spectral sensitizing dye of the general formula (1), which is the spectral sensitizing dye for improving the residual color staining property of the present invention, will be described in detail. Examples of the alkyl group substituted in R ₆ and R ₈ of the general formula (1) include hydroxymethyl,
Ethoxycarbonylethyl, ethoxycarbonylmethyl, allyl, benzyl, phenethyl, methoxyethyl,
Examples include groups such as methanesulfonylaminoethyl and 3-oxobutyl, examples of unsubstituted alkyl groups include lower alkyl groups such as methyl, ethyl, propyl and butyl, and examples of alkenyl groups include vinyl group and allyl group. Is mentioned.

Examples of the lower alkyl group represented by R ₇ and R ₉ include groups such as methyl, ethyl, butyl and trifluoroethyl, and examples of the alkyl group substituted with the hydrophilic group include carboxymethyl, carboxyethyl, Methanesulfonylaminoethyl, sulfobutyl, sulfoethyl, sulfopropyl, sulfopentyl, 6-sulfo-
Groups such as 3-oxahexyl, 4-sulfo-3-oxapentyl, 10-sulfo-3,6-dioxadecyl, 6-sulfo-3-thiahexyl, o-sulfobenzyl, p-carboxybenzyl and the like can be mentioned.

Z ₁ , Z ₂ , Z ₃ and Z ₄ are halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.),
Alkyl group (groups such as methyl, ethyl, t-butyl), alkoxy group (methoxy group), alkylthio group (methylthio group), trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl group) Etc.), acyl group (acetyl group), sulfonyl group (methanesulfonyl group), carbamoyl group (N, N-dimethylcarbamoyl, N-morpholinocarbamoyl group, etc.), sulfamoyl group (N, N-dimethylsulfamoyl group, etc.) , An acetylamino group, an acetyloxy group, and an aryl group.

The ion necessary for neutralizing the charge in the molecule represented by X ₂ may be an anion or a cation, and examples of the anion include a halogen ion (an ion such as chlorine, bromine and iodine) and a perk. There are lorate, ethylsulfate, thiocyanate, p-toluenesulfonate, perfluoroborate and the like, and as the cation, for example, hydrogen ion, alkali metal ion (ions such as lithium, sodium and potassium), alkaline earth metal ion (magnesium, Ions such as calcium),
Examples thereof include ammonium ion and organic ammonium ion (triethylammonium, triethanolammonium, tetramethylammonium ion) and the like.

Next, specific examples of the compound (spectral sensitizing dye) represented by the above-mentioned general formula (1) which is preferably used in the present invention are shown, but the invention is not limited thereto.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

As the benzimidazolocarbocyanines spectral sensitizing dye represented by the general formula (1), which is preferably used in the present invention, in addition to the above-mentioned specific examples, for example, Japanese Patent Application No. Hei 5 (1999) -242242.
-261264, Tables 1 and 2, JP-A-5-8829
The compound examples described in Table 1 of No. 3 can be used in the same manner. In order to obtain high sensitivity and to improve residual color contamination, the proportion of the benzimidazolocarbocyanine dye represented by the general formula (1) should be 40% of all dyes in the light-sensitive material.
% Or more is preferable.

The spectral sensitizing dye in the present invention means one that is adsorbed on silver halide grains and contributes to sensitization. The spectral sensitizing dye preferably used in the present invention is adsorbed on silver halide emulsion grains, and the maximum absorption wavelength of the J aggregation band is preferably 555 nm or less when the reflection spectrum is measured. Incidentally, in the application to an X-ray medical light-sensitive material utilizing a fluorescent substance which emits green light, a spectral sensitizing dye preferably used in the present invention is adsorbed on silver halide emulsion grains,
It is preferable that the J-band is formed in the same wavelength range as the green light from the phosphor when its reflection spectrum is measured. That is, the maximum absorption wavelength is preferably 520
It is preferable to select the spectral sensitizing dye so that the J-band having the maximum absorption in the region of ˜555 nm is formed. The thickness is more preferably 530 to 553 nm, and most preferably 540 to 550 nm. The addition temperature of the spectral sensitizing dye of the present invention is preferably 25 to 55 ° C.
More preferably 30 to 45 ° C., and even more preferably 35 to 4
It can be set to any temperature within the range of 3 ° C. The sensitizing aging temperature is preferably 50 to 80 ° C, more preferably 50 to 60 ° C.
It can be set to any temperature within the range.

The spectral sensitizing dye which is the compound represented by the general formula (1) of the present invention may be used in combination with other spectral sensitizing dyes. Dyes used include cyanine, merocyanine, holopolar cyanine, hemicyanine, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes and merocyanine dyes. With these spectral sensitizing dyes,
A dye having no spectral sensitizing property or a substance that does not substantially absorb visible light and exhibits a supersensitizing effect may be added to the emulsion layer.

General formula (1) preferably used in the present invention
The addition amount of the compound represented by is different depending on the type of dye and the structure, composition, ripening condition, purpose and application of the silver halide, but it is a monolayer coating on the surface of each photosensitive grain in the silver halide emulsion. The ratio is preferably less than 65%, more preferably less than 55%. The appropriate amount of the spectral sensitizing dye per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion, but it is 500
It is preferably less than mg, more preferably 400 mg or less.

General formula (1) preferably used in the present invention
When the compound represented by the formula (1) is used, 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, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol.

As the dispersant for the spectral sensitizing dye, there are anionic, cationic, nonionic and amphoteric surfactants as the surfactant, and any of these surfactants can be used. The spectral sensitizing dye is preferably added as a solid fine particle dispersion rather than as a solution of an organic solvent. In particular, it is preferable to disperse it in an aqueous system in which substantially no organic solvent and / or surfactant is present, and to add it in the form of a solid fine particle dispersion that is substantially insoluble in water.

The spectral sensitizing dye preferably used in the present invention may be added during the chemical ripening step, particularly preferably at the beginning of the chemical ripening step, and the desalting step is completed after the nucleation step of the silver halide emulsion. By adding the above, a high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained, but at any time from the end of the desalting process to the chemical ripening process to immediately before the coating process. A spectral sensitizing dye which is the same as or different from the dye added during the period from the nucleation step to the end of the desalting step may be additionally added.

The selenium sensitizers preferably used in the chemical sensitization of the present invention include a wide variety of selenium compounds. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, triethyl N, N, N′-selenourea). , N, N,
N'-trimethyl-N'-heptafluoroselenourea,
N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenacetone, selenacetophenone) Etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates ( For example, tri-p-
Triselenophosphate, etc.), selenides (triphenylphosphine selenide, diethyl selenide,
And diethyl diselenide). Particularly preferred selenium sensitizers are selenides, selenoureas, selenoamides, and selenoketones.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally 10-8 to 10-per mol of silver halide.
Use about 4 moles. The temperature of chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90C, more preferably 45C or more and 80C or less. The pH is 4-9, p
Ag is preferably in the range of 6.0 to 9.5.

Preferably used for the chemical sensitization of the present invention,
Examples useful as tellurium sensitizers include telluroureas (eg, N, N-dimethyltelluroura, tetramethyltelluroura, N-carboxyethyl-N, N'-dimethyltelluroura, N, N'-dimethyl- N'phenyl tellurourea), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg telluroacetamide) , N, N-dimethyl tellurobenzamide),
Examples include telluroketones, telluroesters, and isotellurocyanates. The technique for using the tellurium sensitizer is similar to that for the selenium sensitizer.

In the present invention, it is also preferable to use reduction sensitization together. 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.

In the present invention, the sensitization can be performed with a selenium compound or a tellurium compound, but further with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and sensitization can be performed by combining these methods.

Specific examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, and rhodanine derivatives. Preferred examples include dithiacarbamic acids, polysulfide organic compounds, and simple sulfur. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As the gold sensitizer, 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 ⁻⁹ mol to 1 × 10 ⁻⁴ mol. More preferably, it is 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol.

The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols, other inorganic or organic solvents and adding them in the form of a solution, or by adding a water-insoluble solvent or gelatin. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium. Both sulfur sensitization and gold sensitization may be performed simultaneously or separately and stepwise. In the latter case, favorable results may be obtained if gold sensitization is performed after or during sulfur sensitization appropriately.

Reduction sensitization is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion, as is carried out during the growth of silver halide grains of the silver halide emulsion. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

In the present invention, fine grain silver halide can be added during the process from chemical ripening to coating. Here, during the process from the chemical ripening to the coating includes during the chemical ripening, and thereafter, when it is subjected to coating for constituting a light-sensitive material, fine grain silver halide is added until then. Means that.

For example, when fine grain silver iodide is added for the purpose of enhancing the adsorption of the spectral sensitizing dye, it may be added at any step from the chemical ripening step to immediately before coating. , Preferably in the chemical ripening step. The term "chemical ripening step" as used herein refers to a period from the time when the physical ripening and desalting operations of the emulsion of the present invention are completed to the time when an operation for adding a chemical sensitizer and then stopping the chemical ripening is performed. Refers to. Further, the addition of fine grain silver iodide may be carried out in several times with a time interval, or another chemically ripened emulsion may be added after the addition of fine grain silver iodide. The temperature of the emulsion of the present invention when the fine grain silver iodide is added is preferably in the range of 30 to 80 ° C, and more preferably 40 to 65 ° C.
The range of ° C. is particularly preferred. Further, the present invention is preferably carried out under the condition that after the addition of the fine grain silver iodide to be added and immediately before coating, a part or all of the fine grain silver iodide disappears. More preferable condition is 20% of the fine grain silver halide added. The above is the disappearance just before coating.

The silver halide grains of the silver halide emulsion of the present invention include silver iodobromide, silver chloroiodide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver bromide. Can be optionally used, but silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, and silver chloride are particularly preferable.

In the present invention, the silver chloride content is preferably 20 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more. In the case of silver iodochloride, the content of silver iodide is 0.01 mol% as the average content of silver iodide in the entire silver halide grains.
The above content is preferably 1.0 mol% or less, more preferably 0.01 mol% or more and 0.5 mol% or less.

The tabular silver halide grains used in the present invention will be described below. The tabular silver halide grains used in the present invention may have an even number of parallel twin planes or may not have twin planes.

In the silver halide grains of the silver halide photographic light-sensitive material of the present invention, 50% or more of the total projected area of the emulsion layer has an average aspect ratio (ratio of grain size of silver halide grains / thickness of grains) of 2. The above tabular grains are preferably those having an aspect ratio of 2 or more and 100 or less, and particularly preferably 3 to 20. When the aspect ratio is less than 2, the effect of the present invention is small in terms of sensitivity and rapid processability,
If the aspect ratio is larger than 100, the pressure resistance is extremely deteriorated.

Most of the outer walls of the crystals of the tabular silver halide grains are composed of (111) faces, or (10).
It may be composed of the (0) plane. Also, (111)
It may have both a plane and a (100) plane.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, (standard deviation of thickness / average thickness) × 100 = 25% or less is preferable when the width of the distribution is defined by the width (%) of the thickness distribution, and more preferably 20% or less And particularly preferably 15% or less.

The average silver iodide content of the silver halide emulsion according to the present invention is preferably 1 mol% or less, more preferably 0 to 0.8 mol%. In the grains having a layer structure having different halogen compositions, grains having a high silver iodide phase in the grain interior and the outermost surface layer are preferred. At this time, the silver iodide content of the inner layer (core) having the highest silver iodide content is 2.5 mol%.
The above is preferable, more preferably 5 mol% or more, and the silver iodide content of the outermost surface layer (shell) is 10 mol%.
In the following, it is preferably 0.1 to 4 mol%. The silver iodide distribution in the core is usually uniform, but it may have a distribution. For example, the concentration may increase from the center toward the outside, or may have a maximum or minimum concentration in the intermediate region.

The silver halide grains may be so-called halogen conversion type grains. The amount of halogen conversion is preferably 0.2 mol% to 2.0 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening.

The silver halide grain according to the present invention contains a cadmium salt during the grain formation process and / or the growth process.
At least one metal ion selected from zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (including complex salt) is added to the inside of the particle and / or Alternatively, these metal elements can be contained in the grain surface layer, and reduction sensitization nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

In the silver halide emulsion, unnecessary soluble salts may be removed at the end of the growth of the silver halide grains, or they may remain contained. To remove salts, Research Disclosure (RD) No. 17
It can be performed based on the method described in Item 643, Item II.

The silver halide photosensitive material according to the present invention comprises
Various photographic additives can be used. Known additives include, for example, RD-No. No. 17643 (December 1978); No. 18716 (November 1979) and the same No. 308119 (December 1989). The types of compounds and the locations described in these three RDs are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25 -26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-27 XI 650 Right 1005-6 XI Charge Inhibitor 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1009-4 XXII Support 28 28 XVII 009 XVII

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643-2.
8 and RD-308119, page 1009. A suitable support is polyethylene terephthalate or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve adhesion of the coating layer.

When the present invention is applied to medical X-ray radiography, for example, an intensifying screen containing a phosphor as a main component which emits near-ultraviolet light or visible light upon exposure to penetrating radiation is used. This is brought into close contact with both surfaces of a light-sensitive material obtained by coating the emulsion of the present invention on both surfaces and exposed. The penetrating radiation referred to here is a high-energy electromagnetic wave and means X-rays and γ-rays.

Examples of preferable phosphors used in the fluorescent intensifying screen include those shown below. Tungstate phosphor (CaWO ₄ , MgWO ₄ , CaWO ₄ : P
b), terbium activated rare earth oxysulfide 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, [Y. Gd] O ₂
S: Tb, Tm, etc.], terbium-activated rare earth phosphate phosphor (YPO ₄ : Tb, GdPO ₄ : Tb, LaP
O ₄ : Tb), terbium-activated rare earth oxyhalide-based phosphors (LaOBr: Tb, LaOBr: Tb.
Tm, LaOCl: Tb, LaOCl: Tb. Tm. L
aOBrTb GdOBr: Tb GdOCl: Tb
Etc.), thulium-activated rare earth oxyhalide-based phosphors (LaOBr: Tm, LaOCl: Tm, etc.), barium sulfate-based phosphors (BaSO ₄ : Pb, BaSO ₄ : Eu).
²⁺ , [Ba. Sr] SO ₄ : Eu ²⁺ etc.) divalent eurobium-activated alkaline earth metal phosphate-based phosphor ([B
a ₂ PO ₄ ] ₂ : Eu ^2+, etc.) Divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor (BaF)
Cl: Eu ²⁺ , BaFBr: Eu ²⁺ , BaFCl:
Eu ²⁺ . Tb, BaFBr: Eu ²⁺ . Tb, BaF
₂・ BaCl ・ KCl: Eu ²⁺ , [Ba ・ Mg] F ₂
* BaCl * KCl: Eu < ^2- > etc., iodide type fluorescent substance (CSI: Na, CSI: Tl, NaI, KI: Tl).
Etc.), sulfide-based phosphor (ZnS: Ag [Zn.Cd])
S: Ag, [Zn. Cd] S: Cu, [Zn. Cd]
S: Cu. Al, etc.), Hafnium phosphate-based phosphor (HfP
₂ O ₇ : Cu, etc., tank-phosphate-based phosphor (YTa
O ₄ , YTaO ₄ : Tm, YTaO ₄ : Nb, [Y. S
r] TaO ₄ : Nb, GdTaO ₄ : Tm, Gd ₂ O _{3
· Ta 2 O 5 · B 2} O 5: Tb , etc.), provided that the phosphor used in the present invention is not limited to, as long as to emit light in the visible or near-ultraviolet region by irradiation Can be used.

The fluorescent intensifying screen is preferably filled with the phosphor in a gradient grain size structure. In particular, it is preferable to coat large-sized phosphor particles on the surface protective layer side, and to coat small-sized phosphor particles on the support side.
In the case of a particle having a large particle diameter of 10 μm, the range of 10 to 30 μm is preferable.

The fluorescent intensifying screen is manufactured by a step of forming a phosphor sheet composed of a binder and a phosphor, placing the phosphor sheet on a support, and at a temperature equal to or higher than the softening temperature or melting point of the binder. It is preferably produced in a step of adhering the phosphor sheet to a support while compressing.

For the phosphor sheet to be the phosphor layer of the fluorescent intensifying screen, the coating solution in which the phosphor is uniformly dispersed in the binder solution is applied onto a temporary support for forming the phosphor sheet and dried. After that, it can be manufactured by peeling from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent and mixed by stirring to prepare a coating liquid in which the phosphor is uniformly dispersed in the binder.

The binder has a softening temperature or melting point of 30.
A thermoplastic elastomer at ~ 150 ° C is used alone or together with another binder. Since the thermoplastic elastomer has elasticity at normal temperature and becomes fluid when heated, it is possible to prevent the phosphor from being damaged by the pressure at the time of compression. Examples of the thermoplastic elastomer are selected from the group consisting of polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least one thermoplastic elastomer may be mentioned. The mixing ratio of the thermoplastic resin in the binder may be 10% by weight or more and 100% by weight or less, but the binder is composed of as many thermoplastic elastomers as possible, particularly 100% by weight of the thermoplastic elastomer. preferable.

Examples of the solvent for preparing the coating solution include lower alcohols such as methanol, ethanol, n-propanol and n-butanol, chlorine atom-containing hydrocarbons such as methylene chloride and ethylene chloride, acetone, methyl ethyl ketone and methyl isobutyl ketone. And ketones, esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate and butyl acetate, ethers such as dioxane, ethylene glycol monoethyl ester and ethylene glycol monomethyl ester, and mixtures thereof.

The mixing ratio of the binder and the phosphor in the coating liquid varies depending on the characteristics of the target intensifying screen, the kind of the phosphor, etc., but generally the mixing ratio of the binder and the phosphor is 1: 1 to 1. : 100 (weight ratio), particularly preferably 1: 8 to 1:40 (weight ratio).
The coating liquid may be a dispersant for improving the dispersibility of the phosphor in the coating liquid, or a plasticizer for improving the binding force between the binder and the phosphor in the phosphor layer after formation. Etc., various additives may be mixed.

Examples of dispersants include phthalic acid, stearic acid, caproic acid, lipophilic surfactants and the like. Examples of the plasticizer include triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, and other phosphoric acid esters, diethyl phthalate, dimethoxyethyl phthalate, and other phthalic acid esters, glycol glycolate such as ethylphthalylethyl glycolate, and butylphthalbutyl glycolate. Acid ester,
Examples thereof include polyesters of triethylene glycol and adipic acid, polyesters of polyethylene glycol such as polyesters of diethylene glycol and succinic acid, and aliphatic dibasic acids.

The coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for sheet formation to form a coating film of the coating solution. As the coating means, for example, a doctor blade, a roll coater, a knife coater or the like can be used.

As the temporary support, for example, those made of various materials such as glass, wool, cotton, paper and metal can be used, but as the information recording material, a flexible sheet in handling. Alternatively, those that can be processed into rolls are preferable. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, aluminum foil,
Metal sheets such as aluminum alloy foil, general paper, and base paper for printing such as photographic base paper, coated paper, or art paper, baryta paper, resin-coated paper, and Belgian Patent No. 784,615. Particularly preferred are papers sized with such polysaccharides, pigment papers containing pigments such as titanium dioxide, and processed papers such as papers sized with polyvinyl alcohol.

A coating solution for forming a phosphor layer is applied onto a temporary support, dried, and then peeled from the temporary support to obtain a phosphor sheet which becomes a phosphor layer of an intensifying screen. Therefore, it is preferable that the surface of the temporary support is coated with a release agent in advance so that the formed phosphor sheet is easily separated from the temporary support.

The above will be described. A support for setting the phosphor formed as described above is prepared. This support can be arbitrarily selected from the materials listed for the temporary support. In order to strengthen the bond between the support and the phosphor layer, the fluorescent intensifying screen may be coated with a high molecular substance such as gelatin on the surface of the support to provide an undercoat layer to provide adhesiveness, sensitivity, image quality (sharpness). In order to improve (granularity), a light reflecting layer made of a light reflecting substance such as titanium dioxide or a light absorbing layer made of a light absorbing substance such as carbon black may be provided. The support used in the present invention can also be provided with these various layers, and the constitution thereof can be arbitrarily selected according to the desired purpose and application of the intensifying screen.

The phosphor sheet obtained by the above is placed on a support, and the phosphor sheet is adhered on the support while being compressed at the softening temperature or the melting point or higher of the binder.

By utilizing the method of pressing the phosphor sheet on the support without fixing it in advance in this manner, the sheet can be spread thinly and not only the damage of the phosphor is prevented but also the sheet is not damaged. It is possible to obtain a high phosphor filling rate even at the same pressure as compared with the case of fixing and pressurizing.

Examples of the compression device used for the compression treatment include calender rolls, hot presses and the like which are generally known. For example, the compression treatment with a calender roll is carried out by placing the phosphor sheet obtained by on a support and passing it between rollers heated to a softening temperature or melting point of the binder or higher at a constant speed. The pressure during compression is 50 kg / cm
^It is preferably ² or more.

Usually, the fluorescent intensifying screen has a phosphor layer physically formed on the surface of the phosphor layer on the side opposite to the side in contact with the support.
A transparent protective film is provided for chemical protection. It is preferable to install such a transparent protective film also in the fluorescent intensifying screen of the present invention. The thickness of the protective film is generally in the range of 0.1 to 20 μm.

The transparent protective film is, for example, cellulose acetate,
A solution prepared by dissolving a cellulose derivative such as nitrocellulose, or a synthetic polymer substance such as polymethyl methacrylate, polyethylene terephthalate, polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer in an appropriate solvent. Can be formed on the surface of the phosphor layer.

Alternatively, a plastic sheet made of polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyvinylidene chloride, polyamide or the like, and a protective film forming sheet such as a transparent glass plate are separately prepared and appropriately adhered to the surface of the phosphor layer. It can be formed by a method such as bonding with an agent.

As the protective layer used in the fluorescent intensifying screen of the present invention, a film formed of a coating film containing a fluorine-based resin soluble in an organic solvent is particularly preferable. The fluorine-based resin refers to a polymer of an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer. The film formed by the coating film of the fluorine-based resin may be cross-linked. Fluorine-based protective film has the advantage that stains such as plasticizers that come out of the film when it comes into contact with other materials or X-ray film do not easily soak into the protective film, so that stains can be easily removed by wiping, etc. There is.

When an organic solvent-soluble fluorine resin is used as the protective film forming material, this resin was prepared by dissolving it in an appropriate solvent. That is, the protective film is formed by uniformly applying a protective film-forming material coating solution containing an organic solvent-soluble fluorine-based resin on the surface of the phosphor layer using a doctor blade or the like, and drying the applied solution. The formation of this protective film may be performed simultaneously with the formation of the phosphor by simultaneous multilayer coating.

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component, and includes polytetrafluoroolefin, polychlorotrifluoroethylene, poly Examples thereof include ethylene fluoride, polyvinyl fluoride, polyvinylidene fluoride, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluoroolefin-vinyl ether copolymer.

Fluorine-based resins are generally insoluble in organic solvents, but a copolymer containing a fluoroolefin as a copolymer component becomes soluble in an organic solvent due to a constitutional unit other than the fluoroolefin to be copolymerized. The protective layer can be easily formed by applying a solution prepared by dissolving in a suitable solvent onto the phosphor layer and drying. Examples of such copolymers include fluoroolefin-
A vinyl ether copolymer can be mentioned. Also,
Since polytetrafluoroethylene and its modified products are also soluble in a suitable fluorine-based organic solvent such as a perfluoro solvent, a protective film can be formed by coating in the same manner as a copolymer containing the above fluoroolefin as a copolymer component. Can be formed.

The protective film may contain a resin other than a fluorine-based resin, and may contain a crosslinking agent, a film hardener, an anti-yellowing agent and the like. However, in order to sufficiently achieve the above-mentioned object, the content of the fluorine-based resin in the protective film is preferably 30% by weight or more, more preferably 50% by weight or more, and most preferably 70% by weight or more. is there.

Examples of the resin other than the fluorine-based resin contained in the protective film include polyurethane resin, polyacrylic resin, cellulose derivative, polymethylmethacrylate, polyester, epoxy resin and the like.

The protective film of the fluorescent intensifying screen used in the present invention is either a polysiloxane skeleton-containing oligomer or a perfluoroalkyl group-containing oligomer,
Or you may form from the coating liquid containing both.

The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton, and preferably has at least one functional group, for example, a hydroxyl group, and has a molecular weight of 500 to 10
It is preferably in the range of 10,000. In particular, the molecular weight is preferably in the range of 1,000 to 100,000, more preferably 3,000 to 100,000. The oligomer containing a perfluoroalkyl group, for example, a tetrafluoroethylene group, desirably has at least one functional group, for example, a hydroxyl group in the molecule, and has a molecular weight of 500 to 100,0.
It is preferably in the range of 00. Especially the molecular weight is 1,0
It is preferably in the range of 00 to 100,000.

If an oligomer containing a functional group is used, a cross-linking reaction occurs between the oligomer and the protective layer film forming resin during formation of the protective film, and the oligomer is incorporated into the molecular structure of the film forming resin. Since the oligomer is not removed from the protective layer even by an operation such as repeated use of the fluorescent intensifying screen for a long period of time or cleaning of the protective layer surface, the addition effect of the oligomer is effective for a long period of time, so that the functional group has a functional group. The use of oligomers is advantageous.
The oligomer is preferably contained in the protective layer in an amount of 0.01 to 10% by weight, and particularly preferably 0.1 to 2% by weight.

The protective layer may contain perfluoroolefin resin powder or silicon resin powder.
As the perfluoroolefin resin powder or the silicon resin powder, those having an average particle diameter of 0.1 to 10 μm are preferable, and particularly preferable is an average particle diameter of 0.3 to 5
It is in the range of μm. These perfluoroolefin resin powders or silicone resin powders are preferably contained in the protective layer in an amount of 0.5 to 30% by weight, and further in an amount of 2 to 20% by weight, based on the weight of the protective film. Is preferred, and most preferably in an amount of 5 to 15% by weight.
The protective film of the fluorescent intensifying screen is preferably a transparent synthetic resin layer having a thickness of 5 μm or less formed by coating on the phosphor layer. By using such a thin protective layer, the distance from the phosphor of the fluorescent intensifying screen to the silver halide emulsion layer is shortened, which contributes to the improvement of the sharpness of the obtained X-ray image.

The filling rate of the phosphor as referred to in the present invention can be determined from the porosity of the phosphor layer formed on the support by the following formula.

[0102]

[Equation 1] However, V: total volume of the phosphor layer Vair: air volume in the phosphor A: total weight of the phosphor px: density of the phosphor py: density of the binder pair: air density a: weight of the phosphor b: Weight of Binder Further, in the formula (1), since the pair is almost 0, the formula (1) can be approximately represented by the following formula (2).

[0103]

[Equation 2] However, the definitions of V, Vair, A, px, py, a, and b are the same as in formula (1). In the present invention, the porosity of the phosphor layer is calculated by the equation (2). The filling rate of the phosphor can be calculated by the following equation (3).

[0104]

(Equation 3) However, the definitions of V, Vair, A, px, py, a, and b are the same as in formula (1).

In the present invention, the X-ray energy of 80 is obtained by the X-ray generator whose intrinsic filtration is equivalent to 2.2 mm of aluminum.
It preferably exhibits an absorption amount of 45% or more for kVp X-rays. It is more preferably 50% or more. The X-ray absorption amount of the fluorescent intensifying screen is measured by the following method.

3 mm of X-rays generated from a tungsten target tube operated at 80 kVp with three-phase power supply
Through the aluminum plate of the target tube to reach the sample fluorescent intensifying screen fixed at a position of 200 cm from the tungsten anode of the target tube, and then the amount of X-rays transmitted through the fluorescent intensifying screen was measured. The absorption amount of X-rays is obtained by measurement using an ionization type dosimeter at a position 50 cm after the phosphor layer. In addition, as a reference, the X-ray dose measured by the above-described measuring device without passing through the fluorescent intensifying screen can be obtained. The thickness of the phosphor is preferably 135 μm or more and 200 μm or less. More preferably, the filling rate of the phosphor at this time is 68% or more.

Next, preferable development processing of the light-sensitive material of the present invention will be described. The developer for developing the light-sensitive material of the present invention does not contain a dihydroxybenzene-based agent as a developing agent, and is treated with a developing treatment solution containing the developing agent represented by the general formula (2).

In formula (2), R ₁₀ and R ₁₁ each represent a hydroxy group, —OM, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. , M represents an alkali metal atom or an ammonium group. Preferred examples of R ₁₀ and R ₁₁ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. P and Q represent a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a mercapto group, an alkyl group or an aryl group,
Alternatively, P and Q represent an atomic group forming a 5- to 8-membered ring together with the vinyl carbon atom to which R ₁₀ and R ₁₁ are bonded and the carbon atom to which Y is bonded. Y represents = O or = _{N-R 12,.} R ₁₂ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. More preferred are a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring and a uracil ring. The developing agent represented by the general formula (2) is 0.005 to 1 liter of the developing solution.
It is preferable to use 0.5 mol, and more preferably 0.
It is from 02 to 0.4 mol.

The developing agents represented by the above general formula (2) are shown below, but the present invention is not limited thereto.

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

The above compounds are commercially available as ascorbic acid, erythorbic acid or their derivatives, or can be synthesized by a known method.

The developer contains sulfites such as potassium sulfite, sodium sulfite, reductones, as preservatives.
For example, piperidinohexose reductone and the like may be included, and these are preferably 0.2 to 1 mol / liter,
It is more preferable to use 0.3 to 0.6 mol / liter.

The developing solution may have a pH such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate or potassium triphosphate as an alkaline agent.
Contains regulators. Further, borate described in JP-A-61-28708, saccharose described in JP-A-60-93439,
A buffering agent such as acetoxime, 5-sulfosalicylic acid, phosphate or carbonate may be used. The content of these agents is such that the pH of the developer is 9.0 to 13, preferably 10 to 10.
Choose to be 12.5. The solubilizing agent may include polyethylene glycols and their esters, and the sensitizing agent may include, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like. As the silver sludge inhibitor, a silver stain inhibitor described in JP-A-56-106244, a sulfide or disulfide compound described in JP-A-3-51844, and a cysteine derivative or a triazine compound described in JP-A-4-92947 are preferably used. To be

As the azole-based organic inhibitor, for example, indazole-based, imidazole-based, benzimidazole-based, triazole-based, benztriazo-based, tetrazole-based, thiadiazole-based compounds and the like are used. Inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition, L. F. A. Menson's "Photographic Processing Chemistry" published by Focal Press (1966), 226-2
29, U.S. Pat. Nos. 2,193,015 and 2,59
Those described in 2,364, JP-A-48-64933 and the like may be used.

As a chelating agent for masking calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate-stabilizing constant with iron of 8 or more as an organic chelating agent described in JP-A No. 1-193853 is used. Is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate. As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

In the present invention, the processing temperature of the developing solution is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The developing time is 5 to 90 seconds, more preferably 8
~ 60 seconds. In the processing method of the present invention, the total processing time is 1
It is preferably processed by an automatic developing machine for 0 to 45 seconds. The total processing time referred to here is Dry to Dry.
The running time from the insertion of the film to the completion of drying is preferably 10 to 30 seconds.

The replenishment in the present invention replenishes the treatment agent fatigue and oxidative fatigue. The replenishment method is disclosed in JP-A-55-1.
No. 26243, width and feed speed, replenishment by area, described in JP-A-60-104946,
Area replenishment controlled by the number of continuously processed sheets described in No. 9156 may be used, and a preferable replenishment amount is 15 ml / 4 cutting (194 ml / m ² ) or less. More preferably 7
It is less than or equal to ml / 4 (90 ml / m ² ).

The fixing liquid may include a fixing material generally used in the art. Examples of the fixing agent include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable in view of the fixing speed. Other fixers include preservatives such as sulfite and bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid) and organic acids (citric acid, oxalic acid, malic acid, etc.), if desired. It may contain various acids such as hydrochloric acid, pH adjusting agents such as metal hydroxides (potassium hydroxide, sodium hydroxide) and chelating agents having the ability to soften water. As a fixing accelerator,
For example, JP-B-45-35754 and 58-12253.
5, thiourea derivatives described in JP-A-58-122536,
Examples thereof include thioethers described in US Pat. No. 4,126,459.

The silver halide photographic light-sensitive material of the present invention can be processed with 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 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.

To solidify the processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is coated with a water-soluble binder. Arbitrary means such as forming a coating layer by spraying can be adopted (Japanese Patent Application Nos. 2-1358787 and 2-20).
No. 3165, No. 2-203166, No. 2-20316
No. 7, No. 2-203168, No. 2-300409).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, spray drying granulation and the like are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. 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 pre-ketting machine can be used. The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling properties or dust when used on the user side, cylindrical, so-called tablets are used. preferable. More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing the tablet treating agent is described in, for example, JP-A Nos. 51-61837, 54-155038 and 52-52.
No. 88025, British Patent No. 1213808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-109.
It can be produced by a general method described in the specification of JP-A Nos. 043, 3-39735 and 3-39939. Further, the powder treating agent is described in, for example, JP-A-54-13333.
No. 2, British Patent No. 725892, No. 729862, and German Patent No. 3733861.

[0127] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g ^/ cm ³ ~2.5g ^/ cm 3 is preferably 1. 0
g / cm ³ , in terms of the strength of the solid obtained,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

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.

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably, all components of the treating agent are 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 to add all of the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
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 in the processing 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 a developer, it is necessary to make all the alkali agents and reducing agents into solid processing agents, and in the case of tablets, to make at least 3 agents and most preferably 1 agent. 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 the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Publication No. 63-137783 and 63-9.
There are known methods such as Japanese Patent No. 7522 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 powders, it is disclosed in Japanese Utility Model Application Laid-Open No. 62-819.
64, 63-84151, JP-A-1-29237.
No. 5, the gravity drop method described and the actual exploitation Sho 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, a preferable method is, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent which is previously weighed and divided and packaged is opened in accordance with the processing amount of the light-sensitive material. A method of taking it out is possible. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably one replenishment amount, and the package is separated in two directions or the package A part of it is opened so that it can be taken out. 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 composed of at least two packaging materials sandwiching the solid processing agent is adhered or adhered to each other at their contact surfaces so that the periphery of the solid processing agent can be separated. . 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, it is conceivable that 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 the processing amount information. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. Further, when the treatment agent is packaged and needs to be opened, the driving means for separating or opening based on the obtained supply start signal operates, and the driving means for separating or opening based on the supply stop signal is It can be controlled to stop.

The above-mentioned solid processing agent supply means has a control means for charging a fixed amount of the solid processing agent according to information on the processing amount of the photosensitive material, which is an important requirement in the present invention.
That is, in the automatic developing machine of the present invention, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance. What is the processing amount information of silver halide photographic light-sensitive materials?
It is a value proportional to the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, 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. It indicates indirectly or directly the amount of reduction of the treating agent in the liquid. The detection may be performed at any time before or after the photosensitive material is carried into the processing solution, 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.

In the present invention, the place where the solid processing agent is charged may be in the processing tank, but it is preferable that the solid processing agent is communicated with the processing section for processing the light-sensitive material and the processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the processing section because there is a certain amount of processing liquid circulation between the processing section and the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

[0139]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Example 1 (Em-1 of Preparation) A1 ossein gelatin 24.2g Water _{9657ml HO (CH 2 CH 2 O} ) n- [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) mH ( n + m = 5 to 7, 10% methanol aqueous solution) 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g water 2825 ml D1 ossein gelatin 121 g water 2040 ml HO (CH _{2 CH 2 O) n- [CH (} CH 3) CH 2 O] 17 - (CH 2 CH 2 O) mH (n + m = 5~7,10% aqueous methanol) 5.70ml E1 1.75N potassium bromide aqueous solution below Silver potential control amount

Japanese Patent Publications No. 58-58288 and No. 5 at 35 ° C.
Solution A1 using the mixing stirrer described in No. 8-58289.
Then, 475.0 ml of each of solution B1 and solution C1 was added by the simultaneous mixing method over 2.0 minutes to perform nucleation.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., add the whole amount of D1 and adjust the pH to 5% with 3% KOH.
After adjusting to 5, the solution B1 and the solution C1 were again added by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. The temperature rise from 35 ° C. to 60 ° C. and the solution B1,
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during resimultaneous mixing with C1 was measured with a solution D
1 was used to control to +8 mV and +30 mV, respectively.

After the addition was completed, the pH was adjusted to 6.0 with 3% KOH, and immediately desalted and washed with water. In this emulsion, 90% or more of the total projected area of silver halide grains are hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.090 μm and an average grain size. (Circle diameter conversion)
Was confirmed to be 0.510 μm with an electron microscope.

Subsequently, after the emulsion was heated to 53 ° C.,
The N-halosulfonamide compound of the present invention is added at 2 × 10 ⁻⁵ mol per mol of silver halide, and the polysulfide compound is added at 2 × 10 ⁻⁶ mol per mol of silver halide, and then a predetermined amount of the spectral sensitizing dye is added. After addition as a solid particulate dispersion, 4-hydroxy-6-methyl-1,3,3
Add a mixed solution of a, 7-tetrazaindene (TAI), adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, silver iodide fine grain emulsion and a dispersion of triphenylphosphine selenide, and the total is 2 hours and 30 minutes. Aged. At the end of the aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. The spectral sensitizing dyes and other additives and the addition amounts (per mol of AgX) are shown below. Spectral sensitizing dye (listed in Table 3) 6.5 × 10 ⁻⁴ mol TAI 20 mg adenine 5 mg sodium thiosulfate 5.0 mg ammonium thiocyanate 50 mg chloroauric acid 2.5 mg silver iodide fine grain emulsion (average particle size 0 5 μm) Sensitizer a (triphenylphosphine selenide) 6.0 mg Stabilizer (TAI) 750 mg

The spectral sensitizing dye was prepared as a solid fine particle dispersion according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used at 3.500 rpm
m by stirring 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. Immediately after that, the residual concentration of ethyl acetate was reduced to 0.3 under reduced pressure.
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 in the above experiment.

(Preparation of Em-2) The above Em-1 was used as seed milk.
Tabular silver iodobromide was prepared by using the following four solutions as agents.
A grain emulsion Em-2 was prepared. A2 ossein gelatin 19.04g HO (CH₂CH₂O) n- [CH (CH₃) CH₂O]₁₇-(CH₂CH ₂ O) mH (n + m = 5 to 7, 10% aqueous methanol solution) 2.0 ml Potassium iodide 7.00 g (seed emulsion) Em-1 1.55 mol equivalent Water is made up to 2800 ml. B2 1493 g potassium bromide Make up to 3585 ml with water. C2 Silver nitrate 2131 g Water to make 3585 ml. D2 3% by weight gelatin and silver iodide grains (average grain size 0.05 μm) fine grain emulsion (*) 0.028 mol equivalent (*) 0.06 mol potassium iodide 5.0% by weight
7.06 mol of glass in 6.64 liters of gelatin aqueous solution
That of an aqueous solution containing silver oxide and 7.06 moles of potassium iodide
2 liters of each were added over 10 minutes. Fine particle form
The pH during growth was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C.
I controlled. After particle formation, use sodium carbonate aqueous solution
The pH was adjusted to 6.0.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 55 ° C., and half of the solution B2 and the solution C2 were added thereto by the simultaneous mixing method over 35 minutes, while the pH was adjusted to 5.8. I kept it. After adjusting the pH to 8.8 with a 1% KOH solution, a part of the solution B2 and the solution C2 and the total amount of the solution D2 were added by the simultaneous mixing method. Next, after adjusting the pH to 6.0 with 0.5% citric acid, the solution B2 and the solution C were
The remaining amount of No. 2 was added by a double jet method over 25 minutes. During this time, the pAg was kept at 8.9 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, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. After the addition was completed, desalting, washing with water and redispersion were carried out. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.2 at 40 ° C. When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.91 μm, the average thickness was 0.23 μm,
Average aspect ratio about 4.0, width of particle size distribution 20.5%
It was a tabular silver halide grain.

Subsequently, after the emulsion was heated to 47 ° C.,
As shown in Table 3, the N-halosulfonamide compound of the present invention was 1 × 10 ⁻⁵ mol per mol of silver halide, and the polysulfide compound was 1 mol per mol of silver halide.
× 10 ⁻⁶ mol was added. Then, after adding a predetermined amount of a silver iodide fine grain emulsion and a spectral sensitizing dye as a solid fine grain dispersion, 4-hydroxy-6-methyl-1,3,3a, 7
A mixed aqueous solution of tetrazaindene (TAI), adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and aged for a total of 2 hours and 30 minutes. At the end of the aging, an appropriate amount of TAI was further added as a stabilizer.

The spectral sensitizing dyes and other additives and the addition amounts (per mol of AgX) are shown below. Spectral sensitizing dye (listed in Table 3) 4.5 × 10 ⁻⁴ mol TAI 12 mg adenine 3 mg sodium thiosulfate 3.3 mg ammonium thiocyanate 50 mg chloroauric acid 2.0 mg silver iodide fine grain emulsion 5 mmol sensitizer a (triphenylphosphine selenide) 4.0 mg As a stabilizer (TAI) 750 mg

The silver iodide fine grain emulsion referred to here is 3
Weight% gelatin and silver iodide grains (average grain size 0.05μ
m) which is a fine grain emulsion. The solid fine particle dispersion of the spectral sensitizing dye and the dispersion of the selenium sensitizer are Em-
It was prepared in the same manner as in the case of 1. 60% of each of the emulsions Em-1 and Em-2 sensitized in this way:
An emulsion was prepared by mixing the emulsion at a ratio of 40% and adding the additives described below to prepare an emulsion coating solution. At the same time, a coating solution for the protective layer was prepared.

Next, a polyethylene terephthalate film base for X-rays having a density of 0.15 and having a blue color (thickness: 1
75 μm) on both sides of a support having the following transverse light-shielding layers pre-coated on both sides of the support from the side of the support at the same time so that the emulsion layer coating solution and the protective layer coating solution have the following predetermined coating amounts. And dried.

The additives used in the emulsion are as follows.
The addition amount is shown as an amount per 1 m ^{2 of} silver halide. First layer (transverse light shielding 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 latex (L) 0 0.2 g / 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 hardener (A) 2 mg / m ²

Second Layer (Emulsion Layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (Molecular weight 10,000) 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-dihydroxybenzene-4-sulfonic acid ammonium salt 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 5 mg / m ² compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ C H (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² Dextran (average molecular weight 40,000) 0.2 g / m ² compound (P) 0.2 g / m ² compound (Q) 0.2 g / m ² However, the gelatin was adjusted to 0.8 g / m ² . .

Third layer (protective layer) Gelatin 0.6 g / m² Matting agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 50 mg / m² Formaldehyde 20mg / m² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m² Bis-vinylsulfonyl methyl ether 36mg / m² Latex (L) 0.2 g / m² Polyacrylamide (average molecular weight 10,000) 0.1 g / m² Sodium polyacrylate 30mg / m² Polysiloxane (SI) 20mg / m² Compound (I) 12 mg / m² Compound (J) 2 mg / m² Compound (S-1) 7 mg / m² Compound (K) 15 mg / m² Compound (O) 50 mg / m² Compound (S-2) 5 mg / m² C₉F₁₉-O- (CH₂CH₂O)₁₁-H 3 mg / m² C₈F₁₇SO₂N- (C₃H₇) (CH₂CH₂O)_Fifteen-H 2 mg / m² C₈F₁₇SO₂N- (C₃H₇) (CH₂CH₂O)₄-(CH₂)₄SO ₃ Na 1 mg / m² Hardener (B) 2 mg / m²

[0156]

Embedded image

[0157]

Embedded image

[0158]

Embedded image

The coating amount of the above-mentioned material was for one side, and the coating amount of the emulsion layer was adjusted so as to be 1.3 g / m ² for one side.

(Preparation of Development Processing Agent) The following operations (A to
A developer replenishing tablet and a fixing replenishing tablet were prepared according to D). As the development initiator, the prepared development replenishing tablet and fixing replenishing tablet were dissolved in water and diluted with diluting water to prepare a development initiator.

Tablets for development replenishment were prepared according to the following operations (AB). Operation (A) 13,000 g of sodium erythorbate (exemplified compound 2-1) represented by the general formula (2) as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm.
To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone, and 1635 g of DTPA were added, mixed in a mill for 30 minutes, and mixed in a commercially available stirring granulator at room temperature for about 10 minutes,
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. In this way, polyethylene glycol (# 6000) 2167 was added to the prepared granules.
g was uniformly mixed for 10 minutes in a room where the humidity was controlled to 25 ° C. and 40% RH or less, and then the obtained mixture was mixed with a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho. Filling amount per tablet is 8.715g
After that, the tablets were compressed and compressed into 2,500 developing replenishment tablets A.
It was created.

Operation (B) 19,500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, sodium hydrogen carbonate 3.
25 g, 650 g of glutaraldehyde sulfite adduct, and 1354 g of polyethylene glycol (# 6000) are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 30.0
ml, and after granulation, dried at 50 ° C. for 30 minutes to remove almost completely the moisture of the granulated material. The mixture thus obtained was compressed into tablets using the same tableting machine as described above, with the filling amount per tablet being 9.90 g, to prepare 2500 replenishing tablets B for development.

Next, fixing replenishment tablets were prepared by the following operations (C to D). Operation (C) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide and 2.32 g of ethylenediaminetetraacetic acid disodium are pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 500 ml, and after granulation, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. In this way, the mixture thus obtained was packed in a tableting machine as described above at a loading amount of 8.214 per tablet.
The mixture was compressed to g and compressed to form 2,500 fixing replenishment tablets C.

Operation (D) 1860 g of boric acid, 650 aluminum sulfate and 18 hydrates
0 g, glacial acetic acid 1860 g, sulfuric acid (50% by weight) 925 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 1
The volume of the granules is adjusted to 00 ml, and after granulation, the granules are dried at 50 ° C. for 30 minutes to almost completely remove water. The mixture thus obtained was compressed into tablets by the above-mentioned tableting machine at a filling amount of 4.459 g per tablet to prepare 2500 fixing replenishment tablets D.

127 developing replenishing tablets A, B prepared
Was dissolved in 254 and diluted with diluting water to prepare 16.5 liter of a developer having the following composition and having a pH of 10.70, and 330 ml of a starter was added to adjust the pH to 10.45 to prepare a developing starter solution.

(Development Initiator Solution Composition) Potassium carbonate 120.0 g / l Sodium erythorbate (Exemplified compound 4-1) 40.0 g / l DTPA 5.0 g / l 1-Phenyl-5-mercaptotetrazole 0.05 g / l Sodium hydrogen carbonate 20.0 g / l Phenidone 3.0 3.0 g / l Sodium sulfite 15.0 g / l Polyethylene glycol 15.0 g / l Glutaraldehyde sulfite adduct 4.0 g / l

(Developer starter) 2.10 g of glacial acetic acid,
Water added to 5.30 g of KBr to make 1 liter.
The prepared fixing replenishing tablets C356 tablets and D222 tablets were dissolved and diluted in water, and the pH was adjusted to 4.5 to prepare a fixing start solution.

(Fixing starter composition) Ammonium thiosulfate 160.0 g / l Sodium sulfite 12.0 g / l Boric acid 1.0 g / l Sodium hydroxide 5.0 g / l Glacial acetic acid 10.0 g / l Aluminum sulfate-18-hydrate 35.0 g / l Sulfuric acid (50% by weight) 5.0 g / l Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g / l

For development, a solid processing agent charging member was mounted on an automatic processor SRX-503 (manufactured by Konica Corporation), and the total processing time (d
It was run for 15 seconds after being modified so that it could be processed in 15 seconds. Processing conditions Development 35 ° C 5.0 seconds Fixing 33 ° C 3.0 seconds Washing with water Normal temperature 2.5 seconds Squeeze 1.5 seconds Dry 40 ° C 2.0 seconds Total 15.0 seconds

Replenishment was carried out by adding to the developer 1 tablet A, ² tablets B and 20 ml of water per 1 m ² of the light-sensitive material,
The fixing solution was prepared by adding 4 tablets C, ² tablets D and 50 ml of water per 1 m ² of the light-sensitive material. The addition of water was started in synchronization with the addition of each treating agent, and was performed at a constant speed for 10 minutes substantially in proportion to the dissolution rate of the treating agent.

(Preparation of fluorescent intensifying screen) A fluorescent intensifying screen comprising a support, an undercoat layer, a phosphor layer and a transparent protective layer was prepared as follows. Phosphor Gd0.2O2S: Tb (average particle size 1.8μ) 200g Binder Polyurethane thermoplastic elastomer (Demolac TPKL-5-2 625 Solid content 40% Sumitomo Bayer Urethane Co. 20g Nitrocellulose (nitrification degree 11.5% 2 g Methyl ethyl ketone solvent was added to the above composition and dispersed by a propeller-type mixer to prepare a phosphor layer-forming coating solution having a viscosity of 25 ps (25 ° C.) (binder / phosphor = 1/2).
2). Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose were dispersed and mixed by adding methyl ethyl ketone as a coating liquid for forming an undercoat layer and a viscosity of 3 to 6 ps (25
C) dispersion was prepared.

A 250 μm-thick polyethylene terephthalate base (support) in which titanium dioxide was kneaded was placed horizontally on a glass plate, and the coating solution for forming the undercoat layer was uniformly applied on the support using a doctor blade. 25 ° C after coating
To 100 ° C., the coating film was dried to form an undercoat layer having a thickness of 15 μm.

On the undercoat layer, the coating solution for forming a phosphor layer was uniformly coated and dried to a film thickness of 2400 μm using a doctor blade, and then 800 kg using a calender roll.
The compression was performed at a pressure of w / cm ² and a temperature of 80 ° C. Further, a transparent protective layer having a thickness of 3 μm was formed by the method described in Example 1 of JP-A-6-75097.

<Evaluation> The obtained sample was sandwiched between the above-mentioned two fluorescent intensifying screens, irradiated with X-rays through a penetrometer B type (manufactured by Konica Medical Co., Ltd.), and then subjected to the above-mentioned development treatment to obtain sensitivity, fog, and The residual color property was evaluated. The sensitivity is sample No. 1 is a relative value with the reciprocal of the X-ray exposure amount required to obtain the minimum density being 100. The residual color was evaluated by developing the unexposed sample and measuring the density at 510 nm with a spectrophotometer. The residual color in the table indicates the sample No. The value of 1 is 10
It was expressed as a relative value when it was set to 0. Tables 1 and 2 summarize these results.

[0175]

[Table 1]

[0176]

[Table 2]

As is clear from Tables 1 and 2, the samples in which the inhibitors according to the present invention were used in combination were able to obtain a silver halide photographic light-sensitive material having excellent residual color, low fog and high sensitivity. I understand. Similar results were obtained using silver chloride grains.

Example 2 After preparing Em-1 in the same manner as in Example 1, Em-1 was heated to 53 ° C.
In the same manner as in Example 1, silver iodide fine particles and a spectral sensitizing dye were added as a solid fine particle dispersion. Then, a sulfur sensitizer, a selenium sensitizer, and a gold sensitizer were further added, and aging was carried out for a total of 2 hours and 30 minutes.
A suitable amount of AI and the compound of the present invention N-halosulfonamide compound is 1 × 10 ⁻⁴ mol per mol of silver halide, and polysulfide compound is 1 per mol of silver halide.
× 10 ⁻⁵ mol was added.

On the other hand, after preparing Em-2 in the same manner as in Example 1, the temperature of Em-2 was set to 47 ° C., and silver iodide fine particles and a spectral sensitizing dye were added as a solid fine particle dispersion in the same manner as in Example 1. did. Then, a sulfur sensitizer, a selenium sensitizer, and a gold sensitizer were further added, and aging was carried out for a total of 2 hours and 30 minutes. At the end of aging, an appropriate amount of TAI and the compound N- of the present invention were used as a stabilizer.
The halosulfonamide compound was added at 1 × 10 ⁻⁴ mol per mol of silver halide, and the polysulfide compound was added at 1 × 10 ⁻⁵ mol per mol of silver halide. An emulsion layer coating solution and a protective layer coating solution were prepared to prepare a film sample.

Emulsion Em-1 thus sensitized
And Em-2 were mixed at a ratio of 60%: 40% to prepare an emulsion, and a sample was prepared in the same manner as in Example 1 below.

Regarding the obtained sample, the following developing treatment agent-1 was used.
Alternatively, the photographic performance was evaluated after development processing using the development processing agent-2 under the following processing conditions. The obtained results are shown in Tables 6 and 7. (Preparation of Development Processing Agent-1) Development processing agent-1 was prepared in the same manner as the preparation of the development processing agent of Example 1. (Preparation of Development Processing Agent-2) A development replenishment tablet and a fixing replenishment tablet were prepared according to the following operations (E to H).

Tablets for development replenishment were prepared by the following operations. Operation (E) 3000 g of hydroquinone as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder, 3000 g of sodium sulfite, 2000 g of potassium sulfite, 1000 of dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone)
g, and mixed in a mill for 30 minutes and granulated by adding 30 ml of water in a commercially available stirred granulator at room temperature for about 10 minutes, and then the granulation product was mixed in a fluidized bed drier at 40 The granulated product is dried at 2 ° C for 2 hours to almost completely remove water. 100 g of polyethylene glycol # 6000 was uniformly mixed with the granulated product thus prepared for 10 minutes in a room where the humidity was adjusted to 25 ° C. and 40% RH or less, and then the obtained mixture was mixed with Kikusui Using a tableting machine modified from Tough Presto Correct 1527HU manufactured by Seisakusho Co., Ltd., compression filling was carried out with the filling amount per tablet being 3.84 g, and 2500 developing replenishing tablets E were prepared.

Operation (F) Diethylenetriamine pentaacetic acid, 5 sodium salt (DTPA)
100 g, potassium carbonate 4000 g, 5-methylbenzotriazole 10 g, 1-phenyl-5-mercaptotetrazole 7 g, 2-mercaptohypoxanthine 5 g,
200 g of KOH and 13.3 g of N-acetyl-D, L-penicillamine are ground and granulated in the same manner as in the operation (E). 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 compressed into tablets using the same tableting machine as described above, with the filling amount per tablet being 1.73 g.
00 developing replenishing tablets F agent were prepared.

Prepared developing replenishing tablets E783 pieces, F1
To 16.5 liters of a developing solution of pH 10.70 having the following composition prepared by dissolving 031 pieces in water and diluting with diluted water, 330 ml of a starter was added to adjust the pH to 10.45 to obtain a developing starter solution.

(Developer composition) Potassium carbonate 100.0 g / l Hydroquinone 57.0 g / l Dimezone S 25.0 g / l DTPA 2.5 g / l 5-Methylbenzotriazole 0.25 g / l 1-Phenyl-5 Mercaptotetrazole 0.18 g / l 2-mercaptohypoxanthine 0.13 g / l sodium sulfite 75.0 g / l potassium sulfite 62.5 g / l KOH 5.0 g / l diethylene glycol 125.0 g / l N-acetyl-D, L -Penicillamine 0.25 g / l

(Developer starter) 2.98 g of glacial acetic acid,
Water added to 4.0 g of KBr to make 1 liter.

(Fixing start composition to pH 4.50) Ammonium thiosulfate 84.0 g / l Potassium thiosulfate 196.0 g / l Sodium sulfite 30.0 g / l Boric acid 20.0 g / l Sodium hydrogen acetate 60.0 g / l Glacial acetic acid 34.6 g / l Aluminum sulphate-18-hydrate 16.8 g / l Sodium acetate 25.4 g / l Tartaric acid 4.0 g / l Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g / l

Next, fixing replenishing tablets were prepared by the following operations (G) and (H). Operation (G) Ammonium thiosulfate / sodium sulfate (weight ratio 70 /
30) 14,000 g and 1500 g of sodium sulfite are pulverized and granulated in the same manner as in the operation (E) and uniformly mixed with a commercially available mixer. Then, in the same manner as in the operation (E), the amount of water added is set to 500 ml, and granulation is performed.
For 30 minutes to remove the moisture of the granules almost completely. The mixture thus obtained was compressed into tablets by the above-mentioned tableting machine at a filling amount of 6.202 g per tablet to prepare 2500 fixing replenishing tablets G.

Operation (H) Boric acid 1000 g, aluminum sulfate · 18-hydrate 1500
g, sodium hydrogen acetate (equimolar mixture of glacial acetic acid and sodium acetate and dried) 3000 g, tartaric acid 200 g
Are pulverized and granulated in the same manner as in the above operation (E). The amount of water added is 100 ml, and after granulation, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product. The mixture thus obtained was compressed into tablets by the above-mentioned tableting machine at a filling amount of 4.562 g per tablet.
Zero fixer refill tablets H were made.

Prepared fixing replenishing tablets G825, H4
Twelve pieces were dissolved in water, diluted with diluting water to prepare a solution, which was used as a fixing start solution. The photographic performance of the obtained sample was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 3 and 4.

[0191]

[Table 3]

[0192]

[Table 4]

As is clear from Tables 3 and 4, the sample of the present invention can provide a silver halide photographic light-sensitive material having excellent residual color, low fog and high sensitivity even in the development process containing no hydroquinone. I understand.

Example 3 (Preparation of Seed Emulsion EM-3) A3 ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g distilled water to 7500 ml B3 silver nitrate 1500 g distilled water to 2500 ml C3 KI 4 g NaCl 140 g Distilled water to 684 ml D3 NaCl 375 g Distilled water to 1816 ml

At 40 ° C., the solution A3 in the mixing stirrer described in JP-B-58-58288 was mixed with the solution B3 at 684 m.
1 and the total amount of solution C3 were added over 1 minute. The EAg was adjusted to 149 mV, and after aging for 20 minutes in Ostwald, the total amount of the remaining solution A3 and the total amount of the solution D3 were added over 40 minutes. Meanwhile, EAg was controlled at 149 mV. Immediately after the completion of addition, desalting and washing with water were carried out to obtain a tabular seed emulsion EM-
It was set to 3. In the resulting seed emulsion, 60% or more of the total projected area of silver halide grains consisted of tabular grains having the (100) plane as the main plane, and the average thickness was 0.07 μm and the average diameter was 0.
It was found by electron microscope observation that the variation coefficient was 5 μm and the variation coefficient was 25%.

(Preparation of high silver chloride emulsion EM-4) The following 4
Tabular high silver chloride emulsions were made using different solutions. A4 ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n- (CH [CH 3] CH 2 O) 17 - (CH 2 C H 2 O) mH (n + m = 5~7,10% aqueous methanol ) 1.25 ml seed emulsion EM-3 0.98 mol equivalent Equal to 3000 ml with distilled water B4 3.50N AgNO ₃ aqueous solution 2240 ml C4 NaCl 455 g Distilled water with 2240 ml D4 1.75N NaCl aqueous solution Silver potential control amount below

At 40 ° C., using a mixing stirrer described in JP-B-58-58288, the total amount of solution B4 and solution C4 was simultaneously mixed with solution A4 by the double mixing method at the start of addition. The additional growth was performed for 110 minutes so that the flow rate would be three times the flow rate of the above.

The silver potential during this period was +12 using the solution D4.
It controlled so that it might be set to 0 mV. After completion of the addition, precipitation and desalting were performed by the method described below to remove excess salts.
1) The reaction solution after mixing is brought to 40 ° C.
20 g of Compound G-3, an example of the aggregating gelatin agent described in No. 37
/ AgX (1 mol) is added, and 56 wt% acetic acid is added to lower the pH to 4.30, and the mixture is left standing and decanted.
2) Add 1.8 liters of pure water at 40 ° C./1 mol of AgX and stir for 10 minutes, then leave still and decant. 3) Repeat step 2 above once more. 4) Next, add 15 g of post-gelatin, 1 mol of AgX, sodium carbonate and water to adjust the pH to 6.0 and disperse to 450 ml.
/ AgX 1 mol.

Approximately 3,000 emulsions EM-4 thus obtained were observed and measured by an electron microscope to analyze the shape, and 80% or more of the total projected area had the (100) plane as the main plane.
The tabular grains had an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 24%.

Subsequently, 4 parts of this high silver chloride emulsion EM-4 were added.
After the temperature was adjusted to 3 ° C. (addition position A), the N-halosulfonamide compound of the present invention was added at 1 × 10 6 per mol of silver halide.
^-5 mol, and polysulfide compound as silver halide 1
1 × 10 ⁻⁶ mol was added per mol. After adding the compound of the present invention, the following predetermined amounts of silver bromide fine particles and spectral sensitizing dyes were added as a solid fine particle dispersion. Then, after further adding a sulfur sensitizer, a selenium sensitizer and a gold sensitizer, the temperature was raised to 55 ° C. and aging was conducted for a total of 90 minutes. At the end of aging, 4-hydroxy-6-methyl- 1,
3,3a, 7-tetrazaindene (TAI) in appropriate amount,
(Addition position B) The compound of the present invention N-halosulfonamide compound is 1 × 10 ⁻⁴ mol per mol of silver halide, and the polysulfide compound is 1 per mol of silver halide.
× 10 ⁻⁵ mol was added (the amount of the compound added in the aging step and AgX per mol).

Silver bromide fine grain emulsion 5 mmol equivalent Spectral sensitizing dye 1-61 5.5 × 10 ⁻⁴ mol Spectral sensitizing dye (1) 30 mg Sulfur sensitizer (S) 2.0 mg Gold sensitizer (R) 1.0 mg Selenium sensitizer (triphenylphosphine selenide) 0.5 mg Tellurium sensitizer (butyl-diisopropylphosphine telluride) 0.5 mg Stabilizer (TAI) 50 mg

[0202]

Embedded image

The term "silver bromide fine grain emulsion" used herein means
3% by weight of gelatin and silver bromide grains (average grain size: 0.05μ
m) which is a fine grain emulsion. The spectral sensitizing dye is a solid fine particle dispersion in Japanese Patent Application No. 4-9943.
What was prepared by the method according to the method described in No. 7 was used. The same additives as in Example 1 were added to the obtained emulsion to prepare an emulsion coating solution. Similarly, a protective layer coating solution was prepared in the same manner as in Example 1.

Next, a polyethylene terephthalate film base for X-rays (with a thickness of 1
(75 .mu.m) on both sides of a support having a transverse light-shielding layer similar to that of Example 1 previously coated on both sides, the emulsion layer coating solution and the protective layer coating solution described above were simultaneously layered and dried. The results of treating the obtained sample in the same manner as in Example 1 are shown in Tables 5 and 6.

[0205]

[Table 5]

[0206]

[Table 6]

As can be seen from Tables 5 and 6, the samples of the present invention can provide a silver halide photographic light-sensitive material having low fog and high sensitivity. Similar results were obtained even when silver iodobromide grains were used.

[0208]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide photographic light-sensitive material having a low fog and an excellent residual color, a low fog even when processed with a developer containing no hydroquinone, a high sensitivity and an excellent residual color, and a method thereof are provided. A treatment method was obtained.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains an N-halosulfonamide compound. Silver halide photographic light-sensitive material. 2. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains an N-halosulfonamide compound and a polysulfide compound. A characteristic silver halide photographic light-sensitive material. 3. The halogenated compound according to claim 1, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto contains a compound represented by the following general formula (1). Silver photographic light-sensitive material. Embedded image In the formula, R ₆ and R ₈ each represent a substituted or unsubstituted alkyl group or alkenyl group, R ₇ and R ₉ represent a lower alkyl group, and at least one of R ₇ and R ₉ represents a hydrophilic group. Represents a substituted alkyl group. X ₂ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1. Z ₁ , Z
₂ , Z ₃ and Z ₄ are halogen atom, alkyl group, alkoxy group, alkylthio group, trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group, acyl group, sulfonyl group, carbamoyl group, sulfamoyl group, acetylamino group Represents an acetyloxy group and an aryl group. 4. The silver halide grain contained in the silver halide emulsion layer is selenium sensitized and / or tellurium sensitized, according to any one of claims 1 to 3. The described silver halide photographic light-sensitive material. 5. A silver halide characterized in that the silver halide photographic light-sensitive material according to any one of claims 1 to 4 is processed in a processing step including a developing step (fixing step and drying step if necessary). Processing method of photographic light-sensitive material. 6. The processing of a silver halide photographic light-sensitive material according to claim 5, wherein the developing solution is processed with a developing solution containing at least one compound represented by the following general formula (2). Method. Embedded image In the formula, R ₁₀ and R ₁₁ are a hydroxy group and —O, respectively.
M represents an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group, and M represents an alkali metal atom or an ammonium group. P and Q represent a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a mercapto group, an alkyl group or an aryl group,
Alternatively, P and Q represent an atomic group necessary for forming a 5- to 8-membered ring by bonding. Y represents = O or = _{N-R 12,.} R ₁₂ is a hydrogen atom, a hydroxyl group, an alkyl group,
Acyl group, hydroxyalkyl group, sulfoalkyl group,
Represents a carboxyalkyl group.