JPH04333042A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To decrease the changed in sensitivity and to obtain excellent picture quality even when the compsn. of a developer varies in a super rapid treatment process by incorporating a specified amt. of irridium into a silver halide emulsion and specifying the amt. of gelatine in the emulsion layer side. CONSTITUTION:The photographic sensitive material has at least one photosensitive silver halide emulsion layer and at least one protective layer both provided on one surface of a supporting body. The photosensitive silver halide emulsion contains <=10<-5>mol irridium compd. to 1mol silver halide and is sensitized with a selenium sensitizer. Moreover, the total amt. of gelatine applied on the emulsion layer side is specified to <=2.5g/m<2>. The amt. of gelatine applied for the protective layer is specified to <=0.5g/m<2>. Further, the photosensitive material contains at least one kind of polyhydroxy benzene compd. expressed by the formula. In the formula, X and Y are H, halogen atom, phenyl group, etc. This photosensitive material is processed with an autodeveloping machine which takes within 60 seconds for processes from developing, fixing, water washing to drying at 1500mm/min or higher traveling rate of a film.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material.More specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, the sensitivity change is small when the developer composition changes during high-intensity short-time exposure, and the light-sensitive material is stable over time. The present invention relates to a silver halide photographic material that has high properties and can be rapidly processed, and a processing method thereof.

0002

BACKGROUND OF THE INVENTION In recent years, scanner systems have been widely used in the field of printing plate making. There are various types of recording devices that use scanner-based image forming methods, and the recording light sources of these scanner-type recording devices include glow lamps,
Examples include xenon lamps, tungsten lamps, LEDs, He-Ne lasers, argon lasers, and semiconductor lasers. The photosensitive materials used in these scanners are required to have various properties, especially 10-3 to 10-3.
Even under such conditions, high sensitivity and high contrast are essential conditions since exposure is performed for a short time of 10-8 seconds. However, silver halide emulsions exposed to high illumination for a short period of time are characterized by slow development progress, and sensitivity fluctuations increase when the composition of the processing solution changes, or when the development temperature or time changes. . Furthermore, in recent years, there has been a strong desire to improve the efficiency and speed of work in the printing industry, and there is a wide range of needs for faster scanning and shorter processing times for photosensitive materials. In order to meet these needs in the printing field, exposure machines (scanners, plotters) are required to speed up scanning, increase the number of lines and narrow the beam for higher image quality, and silver halide photographic sensitizers Materials are desired to have high sensitivity, excellent stability, and rapid development processing. The rapid development process here refers to the leading edge of the film being inserted into the automatic developing machine, passing through the developing tank, transition area, fixing tank, transition area, washing tank, and drying area, and then the leading edge of the film emerges from the drying area. The time it came was 15-6
This refers to a process that takes 0 seconds. By the way, many patents describe that chemical sensitization using selenium compounds increases sensitivity. For example, Japanese Patent Publication No. 44-15748, Japanese Patent Publication No. 43-13489, Japanese Patent Application No. 2-13097,
Various examples of compounds are listed in Japanese Patent Application No. 2-229300. Further, Japanese Patent Publication No. 57-22090 describes that sensitivity can be increased at high illuminance by using it in combination with a water-soluble iridium compound. However, although these methods can certainly increase sensitivity, the developing solution is easily fatigued by being oxidized by the processing of the sensitive material and by oxygen in the air, and it is difficult to maintain the same composition as the fresh solution. difficult. Therefore, as a photosensitive material, fresh developer solution is recommended.
It is desirable that the difference in sensitivity between processing with liquid and fatigue liquid be as small as possible. Especially in rapid processing, development time is inevitably shortened, making the material more susceptible to liquid composition dependence and strengthening the structure of the sensitive material. That was what was hoped for.

0003

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce the sensitivity fluctuations of a photosensitive material when the developer composition changes even during rapid processing, and to improve the line width and density when output by a scanner. The aim is to eliminate vibration and provide a more stable system. Furthermore, the purpose is to reduce the change in sensitivity of the photosensitive material over time to provide a more stable photosensitive material-processing solution-transformer system, and even when the amount of replenishment of processing agent is reduced (conventional system 1/2) Our objective is to provide a stable, high-quality system that does not pollute the global environment with waste liquid.

0004

[Means for Solving the Problems] The object of the present invention is to provide a silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer and at least one protective layer on the same side of a support. The photosensitive silver halide emulsion contains 10-5 mol or less of an iridium compound per mol of silver halide, is sensitized with a selenium sensitizer, and further has a total amount of gelatin coated on the silver halide emulsion layer side. 2.5
This can be achieved by reducing the amount to below g/m2. Furthermore, this effect becomes more pronounced by setting the amount of gelatin applied in the protective layer to 0.5 g/m2. Furthermore, by containing at least one polyhydroxybenzene compound, both the liquid composition dependence and the stability over time could be further improved.

Next, a specific configuration of the present invention will be explained in detail. The silver halide photographic emulsion according to the present invention contains silver chloride, silver chlorobromide or silver chloroiodobromide as silver halide. At this time, silver chloride is contained in an amount of 30 mol % or more, more preferably 60 mol % or more. Further, the silver iodide content is preferably 5 mol% or less, more preferably 2 mol% or less. The shape of the silver halide grains may be cubic, tetradecahedral, octahedral, amorphous, or plate-like, but cubic or plate-like is preferable. The average particle size of silver halide grains is 0.01 μm to 1
μm is preferable, but it is more preferably 0.4 μm or less, and the coefficient of variation expressed by {(standard deviation of particle size)/(average particle size)}×100 is 15% or less, more preferably 10
% or less is preferable. The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

The photographic emulsion used in the present invention is P. Gl
Chimie et Physi by afkides
que Photographique (Paul M.
ontel, 1967), G. F. Duff
Written by in Photographic Emulsion
Chemistry (The Focal Pres.
s publication, 1966), V. L. Zelikman
Making and Coating by et al.
Photographic Emulsion (Th
e Focal Press, 1964). That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and any one-sided mixing method, simultaneous mixing method, combination thereof, etc. may be used to form the reaction between the soluble silver salt and the soluble halogen salt. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

[0007] Furthermore, in order to make the particle size uniform,
British Patent No. 1,535,016, Special Publication No. 1973-3689
0. As described in No. 52-16364, there is a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, and British Patent No. 4,242,445.
It is preferable to use a method of varying the concentration of an aqueous solution as described in JP-A No. 55-158124 to grow rapidly within a range that does not exceed the critical saturation level. Grain formation of the silver halide emulsion of the present invention is preferably carried out in the presence of a silver halide solvent such as a tetrasubstituted thiourea or an organic thioether compound. Preferred tetrasubstituted thiourea silver halide solvents used in the present invention include JP-A-53
-82408, 55-77737, etc., and is a compound represented by the following general formula (II).

[0008]

[Case 2]

Examples of compounds that can be used in the present invention include the following compounds.

0010

[Chemical formula 3]

[0011]

[C4]

0012

[C5]

The organic thioether silver halide solvent preferably used in the present invention is, for example, disclosed in Japanese Patent Publication No. 47-11386.
Compounds containing at least one group in which an oxygen atom and a sulfur atom are separated by ethylene (e.g. -O-CH2 CH2 -S-) described in JP-A No. 3,574,628, etc. No. 54-155828 (U.S. Pat. No. 4,276,374), an alkyl group at both ends (each alkyl group has at least two substituents selected from hydroxy, amino, carboxy, amide, or sulfone) ) is a chain-like thioether compound. Specifically, the following examples can be given.

[0014]

[C6]

The amount of the silver halide solvent added varies depending on the type of compound used, the intended grain size, the halogen composition, etc., but it is 10-5 per mole of silver halide.
~10 −2 mol is preferred. If the grain size exceeds the desired size due to the use of a silver halide solvent, the desired grain size can be achieved by changing the temperature during grain formation, the addition time of the silver salt solution, the halide salt solution, etc.

[0016] As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, halogenated iridium (III) compounds, halogenated iridium (IV) compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III).
Or (IV) complex salt, hexaammineiridium (I
II) or (IV) complex salts, trioxalatoiridium (III) or (IV) complex salts, and the like. In the present invention, among these compounds, III-valent compounds and IV-valent compounds can be used in any combination. These iridium compounds are used after being dissolved in water or an appropriate solvent, but methods commonly used to stabilize solutions of iridium compounds include aqueous hydrogen halide solutions (e.g., hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.). , or alkali halides (e.g. KCl, NaCl,
KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve other silver halide grains doped with iridium in advance during the preparation of silver halide grains. The total amount of iridium compounds used in the present invention is 1×1 per mole of silver halide finally formed.
0-8 to 1 x 10-6 mol is appropriate, preferably 5
x10-8 to 1 x 10-6 mol. These compounds can be added as appropriate during the production of the silver halide emulsion and at each stage before coating the emulsion, but in particular, they can be added during grain formation and incorporated into the silver halide grains. preferable. Specific compounds include iridium (III) chloride and iridium (III) bromide.
), secondary iridium (IV) chloride, sodium hexachloroiridate (III), hexachloroiridium (III) salt, hexamine iridium (IV) salt, trioxalatoiridium (III) salt, trioxalatoiridium (IV) salt Preferred are halogen amines such as , and oxalate complex salts.

The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, preferably an iron salt or iron complex salt that is water-soluble within the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate hydroxide ferrous iodide Ferrous lactate Ferrous oxalate Ferrous phosphate Ferrous succinate Ferrous sulfate Ferrous thiocyanate Ferrous nitrate Ferrous nitrate Ammonium basic Ferric acetate Ferrous albumate Ferric acetate Ammonium Bromide Ferric chloride Ferric chlorate Ferric citrate Ferric fluoride Ferric formate Glycero phosphate Ferric hydroxide Ferric acid phosphate Ferric Nitrate Ferric Phosphate Ferric Pyrophosphate Ferric Pyrophosphate Sodium Thiocyanide Ferric Sulfate Ferric Ammonium Sulfate Ferric Sulfate Guanidine Ferric Ammonium Citrate Hexane Cyanoferrous Potassium (II) acid Potassium bentacyanoammine Ferrous potassium Ethylene dinitrilotetraacetic acid Ferrous sodium Sodium hexacyanoferrate(III) acid Tris(dipyridyl) ferric chloride Bentacyano nitrosyl Ferric potassium Hexarea Ferric chloride Especially hexacyano Iron (II) salt, hexacyanoferrate (I
II) Acid salts, ferrous thiocyanate and ferric thiocyanate exhibit remarkable effects.

[0018] The rhenium, ruthenium, and osmium compounds used in the present invention are disclosed in European published patent (EP) 0.
No. 336689A, No. 0336427A1, No. 033
The hexacoordination complexes described in No. 6425A1 and No. 0336426A1 are preferred, and those containing at least four cyanide ligands are particularly preferred. In preferred embodiments, these compounds can be represented by the following formulas. [M(Cn)6-yLy]n where M is rhenium, ruthenium, osmium, L is a bridging ligand, y is an integer 0, 1, or 2, and n is -2, -3 or -4. A specific example is [Re(CN)5]-4
[Ru(CN)5]-4 [Os(CN)
)5]-4 [ReF(C
N)5]-4 [RuF(CN)5]-4
[OsF(CN)5]-4
[ReCl(CN)5]-4
[RuCl(CN)5]-4 [OsC
l(CN)5]-4 [ReBr(
CN)5]-4 [RuBr(CN)5]-
4 [OsBr(CN)5]-4
[ReI(CN)5]-4
[RuI(CN)5]-4 [Os
I(CN)5]-4 [ReF
2 (CN)4]-4 [RuF2 (CN)
)5]-4 [OsF2 (CN)
5]-4 [ReCl2 (CN)4]-4
[RuCl2 (CN)4]-4
[OsCl2 (CN)4]-4
[RuBr2 (CN)4]-4 [O
sBr2 (CN)4]-4 [ReB
r2 (CN)4]-4 [RuI2 (C
N) 4]-4 [OsI2 (CN
)5]-4 [Ru(CN)5(OCN)]
-4 [Os(CN)5(OCN)]-4
[Ru(CN)5(SCN)]-4 [O
s(CN)5(SCN)]-4 [Ru(C
N)5(N3)]-4 [Os(CN)
5(N3)]-4 [Ru(CN)5(H2
O)]-3 [Os(CN)5(H2O)]
-3 can be mentioned.

The above iron, rhenium, ruthenium, and osmium compounds are preferably added during the formation of silver halide grains. The addition position may be uniformly distributed in the particles or localized at the early, middle, or late stages of particle formation;
Preferably, it is added after 0%, more preferably 80%, has been formed. The amount added is 10-3 mol or less, preferably 10-6 to 10-4 mol, per 1 mol of silver. In the present invention, other metals included in Group VIII, such as cobalt, nickel, rhodium, palladium, and platinum, may be used in combination. In particular, the combination with rhodium salts such as rhodium chloride and ammonium hexachlorodate(III) is advantageous because a high-contrast emulsion can be obtained.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, it is usually used by adding an unstable selenium compound and/or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. As unstable selenium compounds, Japanese Patent Publication No. 44-15748, Japanese Patent Publication No. 43-13489,
It is preferable to use compounds described in Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-229300, and the like. Specific unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2-
selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. can give. Although preferred types of unstable selenium compounds have been described above, these are not intended to be limiting. Those skilled in the art understand that when it comes to unstable selenium compounds used as sensitizers in photographic emulsions, the structure of the compound is not particularly important as long as selenium is unstable; It is generally understood that the moiety has no role other than to support the selenium and allow it to exist in an unstable form in the emulsion. In the present invention, unstable selenium compounds having such a broad concept are advantageously used. As the non-unstable selenium compound used in the present invention, the compounds described in Japanese Patent Publication No. 46-4553, Japanese Patent Publication No. 34492-1982, and Japanese Patent Publication No. 34491-1988 are used. Non-labile selenium compounds include, for example, selenite, potassium selenocyanide, selenazole compounds, quaternary salts of selenazole compounds, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, Examples include 2-selenoxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formula (I
II) and (IV). General formula (III)

[0021]

[C7]

In the formula, Z1 and Z2 may be the same or different, and represent an alkyl group (for example, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group), an alkenyl group (for example, vinyl group, propenyl group), aralkyl group (e.g. benzyl group, phenethyl group), aryl group (e.g. phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group) ,
α-naphthyl group), heterocyclic group (e.g. pyridyl group, chenyl group, furyl group, imidazolyl group), -NR1 (
R2), -OR3 or -SR4. R1
, R2, R3 and R4 may each be the same or different and represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl group, aralkyl group,
Examples of the aryl group or heterocyclic group include the same examples as Z1. However, R1 and R2 are hydrogen atoms or acyl groups (e.g., acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group) (base) may be used. In general formula (III), preferably Z1 represents an alkyl group, an aryl group or -NR1 (R2), and Z2 represents -NR5 (R6). R1, R2, R5
and R6 may be the same or different,
Represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In general formula (III), more preferably N,N-
Dialkylselenourea, N,N,N'-trialkyl-
N'-acylselenourea, tetraalkylselenourea,
Represents N,N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide. General formula (IV)

[0023]

[Chemical formula 8]

In the formula, Z3, Z4 and Z5 may be the same or different, and are an aliphatic group, an aromatic group, a heterocyclic group, -OR7, -NR8 (R9), -S
R10, -SeR11, X represents a hydrogen atom. R7,
R10 and R11 are an aliphatic group, an aromatic group, a heterocyclic group,
represents a hydrogen atom or a cation, R8 and R9 represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom,
X represents a halogen atom. In general formula (IV), Z
3, Z4, Z5, R7, R8, R9, R1
The aliphatic group represented by 0 and R11 is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (e.g. methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group). , n-butyl group, n
-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In general formula (IV), Z3, Z4, Z5, R7
, R8, R9, R10 and R11 are monocyclic or condensed aryl groups (e.g., phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-sulfophenyl group, α-naphthyl group). , 4-methylphenyl group). In general formula (IV), Z3
, Z4, Z5, R7, R8, R9, R10 and R11 are 3- to 10-membered saturated or unsaturated heterocyclic groups containing at least one of nitrogen, oxygen, or sulfur atoms. represents a group (eg, pyridyl group, chenyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (IV), the cations represented by R7, R10 and R11 represent an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In general formula (IV),
Preferably Z3, Z4 or Z5 represents an aliphatic group, an aromatic group or -OR7, and R7 represents an aliphatic group or an aromatic group. In general formula (IV), more preferably it represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Below is the general formula (
Specific examples of the compounds represented by III) and (IV) are shown below, but the present invention is not limited thereto.

[0025]

[Chemical formula 9]

[0026]

[Chemical formula 10]

[0027]

[Chemical formula 11]

[0028]

[Chemical formula 12]

[0029]

[Chemical formula 13]

[0030]

[Chemical formula 14]

[0031]

[Chemical formula 15]

[0032]

[Chemical formula 16]

Regarding the selenium sensitization method, US Pat. No. 15
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447, No. 3320069, No. 3408196, No. 34
No. 08197, No. 3442653, No. 34206
No. 70, No. 3591385, French Patent No. 269
No. 3038, No. 2093209, Special Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
No. 57-22090, JP-A No. 59-180536,
No. 59-185330, No. 59-181337, No. 59-187338, No. 59-192241, No. 6
No. 0-150046, No. 60-151637, No. 61
-246738, Japanese Patent Application Publication No. 3-4221, Patent Application No. 1-
No. 287380, No. 1-250950, No. 1-254
No. 441, No. 2-34090, No. 2-110558, No. 2-130976, No. 2-139183, No. 2
-229300 Furthermore, British Patent No. 255846, British Patent No. 861984 and H. E. Spencer et al., Journal of Photographic
It is disclosed in Science magazine, volume 31, pages 158-169 (1983).

These selenium sensitizers may be dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixture thereof, or as disclosed in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, but two or more of the above selenium sensitizers can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used together. The amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and preferably silver halide 1 It is 1×10 −8 mole or more per mole. More preferably, it is 1×10 −7 mol or more and 1×10 −5 mol or less. When a selenium sensitizer is used, the temperature for chemical ripening is preferably 45°C or higher. More preferably 50°C or higher, 8
The temperature is below 0°C. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained over a wide range of pH from 4 to 9. Selenium sensitization is more effective when carried out in the presence of a silver halide solvent.

Examples of silver halide solvents that can be used in the present invention include US Pat. No. 3,271,157, US Pat. No. 3,531,289, US Pat. (a) Organic thioethers described in No. 1019, No. 54-158917, etc., JP-A-53-82
(b) Thiourea derivatives described in No. 408, No. 55-77737, No. 55-2982, etc., JP-A-53-1
(c) A silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in No. 44319, (d) Imidazole as described in JP-A-54-100717, ( Examples include e) sulfites and (f) thiocyanates. Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1.times.10@-4 mol or more and 1.times.10@-2 mol or less per 1 mol of silver halide.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combining sulfur sensitization and/or gold sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. Further, gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples include thiosulfate, thioureas, allyl isothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patent No. 1,574,9
No. 44, No. 2,410,689, No. 2,278,
No. 947, No. 2,728,668, No. 3,501
, 313 and 3,656,955, German Patent No. 1,422,869, and Japanese Patent Publication No. 1983-24937.
Sulfur sensitizers described in JP-A-55-45016 and the like can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but it is between 1 x 10-7 mol and 5 mol per mol of silver halide.
x10-4 mol or less is preferable.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds commonly used as gold sensitizers can be used. Typical examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of gold sensitizer added varies depending on various conditions, but as a rough guide, it is preferably from 1.times.10@-7 mol to 5.times.10@-4 mol per mol of silver halide. During chemical ripening, there is no need to set particular restrictions on the timing and order of addition of silver halide solvents and selenium sensitizers, or sulfur sensitizers and/or gold sensitizers that can be used in combination with selenium sensitizers. Rather, the above compounds can be added simultaneously or at different times, for example, at the beginning (preferably) of chemical ripening or during the course of chemical ripening. Also, when adding
The above compound may be added after being dissolved in water or an organic solvent miscible with water, such as methanol, ethanol, acetone, etc., either alone or in a mixture.

As the polyhydroxybenzene used in the present invention, compounds of the following general formula are preferably used.

[0039]

[Chemical formula 17]

X and Y are -H, -OH, halogen atom, -OM (M is an alkali metal ion), -alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated group, respectively. Alkyl group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group, alkyl ether group, alkylphenyl group, alkylthioether group, or phenylthioether group be. Specific examples of the polyhydroxybenzene compound used in the present invention include the following compounds.

[0041]

[Chemical formula 18]

[0042]

[Chemical formula 19]

[0043]

[C20]

The polyhydroxybenzene compound may be added to the emulsion layer of the sensitive material, or may be added to a layer other than the emulsion layer. The amount added is preferably in the range of 10-5 to 1 mol, and particularly effective in the range of 10-3 to 10-1 mol.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholic cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Ite.
m 17643 Section IV-A (December 1978 p.
．． 23), Item 1831X (August 1979)
Mon p. 437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, for A) argon laser light source, JP-A-60-1
No. 62247, JP-A No. 2-48653, U.S. Patent No. 2,
No. 161,331, the simple merocyanines described in West German Patent No. 936,071;
For trinuclear cyanine dyes shown in No. 8726 and No. 59-102229, and C) for LED light sources,
No. 42172, No. 51-9609, No. 55-3981
8, thiacarbocyanines described in JP-A No. 62-284343, and D) tricarbocyanines described in JP-A-59-191032 and JP-A-60-80841 for semiconductor laser light sources. Class, JP-A-59-19
Dicarbocyanines containing a 4-quinoline nucleus, such as those described in No. 2242, are advantageously selected. Representative compounds of those sensitizing dyes are shown below. Specific compound examples of A)

[0046]

[C21]

Specific compound examples of B)

[0048]

[C22]

Specific compound examples of C)

[0050]

[C23]

[0051]

[C24]

Specific compound examples of D)

[0053]

[C25]

Although these sensitizing dyes may be used alone, it is more effective to use them in combination with a compound of the following general formula (VI).

[0055]

[C26]

In the formula, Z3 represents a nonmetallic atom group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as thiazoliums {such as thiazolium, 4-methylthiazolium, benzothiazolium, -Methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6
-methoxybenzothiazolium, naphtho[1,2-d]
thiazolium, naphtho[2,1-d]thiazolium, etc.}, oxazoliums {e.g., oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5- Methylbenzoxazolium, naphtho [1
, 2-d] oxazolium, etc.}, imidazoliums (
For example, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,
6-dichlorobenzimidazolium, 1-allyl-5-
trichloromethyl-6-chloro-benzimidazolium, etc.), selenazoliums [e.g. benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho[1, 2-d] selenazolium, etc.]. R13 represents a hydrogen atom, an alkyl group (having 8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), or an alkenyl group (such as an allyl group). R14 represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). X2 is an acid anion (e.g. Cl-, Br-, I-, ClO4
-, p-toluenesulfonic acid, etc.), thiazoliums are preferably used among Z3. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used. Specific examples of the compound represented by general formula (VI) are shown below. However, the present invention is not limited to only these compounds.

[0057]

[C27]

[0058]

[C28]

[0059]

[C29]

[0060]

[C30]

[0061]

[Chemical formula 31]

The compound of general formula (VI) above is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) between the sensitizing dye of the present invention and the compound represented by general formula (VI) is 1/1 to 1. A range of /300 is advantageously used, in particular a range of 1/2 to 1/50. The compound represented by the general formula (VI) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or It is also possible to dissolve a plurality of these solvents in a mixed solvent and add it to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. General formula (VI
The compound represented by ) may be added to the emulsion before or after the addition of the infrared sensitizing dye of the invention described above. Alternatively, the compound of general formula (VI) and the infrared sensitizing dye may be dissolved separately and added to the emulsion separately and simultaneously, or they may be mixed and then added to the emulsion. The combination according to the invention can further include compounds of the following general formula (VII).

[0063]

[C32]

[0064] Here, A represents a divalent aromatic residue. R
21, R22, R23, and R24 are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, a substituted or unsubstituted alkylamino group , represents a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group. However, at least one of A, R21, R22, R23 and R24 has a sulfo group. W3 and W4 represent -CH= or -N=. However, at least one of W3 and W4 is −N=
represents. General formula (VII) will be explained in more detail. In the formula, -A- represents a divalent aromatic residue, and these are -
SO3 M group [where M represents a hydrogen atom or a cation (eg, sodium, potassium, etc.) that provides water solubility. ] may be included. -A- is, for example, the following -A1
- or -A2 - are useful. However, when R21, R22, R23 or R24 does not contain -SO3M, -A- is selected from the group -A1 -.

[0065]

[Chemical formula 33]

[0066]

[C34]

[0067]

[C35]

R21, R22, R23 and R24 are each a hydrogen atom, a hydroxy group, or a lower alkyl group (preferably 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.) ), an alkoxy group (the number of carbon atoms is preferably 1 to 8; for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.),
Aryloxy group (e.g. phenoxy group, naphthoxy group,
o-troxy group, p-sulfophenoxy group, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.), heterocyclic nuclei (e.g., morpholinyl group, piperidyl group, etc.), alkylthio groups (e.g., methylthio group, ethylthio group, etc.)
, heterocyclylthio groups (e.g. benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (e.g. methylamino group) group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di-(β-hydroxyethyl)amino group, β-sulfoethylamino group) , arylamino group, or substituted arylamino group (
For example, anilino group, o-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group, m-carboxyanilino group, p- Carboxyanilino group, o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisidino group, m-anisidino group, p-anisidino group, o-acetaminoanilino group, hydroxy Anilino group, disulfophenylamino group, naphthylamino group,
sulfonaphthylamino group, etc.), heterocyclylamino group (e.g., 2-benzothiazolylamino group, 2-pyridyl-amino group, etc.), substituted or unsubstituted aralkylamino group (e.g., benzylamino group, o-anisylamino group, m -anisyl amino group, p-anisyl amino group, etc.)
, an aryl group (such as a phenyl group), or a mercapto group. R21, R22, R23, and R24 may be the same or different from each other. -A- is selected from the group A2-, R21, R22, R23, R24
At least one of them needs to have one or more sulfo groups (which may be free acid groups or may form salts). W3 and W4 represent -CH= or -N=, and at least one of them is -N=.

Next, specific examples of compounds included in the general formula (VII) will be given. However, it is not limited only to these compounds. (VII-1) 4,4'-bis[4,6-di(
Benzothiazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (VII-2) 4,4'-bis[4,6-
Di(benzothiazolyl-2-amino)pyrimidine-2-
ylamino)] stilbene-2,2'-disulfonic acid disodium salt (VII-3) 4,4'-bis[4,6-di(
naphthyl-2-oxy)pyrimidin-2-ylamino]
Stilbene-2,2'-disulfonic acid disodium salt (
VII-4) 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid disodium salt (V
II-5) 4,4'-bis(4,6-dianilinopyrimidin-2-ylamino)stilbene-2,2'
-Disulfonic acid disodium salt (VII-6) 4,4'-bis[4-chloro-
6-(2-naphthyloxy)pyrimidin-2-ylamino]biphenyl-2,2'-disulfonic acid disodium salt (VII-7) 4,4'-bis[4,6-di(1-phenyltetrazolyl) -5-thio)pyrimidine-
2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (VII-8) 4,4'-bis[4,6-di(
Benzimidazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (VII-9) 4,4'-bis[4,6
-Diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (VII-10) 4,4'-bis[4,6-diphenylthiopyrimidin-2-ylamino)stilbene-2
,2'-disulfonic acid disodium salt (VII-11) 4,4'-bis[4,6-dimercaptopyrimidin-2-ylamino)biphenyl-2,
2'-Disulfonic acid disodium salt (VII-12) 4,4'-bis[4,6-dianilino-triazin-2-ylamino)stilbene-2,
2'-Disulfonic acid disodium salt (VII-13) 4,4'-bis(4-anilino-
6-Hydroxy-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (VII
-14) 4,4'-bis[4-naphthylamino-6
-anilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (VII-1
5) 4,4'-bis[2,6-di(2-naphthoxy)pyrimidin-4-ylamino]stilbene-2,2'
-Disulfonic acid (VII-16) 4,4'-bis[2,6-di(2
-naphthylamino)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt (VI
I-17) 4,4'-bis[2,6-dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (VII-18) 4,4'-bis[2-naphthyl 4,4'-bis[2,6-diphenoxypyrimidin-4-ylamino]stilbene-2,
2'-Disulfonic acid ditriethylammonium salt (VI
I-20) 4,4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidin-4-ylamino]
Stilbene-2,2'-disulfonic acid disodium salt

[
The compound represented by the general formula (VII) is known or can be easily produced according to known methods. The compound represented by the general formula (VII) used in the present invention may be a mixture of two or more thereof. The compound of general formula (VII) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. Sensitizing dye and general formula (VII)
The ratio (weight ratio) of the dye to the compound represented by formula (VII) is preferably in the range of 1/1 to 1/200, particularly 1/2 to 1/50. Ranges are advantageously used. General formula (VI
The compound represented by I) can be directly dispersed in the emulsion, or it can be dissolved in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof and added to the emulsion. You can also do that. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. They can also be dispersed and added into the emulsion by the method described in JP-A-50-80119.

There are no particular restrictions on the various other additives and development processing methods used in the photosensitive material of the present invention, and for example, those described in the relevant sections below can be preferably used. item
Relevant part 1) Silver halide emulsion and its manufacturing method, page 20, lower right column, line 12 of JP-A-2-97937
21st page, lower left column, line 14, and JP-A-2-1
2
Publication No. 236, page 7, upper right column, line 19 to page 8
Lower left column, line 12. 2) Surfactant/antistatic agent JP-A-2-12236
Publication No. 9, upper right column, line 7
7th line of the lower right column and JP-A-2-18542
From line 13 in the lower left column of page 2 to line 18 in the lower right column of page 4
. 3) Anti-fogging agent/stability JP-A-2-10352
Publication No. 6, page 17, lower right column 19 Agent
From line 4 to page 18, top right column, line 1 and bottom right column, page 18
5th line from the eye. 4) Polymer latex, page 18, lower left column 12
From line 20. 5) Compounds with acid groups From page 18, lower right column, line 6 to page 19, upper left column, line 1
Eye and Unexamined Japanese Patent Publication No. 2-553
Publication No. 49, page 8, lower right column 1
From line 3 to page 11, top left column, line 8. 6) Matting agent/slip agent/JP-A-2-10352
Publication No. 6, page 19, upper left column 15 Plasticizer
From line 15, page 19, top right column 15
Row number. 7) Hardening agent JP-A-2
-Publication No. 103536, page 18, upper right column, line 5
Same from the eyes
7th line. 8) Dye Same No. 1
Page 7, lower right column, line 1 to line 18. 9) Binder JP-A-2-1
Publication No. 8542, page 3, bottom right column, line 1?
20th line. 10) Developing solution and developing method JP-A-2-553
Publication No. 49, page 13, bottom right column, line 1
From page 16, top left column, line 10.

The photosensitive material of the present invention has a total processing time of 15 seconds or more.
It exhibits excellent performance in rapid development processing using an automatic processor in 60 seconds. In the rapid development process of the present invention, the temperature and time of development and fixing are each about 25 DEG C. to 50 DEG C. and 25 seconds or less, preferably 30 DEG C. to 40 DEG C. and 4 seconds to 15 seconds. In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed. Here, in the water washing step, water can be saved by using a two to three stage countercurrent washing method. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Furthermore, part or all of the overflow liquid from the washing bath or stabilizing bath can be used as a fixing solution as described in JP-A-60-235133. By doing so, the amount of waste liquid is also reduced, which is more preferable. In addition, in the washing water, mold inhibitors (for example, the compounds described in Horiguchi's "Chemistry of Bacteria and Prevention", Japanese Patent Application Laid-open No. 115154/1983), washing accelerators (sulfites, etc.), chelating agents, etc. May contain. The temperature and time of the water washing or stabilization bath in the above method are 0°C to 50°C for 5 seconds to 30 seconds, preferably 4 seconds to 20 seconds at 15°C to 40°C. The total processing time in the present invention is defined as the time after the leading edge of the film is inserted into the insertion slot of the automatic processor, the film passes through the developing tank, transfer section, fixing tank, transfer section, washing tank, transfer section, and drying section. This is the total time it takes for the tip to emerge from the drying outlet. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[0073]

【Example】

Example 1 Liquid 2 and 3 were added to 1 liquid in Table 1 maintained at 38°C and pH 4.5.
The solution was added simultaneously over 24 minutes with stirring until 0.
．． Particles of 18 μm were formed. Next, add 4 liquids and 5 liquids in Table 1.
Add the solution over 8 minutes and add 0.15 g of potassium iodide.
was added to terminate particle formation. After that, it was washed with water by the flocculation method according to the usual method, gelatin was added, the pH was adjusted to 5.2, the pAg was adjusted to 7.5, 8 mg of sodium thiosulfate and 12 mg of chloroauric acid were added, and the sensitivity reached its maximum at 65°C. Chemically sensitized to give

[0074]

[Table 1]

Further, as a stabilizer, 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene 50
mg, phenoxyethanol as preservative 100pp
m, and finally silver chloride was added to 80 mol%.
A silver iodochlorobromide cubic grain emulsion A having an average grain size of 0.20 μm was obtained. (variation coefficient 9%)

After grain formation was carried out in exactly the same manner as in Emulsion A, the grains were washed with water, gelatin was added, and the pH and pAg were adjusted to be the same as in Emulsion A. Then 4 mg of sodium thiosulfate and N,N-
2 mg of dimethylselenourea, 10 mg of chloroauric acid, 4 mg of sodium benzenethiosulfonate, and 1 mg of sodium benzenethiosulfinate were added, and chemical sensitization was carried out at 55° C. to achieve optimum sensitivity. Additionally, stabilizers and preservatives were added in the same manner as in Emulsion A. This emulsion was designated as B.

Preparation of coating samples Emulsion A was diluted with gelatin to give A-■ to A-■, emulsion B was similarly diluted with gelatin to give B-■ to B-■, and then ortho-sensitizing dye A was added. Ortho sensitization was performed by adding 200 mg/mol Ag of -6. Furthermore, for supersensitization and stabilization, 4,4'-bis-(4,6-dinaphthoxy-pyrimidin-2-ylamino)-stilbendisulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzo 300 each of thiazole iodo salts per mole of silver.
mg and 450 mg were added. In addition, polyethyl allylate latex was added to the gelatin binder ratio at 25% and the particle size was 10.
Colloidal silica of μm was added to the gelatin binder ratio of the emulsion layer at a ratio of 30%, and 2-bis(vinylsulfonylacetamido)ethane was added as a hardening agent at a concentration of 80 mg/m2, and the amount of silver was 3.0 g/m2 on a polyester support. Then, the upper protective layer and the lower protective layer shown in Table 2 were simultaneously applied.

[0078]

[Table 2]

At this time, the amount of gelatin applied and the amount of polyhydroxybenzene added in each layer were as shown in Table 3. Note that polyhydroxybenzene was added to the upper layer of the protective layer.

[0080]

[Table 3]

The sample support used in this example had a back layer and a back protective layer having the following compositions.

[Back layer] Gelatin

2.0g/m2 Sodium dodecylbenzenesulfonate
80mg/m2 dye■

100m
g/m2 dye■

100mg/m2 dye■


100mg/m2 dye■

100mg/m2
1,3-divinylsulfone-2-propanol
60mg/m2

00
83]

[C36]

[Back protective layer] Gelatin

0.5g/m2 polymethyl methacrylate (particle size 4.7μm)
50mg/m2 Sodium dodecylbenzenesulfonate
20mg/m2 Compound■

2mg/m2
Compound■

1mg/m2 silicone oil
100mg/m
2

[0085]

[C37]

Evaluation of Samples 1) Evaluation of Processing Solution Composition Dependency Samples 1 to 17 in Table 3 were exposed to xenon flash light with an emission time of 10-6 sec through an interference filter with a transmission peak at 488 nm and a continuous wedge. Sensitometry was performed using an automatic processor FG710NH manufactured by Fuji Photo Film Co., Ltd. at the temperature and time shown below. Development 38℃
Fixed for 14 seconds at 37℃
Wash with water for 9.7 seconds at 30℃
9 second squeeze
Dry for 2.4 seconds 5
5℃ 8.3 seconds total
43.4 seconds At this time, the developer and fixer used had the compositions shown in Tables 4 and 5. Sensitivity is expressed by taking the logarithm of the reciprocal of the exposure amount that gives a density of 3.0, and the sensitivity difference (△
log E) was taken as treatment liquid composition dependence. The smaller the difference in sensitivity, the more stable and desirable it is in terms of performance.

[0087]

[Table 4]

[0088]

[Table 5]

As is clear from Results Table 3, the total amount of gelatin applied was 2.5g.
/m2 or less and samples made of emulsions subjected to selenium sensitization are found to have less dependence on processing solution composition. At this time, when the coating amount of gelatin in the protective layer is 0.5 g/m2 or less, and when polyhydroxybenzene is used in combination, the dependence on liquid composition is significantly improved, and the effects of the present invention can be seen.

Example 2 Liquids 2 and 3 were added simultaneously over 30 minutes with stirring to the liquid 1 shown in Table 6 maintained at 40°C and pH=4.5.
．． Particles of 15 μm were formed. Next, liquids 4 and 5 in Table 6
The solution was added over 10 minutes and 30 cc of a 1% solution of potassium iodide was added to complete particle formation. After that, it was washed with water by the flocculation method according to the usual method, gelatin was added, the pH was adjusted from 5.2 pAg to 7.5, 10 mg of sodium thiosulfate and 15 mg of chloroauric acid were added, and the pH was adjusted to 7.5.
Chemical sensitization was performed to achieve maximum sensitivity at 5°C.

[0091]

[Table 6]

Further, as a stabilizer, 50 m of 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene
g, 100 ppm of phenoxyethanol as a preservative
Finally, a silver iodochlorobromide cubic emulsion C containing 60 mol % of silver chloride and having an average grain size of 0.15 μm was obtained. After grain formation was carried out in the same manner as in Emulsion C, it was washed with water, gelatin was added, and the pH was adjusted from 5.2 pAg to 7.5. After that, 6 mg of sodium thiosulfate, 4 mg of N,N-dimethylselenourea, 15 mg of chloroauric acid, 5 mg of sodium benzenethiosulfonate, and 1 mg of sodium benzenethiosulfinate were added, and chemically amplified at 60°C to obtain the optimum sensitivity. I felt it. Further, stabilizers and preservatives were added in the same manner as in Emulsion C to obtain Emulsion D.

Preparation of coating samples Emulsions C and D were diluted with gelatin to prepare C-■ to ■ and D-■ to ■.
Color sensitization was performed by adding 0 mg/mol Ag. Furthermore, for supersensitization and stabilization, 4,4'-bis-(4,6-dinaphthoxy-pyrimidin-2-ylamino)-stilbendisulfonic acid disodium salt and 2,5-dimethyl-3
-Allyl-benzothiazole iodo salts were added in an amount of 300 mg and 450 mg per mole of silver, respectively. In addition, polyethyl allylate latex is added to the gelatin binder ratio of 2.
Colloidal silica with a grain size of 5% and a particle size of 10 μm was added to the gelatin binder ratio of the emulsion layer at a ratio of 30%, and 2-bis(vinylsulfonylacetamido)ethane was added as a hardening agent at a concentration of 80 mg/m2 to form a silver amount of 3 on a polyester support. .2g/
m2, and the upper protective layer and lower protective layer described in Tables 7 and 8 were simultaneously coated.

[0094]

[Table 7]

[0095]

[Table 8]

At this time, the amount of gelatin applied and the amount of polyhydroxybenzene added in each layer were as shown in Table 9. At this time, polyhydroxybenzene was added to the emulsion layer.

[0097]

[Table 9]

[0098] The support for the coated sample here is as shown in Example-
The same back and back protective layer as used in 1 was used.

Sample evaluation 1) Processing liquid composition dependence Samples 18 to 29 in Table 9 were exposed to xenon flash light with an emission time of 10-6 sec through an interference filter with a transmission peak at 633 nm and a continuous wedge. Then, sensitometry was carried out at the temperature and time shown below using a modified automatic processor FG460A to increase the linear velocity. Development 38℃
Fixed for 12 seconds
38℃ 9 seconds water
Wash at 35℃ for 9 seconds
squeeze
2 seconds dry
55℃ 12 seconds Total 44 seconds
The linear velocity was 2050 mm/min. The developing solution and fixing solution used at this time were the same as those used in Example-1, and the evaluation was carried out in the same manner.

2) Evaluation of the aging properties of the thermosensitive material was performed when the material was stored for 5 days at 50°C and a relative humidity of 5 to 10% (stored in a ventilated can).
Changes in sensitivity and fog values were expressed as differences from samples stored at room temperature without being placed in a ventilated can. At this time, the automatic processor used was a modified FG460A, which was the same as that used for the evaluation of processing dependence, and the developer used was as shown in (a) in Table 4 above.

[0101] It is clear from Results Table 9 that the total amount of gelatin applied was 2.5 g/m
It can be seen that the emulsions with a value of 2 or less and subjected to selenium sensitization have improved both processing solution composition dependence and thermostatic properties. Furthermore, it can be seen that when the coating amount of gelatin in the protective layer is 0.5 g/m2 or less and when polyhydroxybenzene is added, the composition dependence and thermostatic properties are further improved.

Example 3 Liquids 2 and 3 were added simultaneously over 24 minutes to the liquid 1 shown in Table 10 maintained at 40°C and pH 4.5 while stirring.
Particles were formed. Subsequently, liquids 4 and 5 shown in Table 10 were added over 8 minutes, and 0.4 g of potassium iodide was added to complete particle formation.

[0103]

[Table 10]

[0104] After that, it was washed with water by the flocculation method according to a conventional method, and after adding gelatin, the pH was adjusted to 5.2p.
Ag was adjusted to 7.5, 5 mg of sodium thiosulfate and 10 mg of chloroauric acid were added, and chemically sensitized at 65°C to achieve maximum sensitivity, containing 40 mol% of silver chloride and having an average particle size of 0.16μ.
A monodisperse silver iodochlorobromide cubic emulsion E of m was obtained. (Coefficient of variation: 10%) Emulsion F is an emulsion which is formed in the same manner as emulsion E, except that the amount of ammonium hexachlororhodium(III) acid solution used is increased by 1.2 times to form grains and to chemically sensitize the emulsion. After forming grains in exactly the same manner as in Emulsions E and F, adding gelatin and adjusting the pH and pAg, 4 mg of the following compound (A), 3 mg of sodium thiosulfate, 20 mg of chloroauric acid, and benzenethiosulfone were added during chemical sensitization. acid soda 4mg
After adding 1 mg of sodium benzenethiosulfinate, chemical sensitization was carried out at 60° C. to achieve optimum sensitivity.

[0105]

[C38]

These emulsions were designated as G and H. These emulsions E
~H is 2-methyl-4-hydroxy-1, as a stabilizer
100 mg of 3,3a,7-tetrazaindene and phenoxyethanol as a preservative were added at a concentration of 100 ppm.

Preparation of coating samples Two types of emulsions with different gelatin concentrations were prepared from the above emulsions E to H, and infrared sensitizing dye D-7 was added at 200 mg/mol Ag.
In addition, color sensitization was performed. Furthermore, for supersensitization and stabilization, 4,4'-bis-(4,6-dinaphthoxy-pyrimidin-2-ylamino)-stilbenedisulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzo Thiazole iodo salts were added in amounts of 300 mg and 450 mg, respectively, per mole of silver. In addition, polyethyl allylate latex was added to the gelatin binder ratio at 25%, and colloidal silica with a particle size of 10 μm was added to the gelatin binder ratio at 30% in the emulsion layer.
%, and 2-bis(vinylsulfonylacetamido)ethane was added as a hardening agent at a concentration of 80 mg/m 2 , and the protective layer and emulsion layer were each coated in a multilayer manner on a polyester support. At this time, the upper layer of the protective layer is Table-11, and the lower layer of the protective layer is Table-12.
The details of the application sample are shown in the table below.
It was described in 13. Here, polyhydroxybenzene was added to the lower layer of the protective layer.

[0108]

[Table 11]

[0109]

[Table 12]

[0110]

[Table 13]

The amount of silver coated in the emulsion layer was 1.3 g/m2 for each of the upper and lower layers, for a total of 2.6 g/m2. Further, the relative sensitivity ratios of emulsions E to F are shown in Table-14.

[0112]

[Table 14]

The sample coated here uses a support having the same back and back protective layer as used in Example-1.

[0114] Samples 30 to 38 in Sample Evaluation Table-13 were exposed to xenon flash light with an emission time of 10-6 seconds through an interference filter having a transmission peak at 780 nm and a continuous wedge, and the results were as shown in Example-1. The same automatic processor that I used (FG710NH
) and a processing agent, and the dependence on the composition of the processing solution was evaluated in the same manner. The results are summarized in Table 13, and it can be seen that the dependence on the composition of the processing solution is improved by reducing the coating amount of gelatin to 2.5 g/m2 or less and using a selenium-sensitized emulsion.

Claims (5)

[Claims] 1. A silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer and at least one protective layer on the same side of a support, wherein the light-sensitive silver halide emulsion is halogenated. Contains 10-5 mol or less of an iridium compound per 1 mol of silver, is sensitized with a selenium sensitizer, and furthermore, the total amount of gelatin coated on the silver halide emulsion layer side is 2.5 g/m2 or less. Characteristic silver halide photographic material. 2. The silver halide photographic material according to claim 1, wherein the coating amount of gelatin in the protective layer of the light-sensitive silver halide emulsion layer is 0.5 g/m 2 or less. 3. The silver halide photographic material according to claim 1, which contains at least one polyhydroxybenzene compound represented by the following general formula. [Chemical formula 1] [Claim 4] The time from development to fixation to water washing to drying is within 60 seconds, and the film transport speed (linear speed) is 150 seconds or less.
4. The method of developing a photosensitive material according to claim 1, wherein the processing is carried out using an automatic developing machine having a speed of 0 mm/min or more. Claim 5: The replenishment amount of the developer and fixer is
5. The developing method according to claim 4, wherein the amount is 200 cc or less per m2.