JPH04324855A - Silver halide photosensitive material and its treatment method - Google Patents

Abstract

PURPOSE:To obtain a high contrast image by setting the silver chloride content of emulsion to be 50%mol or more with specific iridium compound contained per silver mol, applying chemical sensitization with selenium sensitizer and combining sensitizing coloring matter and compound. CONSTITUTION:Photosensitive material is silver halide with silver chloride being 50%mol or more, contains 10<-9>mol or more iridium compound, is chemically sensitized by selenium compound, provides spectral sensitivity to infrared light or laser light, and contains compound shown in formula I, where A represents bivalent aromatic remaining radical, and each of R21, R22, R23 and R24 represents hydrogen atom, hydroxy group, alkyl group, alkoxy group, arylxy group, halogen atom, hetero ring nucleus, heterocyclothio group, arylthio group, amino group, or etc. However, at least one of A, R21, R22, R23 and R24 has sulfonic group. W3 and W4 are -CH=, or -N=, at least one of W3 and W4 being -N=.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to silver halide photographic light-sensitive materials, and more specifically, in high-intensity short-time exposure,
The present invention relates to a silver halide photographic material having high sensitivity, excellent handling properties under a safe light, and suitability for rapid processing, and a developing 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 utilize scanner-based image forming methods, and the recording light sources of these scanner-type recording devices include glow lamps, xenon lamps, tungsten lamps, LEDs, He-Ne lasers, and argon lasers. and semiconductor lasers. The photosensitive materials used in these scanners are required to have various properties, especially 10-3.
Even under such conditions, high sensitivity and high contrast are essential conditions since exposure is performed for a short time of ~10-7 seconds. In addition, spectral sensitization is usually performed to provide wavelength suitability for various laser light sources. For example, the compound represented by the general formula (I) of the present invention is mainly He-
It has spectral sensitivity suitability for Ne laser, and has the general formula (I
The compounds represented by I) and (III) have spectral sensitivity suitability mainly for semiconductor lasers. Although the compounds represented by these general formulas are superior to other sensitizing dyes in terms of sensitivity and residual color, they cannot be said to have sufficiently high spectral sensitization efficiency, and depending on the amount added, they may cause inherent desensitization. It may occur. As a method to increase the efficiency of spectral sensitization,
For example, for He-Ne laser light source applications, Japanese Patent Publication No. 49-25500, and for semiconductor laser applications, JP-A-59-19032, JP-A-59-192242, etc. are cited; Problems such as deterioration in quality and residual color may occur. 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. Materials are desired to have high sensitivity, excellent processing stability, and be able to be rapidly developed. The rapid development process here refers to the leading edge of the film being inserted into an automatic developing machine, passing through the developing tank, transition area, fixing tank, transition area, washing tank, and drying area before the leading edge of the film emerges from the drying area. This refers to processing that takes 15 to 60 seconds.

0003

[Problems to be Solved by the Invention] Therefore, it is an object of the present invention to have a spectral sensitivity appropriate to the laser light source used for exposure, and to achieve high sensitivity, high contrast, and process dependence in high-intensity, short-time exposure. The object of the present invention is to provide a silver halide photographic light-sensitive material that has a small amount and can be rapidly processed, and a processing method for the same. Another object of the present invention is to provide a silver halide photographic light-sensitive material and a processing method thereof, in which the photographic properties are less likely to change during long-term operation even if the amount of replenishment of the developer and fixer in an automatic processor is reduced. be. Still another object of the present invention is to provide a silver halide photographic material that is easy to handle under safe light.

0004

[Means for Solving the Problems] These objects of the present invention have at least one photosensitive silver halide emulsion layer on a support, and the silver halide emulsion contains 50 mol% or more of silver chloride. In a silver halide photographic light-sensitive material comprising silver halide grains containing 10-9 mol or more of an iridium compound per mol of silver, the silver halide emulsion has the general formula (I
), (II) or (III), contains a compound of general formula (IV), and is further chemically sensitized with a selenium sensitizer. This was achieved using silver oxide photographic materials.

[0005]

[Chemical formula 8]

[0006]

[Chemical formula 9]

In general formula (II), R1 and R2
may be the same or different, and each represents an alkyl group. R3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z1 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X1 represents an acid anion. m, p and q each independently represent 1 or 2. However, when the dye forms an inner salt, q is 1.

[0008]

[Chemical formula 10]

In the formula, R1' and R2' may be the same or different, and each represents an alkyl group. R3' and R4' each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R5' and R6' each represent a hydrogen atom, or R5' and R6
' are linked to form a divalent alkylene group. R7'
is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or -NW1'(W2')
represents. However, W1' and W2' each independently represent an alkyl group or an aryl group, and W1' and W2' can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Furthermore, R3' and R7' or R4' and R7' can be linked to form a divalent alkylene group. Z' and Z1' each independently represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X1 represents an acid anion, m
' represents 1 or 2. However, when the dye forms an inner salt, m' is 1.

0010

[Chemical formula 11]

[0011] 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,
It represents an arylthio group, an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group. However, A, R21, R22, R23 and R
At least one of 24 has a sulfo group. W
3 and W4 represent -CH= or -N=. However, at least one of W3 and W4 represents -N=.

The specific structure of the present invention will be explained in detail below. The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodochlorobromide, etc., but the content of silver chloride should be 50 mol% or more, particularly 70 mol% or more. It is preferable that there be. The average grain size of the silver halide used in the present invention is fine (for example, 0.7 μm).
(below) is more preferable, and 0.5μ or less is particularly preferable. The shape of the silver halide grains used in the present invention may be cubic, octahedral, dodecahedral, plate-like, or spherical, or may be a mixture of these various shapes.
Cubic, tetradecahedral, and tabular grains are preferred. Preferably, the particle size distribution is monodisperse. The monodisperse grains herein mean a silver halide emulsion having a grain size distribution with a coefficient of variation of 20% or less, particularly preferably 15% or less. The coefficient of variation (%) is expressed as a value obtained by dividing the standard deviation of the grain size of silver halide grains by the average value of the grain size and multiplying the value by 100.

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. In addition, in order to make the particle size uniform, British Patent No. 1,535,
No. 016, Special Publication No. 48-36890, No. 52-1636
As described in No. 4, there is a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4,242,445, and Japanese Patent Application Laid-Open No. 1973-15.
It is preferable to use a method of varying the concentration of an aqueous solution as described in No. 8124 to grow rapidly within a range that does not exceed the critical saturation level. The silver halide grains may have a so-called core/shell type structure in which the interior and surface layers have different halogen compositions.

[0014] 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 by dissolving them in water or a suitable solvent, but methods commonly used to stabilize solutions of iridium compounds include a hydrogen halide aqueous solution (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 5×1 per mole of silver halide finally formed.
0-9 to 1 x 10-4 mol is appropriate, preferably 1
x10-8 to 1 x 10-5 mol, most preferably 5 x 1
It is 0-8 to 5 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,
It is preferably added during grain formation and incorporated into the silver halide grains. Also, VII other than iridium compounds
A compound containing a group I atom and an iridium compound may be used in combination. A combination of two or three types of rhodium salts and iron salts can be advantageously used.

The grain formation of the silver halide emulsion of the present invention is as follows:
Preferably, the reaction is 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 are:
It is a compound represented by the following general formula described in JP-A-53-82408 and JP-A-55-77737.

[0016]

[Chemical formula 12]

In the formula, R1, R2, R3 and R4
is a substituted or unsubstituted alkyl group, alkenyl group (
(allyl group, etc.), or substituted or unsubstituted aryl, which may be the same or different from each other,
The total number of carbon atoms in R1 to R4 is preferably 30 or less. Also, R1 and R2, R2 and R3, or R3
and R4 to form a 5- to 6-membered heterocyclic imidazolidinethione, piperidine, morpholine, etc. Both straight chain and branched alkyl groups are used as the alkyl group. Examples of substituents for alkyl groups include hydroxy groups (-OH), carboxy groups, sulfonic acid groups, amino groups, alkoxy groups (o-alkyl) in which the alkyl residue has 1 to 5 carbon atoms, phenyl groups, It is a 5- or 6-membered heterocycle (such as furan). The substituent for the aryl group is a hydroxy group, a carboxy group or a sulfonic acid group. Here, particularly preferably R1 to R4
Among them, there are three or more alkyl groups, each alkyl group has 1 to 5 carbon atoms, the aryl group is a phenyl group, and R1
The total number of carbon atoms in ~R4 is 20 or less. Examples of compounds that can be used in the present invention include the following.

[0018]

[Chemical formula 13]

[0019]

[Chemical formula 14]

[0020]

[Chemical formula 15]

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.; 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.

[0022]

[Chemical formula 16]

The amount of silver halide solvent added varies depending on the type of compound used, the intended grain size, 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.

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 (V
III) and (IX).

[0025]

[Chemical formula 17]

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 (VIII), 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 (VIII), more preferably N,N-
Dialkylselenourea, N,N,N'-trialkyl-
N'-acylselenourea, tetraalkylselenourea,
Represents N,N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

[0027]

[Chemical formula 18]

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 (IX), 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 (IX), 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 (IX), 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 (IX), 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 (IX),
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 (IX), more preferably it represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Below is the general formula (
Specific examples of the compounds represented by VIII) and (IX) are shown below, but the present invention is not limited thereto.

[0029]

[Chemical formula 19]

[0030]

[C20]

[0031]

[C21]

[0032]

[C22]

[0033]

[C23]

[0034]

[C24]

[0035]

[C25]

[0036]

[C26]

Regarding the selenium sensitization method, US Pat.
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 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.

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 progress 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.

The sensitizing dyes preferably used in the silver halide emulsion of the present invention have optimal spectral sensitivity to He-Ne lasers and semiconductor lasers, and have general formulas (I), (II), ( III). However, when these sensitizing dyes are used alone, the efficiency of spectral sensitization is not sufficient, and when the amount added is increased, the inherent desensitization tends to increase. As a countermeasure against this, it is known to use a compound of general formula (IV) in combination, for example, in Japanese Patent Publication Nos. 60-45414 and 46-1047.
No. 3, JP-A-59-192242, etc. However, when combined with the emulsion of the present invention, the efficiency of spectral sensitization is further increased, and it is not expected by those skilled in the art that the sensitivity when using a He-Ne or semiconductor laser light source will be even higher than that of conventional ones. It was effective. Each general formula will be explained in detail below.

In the above general formula (I) of the sensitizing dye used in the present invention, the nitrogen-containing heterocyclic nucleus completed by Z or Z1 may be the following. Thiazole nucleus {e.g. thiazole, 4-methylthiazole, 4
-phenylthiazole, 4,5-dimethylthiazole,
4,5-di-phenylthiazole etc.}, benzothiazole nucleus {e.g. benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6 -bromobenzothiazole,
5-iodobenzothiazole, 6-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-
Ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5
-Carboxybenzothiazole, 5-fluorobenzothiazole, 5-dimethylaminobenzothiazole, 5-
Acetylaminobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5
-ethoxy-6-methylbenzothiazole, tetrahydrobenzothiazole, etc.}, naphthothiazole core {e.g. naphtho[2,1-d]thiazole, naphtho[1,2-
d]thiazole, naphtho[2,3-d]thiazole, 5
-Methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-methoxynaphtho[
2,3-d]thiazole etc.}, selenazole nucleus {e.g. 4-methylselenazole, 4-phenylselenazole etc.}, benzoselenazole nucleus {e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole sol, 5-methoxybenzoselenazole,
5-methylbenzoselenazole, 5-hydroxybenzoselenazole, etc.}, naphthoselenazole {for example, naphtho[2,1-d]selenazole, naphtho[1,2-d]
] selenazole, etc.}, oxazole nucleus {e.g. oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, etc.}, benzoxazole nucleus {e.g. benzoxazole, 5-fluorobenzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5-methylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5
, 6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6-dimethoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole, 5-acetylbenzoxazole, 5-hydroxybenzoxazole oxazole, etc.}, naphthoxazole nuclei {e.g. naphtho[2,1-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2,3-d]
oxazole, etc.}, 2-quinoline nucleus, imidazole nucleus, benzimidazole nucleus, 3,3'-dialkylindolenine nucleus, 2-pyridine nucleus, thiazoline nucleus, etc. can be used. Particularly preferably, at least one of Z and Z1 is a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, or a benzoxazole nucleus.

The alkyl group represented by R or R1 in the above general formula is an alkyl group having 5 or less carbon atoms {
For example, methyl group, ethyl group, n-propyl group, n-butyl group}, substituted alkyl groups include substituted alkyl groups whose alkyl radical has 5 or less carbon atoms {for example, hydroxyalkyl group (e.g. 2-hydroxyethyl group, 3-hydroxyethyl group, etc.) -hydroxypropyl group, 4-hydroxybutyl group), carboxyalkyl group (e.g. carboxymethyl group, 2-hydroxybutyl group, etc.),
Carboxyethyl group, 3-carboxypropyl group, 4-
Carboxybutyl group, 2-(2-carboxyethoxy)
ethyl group, etc.), sulfoalkyl group (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-(3-sulfopropoxy) ) Ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2-(3-sulfopropoxy)propyl group, 2-[
3-sulfopropoxy)ethoxy]ethyl group, 2-hydroxy-3-(3'-sulfopropoxy)propyl group, etc.), aralkyl group (the number of carbon atoms in the alkyl radical is 1 to
5 is preferred, and the aryl group is preferably a phenyl group, such as benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, p-tolylpropyl group, p-
Methoxyphenethyl group, p-chlorphenethyl group, p-
Carboxybenzyl group, p-sulfophenethyl group, p-
sulfobenzyl group, etc.), aryloxyalkyl group (the number of carbon atoms in the alkyl radical is preferably 1 to 5, and the aryl group of the aryloxy group is preferably a phenyl group, such as phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, p -methylphenoxyethyl group, p-
methoxyphenoxypropyl group, etc.), vinylmethyl group, etc.} Examples of the aryl group include phenyl group, etc. L, L1 and L2 represent a methine group or a substituted methine group =C(R')-. R' is an alkyl group (e.g., methyl group, ethyl group, etc.), a substituted alkyl group (e.g., an alkoxyalkyl group (e.g., 2-ethoxyethyl group, etc.)
, carboxyalkyl group (e.g. 2-carboxyethyl group etc.), alkoxycarbonylalkyl group (e.g. 2-carboxyethyl group etc.)
-methoxycarbonylethyl group, etc.), aralkyl group (
For example, benzyl group, phenethyl group, etc.}, aryl group (for example, phenyl group, p-methoxyphenyl group, etc.)
p-chlorophenyl group, o-carboxyphenyl group, etc.). Further, L and R, and L1 and R1 may each be bonded through a methine chain to form a nitrogen-containing heterocycle. Examples of the substituent attached to the nitrogen atom at the 3-position of the thiazolinone nucleus or imidazolinone nucleus formed by Q and Q1 include an alkyl group (preferably having 1 to 8 carbon atoms, such as a methyl group, ethyl group, propyl group, etc.) , allyl group,
Aralkyl group (alkyl group, radical has 1 to 5 carbon atoms)
are preferable, for example, benzyl group, p-carboxyphenylmethyl group, etc.), aryl group (preferably the total number of carbon atoms is 6 to 9, e.g. phenyl group, p-carboxyphenyl group, etc.), hydroxyalkyl group (carbon number of alkyl radical is preferably 1 to 5, such as a 2-hydroxyethyl group), a carboxyalkyl group (the number of carbon atoms in the alkyl radical is preferably 1 to 5, such as a carboxymethyl group), an alkoxycarbonyl alkyl group (the alkyl radical in the alkoxy moiety is Preferably 1 to 3 carbon atoms,
The number of carbon atoms in the alkyl moiety is preferably 1 to 5, such as a methoxycarbonylethyl group.

[0044] Examples of the anion represented by Examples include methyl sulfate ion and ethyl sulfate ion.

Next, general formula (II) will be explained. In the formula, R1 and R2 may be the same or different, and each represents an alkyl group (including substituted alkyl groups). Preferably 1 to 8 carbon atoms. For example, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl. Examples of substituents include carboxyl groups, sulfo groups, cyano groups, halogen atoms (e.g. fluorine atoms,
chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably 8 or less carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (preferably 7 or less carbon atoms, such as methoxy, ethoxy, propoxy,
butoxy, benzyloxy), aryloxy groups (e.g. phenoxy, p-tolyloxy), acyloxy groups (e.g. phenoxy, p-tolyloxy),
Preferably 3 or less carbon atoms, such as acetyloxy,
propionyloxy), acyl groups (preferably up to 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (e.g. carbamoyl, N
, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl,
morpholinosulfonyl), aryl groups (e.g. phenyl, p-hydroxyphenyl, p-carboxyphenyl,
Examples include alkyl groups substituted with p-sulfophenyl, α-naphthyl, etc. (preferably the alkyl moiety has 6 or less carbon atoms). However, two or more of these substituents may be substituted with an alkyl group in combination.

R3 is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl), or a lower alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy ,
butoxy), phenyl group, benzyl group or phenethyl group. In particular, lower alkyl groups and benzyl groups are advantageously used. V is a hydrogen atom, a lower alkyl group (preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl)
, alkoxy groups (preferably 1 to 4 carbon atoms, e.g. methoxy, ethoxy, butoxy), halogen atoms (e.g. fluorine atoms, chlorine atoms), substituted alkyl groups (preferably 1 to 4 carbon atoms, e.g. trifluoromethyl, carboxymethyl).

Z1 represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus [e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6
-Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-Ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy -6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [
2,1-d]thiazole, naphtho[1,2-d]thiazole, naphtho[2,3-d]thiazole, 5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1- d] Thiazole, 8-methoxynaphtho[2,
1-d]thiazole, 5-methoxynaphtho[2,3-d
[thiazole], selenazole core [e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole,
5-hydroxybenzoselenazole, naphtho[2,1-
d] selenazole, naphtho[1,2-d]selenazole], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole,
5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-
Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-
Dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho[2,1-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2,3-d]oxazole], quinoline nucleus [e.g. 2-quinoline, 3 −
Methyl-2-quinoline, 5-ethyl-2-quinoline, 6
-Methyl-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-
Quinoline, 8-chloro-2-quinoline, 8-fluoro-
4-quinoline], 3,3-dialkylindolenine nucleus (
For example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5- Methylindolenine, 3,
3-dimethyl-5-chloroindolenine), imidazole core (e.g. 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1- Methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1
-Methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzo Imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5
-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho[1,2-d]imidazole), pyridine nuclei (e.g. pyridine, 5-methyl-2-pyridine, 3-methyl- 4-pyridine). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used. m, p and q each independently represent 1 or 2. However, when the dye forms an inner salt, q is 1.

X1 is an acid anion (for example, chloride, bromide, iodide, tetrafluoroborade, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4 −
nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate).

Next, general formula (III) will be explained. In the formula, R1' and R2' may be the same or different, and each represents an alkyl group (including a substituted alkyl group). Preferably 1 to 8 carbon atoms. For example, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl. Examples of substituents include carboxyl group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably 8 or less carbon atoms, e.g. methoxycarbonyl, ethoxy carbonyl, benzyloxycarbonyl, etc.), alkoxy groups (preferably up to 7 carbon atoms, e.g. methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy groups (e.g. phenoxy, p-tolyloxy), acyloxy groups (preferably carbon 3 or less atoms, e.g. acetyloxy, propionyloxy), an acyl group (preferably less than 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (e.g. carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl), aryl groups (e.g. phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) Examples include alkyl groups substituted with (preferably the alkyl moiety has 6 or less carbon atoms). However, two or more of these substituents may be substituted with an alkyl group in combination.

R3' and R4' are hydrogen atoms, lower alkyl groups (preferably 1 to 4 carbon atoms, such as methyl,
ethyl, propyl, butyl), lower alkoxy groups (preferably 1 to 4 carbon atoms, e.g. methoxy, ethoxy,
propoxy, butoxy), phenyl group, benzyl group or phenethyl group. In particular, lower alkyl groups and benzyl groups are advantageously used. R5' and R6' each represent a hydrogen atom, or R5' and R6' are linked to form a divalent alkylene group (eg, ethylene or trimethylene). The alkylene group may contain one, two or more suitable groups, such as alkyl groups (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl,
isopropyl, butyl), a halogen atom (for example, a chlorine atom, a bromine atom), or an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy). R7' is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, etc.), or a lower alkoxy group (preferably having 1 carbon atom).
~4, e.g. methoxy, ethoxy, propoxy, butoxy), phenyl, benzyl group, or -N(W1'
)(W2'). Here, W1' and W2' each independently represent an alkyl group (including substituted alkyl groups. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl,
benzyl, phenylethyl), or aryl groups (including substituted phenyl groups, such as phenyl, naphthyl, tolyl,
p-chlorophenyl, etc.), and W1' and W2
' can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. However, R3' and R7' or R4' and R7' are connected to form a divalent alkylene group (
(synonymous with the divalent alkylene group formed by connecting R5' and R6').

Z' and Z1' represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus [for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzo Thiazole, 6
-Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-
Fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole,
5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho[2,1-d]thiazole, naphtho[1,2
-d]thiazole, naphtho[2,3-d]thiazole,
5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-methoxynaphtho[2,3-d] thiazole], selenazole core [e.g. benzoselenazole, 5-chlorobenzoselenazole,
5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho[2,1-d] selenazole, naphtho[1,2-d]
selenazole], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzo Oxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6- Dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho[2,1-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2
, 3-d]oxazole], quinoline nucleus [e.g. 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-
Quinoline, 6-methyl-2-quinoline, 8-fluoro-
2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8
-fluoro-4-quinoline], 3,3-dialkylindolenine core (e.g., 3,3-dimethylindolenine,
3,3-diethylindolenine, 3,3-dimethyl-5
-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chlorindolenine)
, imidazole core (e.g. 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5
-Chlorbenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole , 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-
5-fluorobenzimidazole, 1-phenyl-5,
6-dichlorobenzimidazole, 1-allyl-5,6
-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1
-Methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho[1,2-d]imidazole)
, a pyridine nucleus (eg pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X1' is an acid anion (eg chloride,
Bromide, iodide, tetrafluoroborade, hexafluorophosphate, methyl sulfate, ethyl sulfate, benzene sulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4
- nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate). m' represents 0 or 1, and is 1 when the dye forms an inner salt. Specific compound examples are shown below. However, the present invention is not limited to these.

[0053]

[C27]

[0054]

[C28]

[0055]

[C29]

[0056]

[C30]

[0057]

[Chemical formula 31]

[0058]

[C32]

[0059]

[Chemical formula 33]

[0060]

[C34]

[0061]

[C35]

[0062]

[C36]

[0063]

[C37]

[0064]

[C38]

[0065]

[C39]

[0066]

[C40]

[0067]

[C41]

[0068]

[C42]

[0069]

[C43]

[0070]

[C44]

[0071]

[C45]

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. useful sensitizing dyes,
Combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are subject to Research Disclosure.
176 volume 17643 (1978 1
Published in February) Page 23, IV, Section J, or the above-mentioned Japanese Patent Publications No. 49-25500, No. 43-4933, and Japanese Patent Publication No. 59-1
9032, 59-192242, etc. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifogging compound, etc. It is desirable to select the optimal amount accordingly, and testing methods for this selection are well known to those skilled in the art. Usually, it is preferably used in a range of 10-7 mol to 1 x 10-2 mol, particularly 10-6 mol to 5 x 10-3 mol, per mol of silver halide.

Next, the compound represented by the general formula (IV) will be explained. In the formula, -A- represents a divalent aromatic residue, and these represent a -SO3M group [where M represents a hydrogen atom or a cation imparting water solubility (eg, sodium, potassium, etc.). ] may be included. -A- is usefully selected from, for example, the following -A1- or -A2-. However, when R21, R22, R23 or R24 does not contain -SO3M, -A- is -A1 -
selected from the group of

[0074]

[C46]

[0075]

[C47]

[0076]

[C48]

R21, R22, R23 and R24 are each a hydrogen atom, a hydroxy group, or a lower alkyl group (the number of carbon atoms is preferably 1 to 8, such as 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. When -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 general formula (IV) will be given. However, it is not limited only to these compounds.

(IV-1) 4,4'-bis[4
,6-di(benzothiazolyl-2-thio)pyrimidine-
2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (IV-2) 4,4'-bis[4,6-di(benzothiazolyl-2-amino)pyrimidin-2-ylamino)]stilbene-2 ,2'-disulfonic acid disodium salt (IV-3) 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt Salt (I
V-4) 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid disodium salt (IV-
5) 4,4'-bis(4,6-dianilinopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (IV-6) 4,4'-bis[4-chloro-6
-(2-naphthyloxy)pyrimidin-2-ylamino]biphenyl-2,2'-disulfonic acid disodium salt (IV-7) 4,4'-bis[4,6-di(1
-phenyltetrazolyl-5-thio)pyrimidine-2-
ylamino]stilbene-2,2'-disulfonic acid disodium salt (IV-8) 4,4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2' -Disulfonic acid disodium salt (IV-9) 4,4'-bis[4,6-diphenoxypyrimidin-2-ylamino)stilbene-
2,2'-disulfonic acid disodium salt (IV-10) 4,4'-bis[4,6-diphenylthiopyrimidin-2-ylamino)stilbene-2,
2'-Disulfonic acid disodium salt (IV-11) 4,4'-bis[4,6-dimercaptopyrimidin-2-ylamino)biphenyl-2,2
'-Disulfonic acid disodium salt (IV-12) 4,4'-bis[4,6-dianilino-triazin-2-ylamino)stilbene-2,2
'-Disulfonic acid disodium salt (IV-13) 4,4'-bis(4-anilino-6
-hydroxy-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (IV-1
4) 4,4'-bis[4-naphthylamino-6-anilino-triazin-2-ylamino)stilbene-2
,2'-disulfonic acid disodium salt (IV-15)
4,4'-bis[2,6-di(2-naphthoxy)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid (IV-16) 4,4'-bis[2,6-di( 2-
naphthylamino)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt (IV-
17) 4,4'-bis[2,6-dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (IV-18) 4,4'-bis[2-naphthylamino] -6-anilinopyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid (IV-19) 4,4'-bis[2,6-diphenoxypyrimidin-4-ylamino]stilbene-2,2
'-Disulfonic acid ditriethylammonium salt (IV-
20) 4,4'-bis[2,6-di(benzimidazolyl-2-thio)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt The compound represented by the general formula (IV) is It is known or can be easily produced according to known methods.

The compound represented by the general formula (V) used in the present invention may be a mixture of two or more thereof. The compound of general formula (V) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. The compound represented by the general formula (V) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in an appropriate solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be added to the emulsion by dissolving it in 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. They can also be dispersed and added into the emulsion by the method described in JP-A-50-80119.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these, dyes represented by general formulas (V), (VI), and (VII) are useful.

[0081]

[C49]

In the formula, R1 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, n
-propyl group, n-butyl group, n-hexyl group, isopropyl group, carboxymethyl group, hydroxyethyl group, etc.) or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms (e.g. methoxy group, ethoxy group, n- butoxy group,
methoxyethoxy group, hydroxyethoxy group, etc.), and R2 and R3 each represent a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (e.g. methyl group, Ethyl group, n-propyl group, n-butyl group, n-hexyl group,
hydroxyethyl group, etc.), substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms (e.g., methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), hydroxy group, carboxyl group, or salt thereof , represents a sulfonic acid group or a salt thereof, and R2 and R3
At least one of them represents a sulfonic acid group or a salt thereof. R4 and R5 are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, sulfoethyl group, methanesulfonamidoethyl group, carboxymethyl group, hydroxyethyl group, carboxypropyl group) group, ethoxycarbonylmethyl group, etc.), and R6 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group,
n-butoxy group, hydroxyethoxy group, etc.),
R7 is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, n-propyl group,
hydroxyethyl group, etc.) or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, hydroxyethoxy group, n-butoxy group, etc.).

[0083]

[C50]

In the formula, Q represents an atomic group necessary to form a heterocyclic nucleus of pyrazolone, barbituric acid, thiobarbituric acid, isoxazolone, 3-oxythionaphthene, and 1,3-indanedione. n represents 0 or 1.

[0085]

[C51]

In the formula, R1, R2, R3, R4,
R5 and R6 may be the same or different and represent a substituted or unsubstituted alkyl group, and Z1 and Z2 each represent a nonmetallic group necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring. Represents a group of atoms. However, R1, R2, R3, R4, R5
, R6, Z1, and Z2 have at least 3, more preferably 4 to 6, acid substituents (e.g., sulfonic acid groups or carboxylic acid groups),
Particular preference is given to groups which make it possible for the dye molecule to have 4 to 6 sulfonic acid groups. In the present invention, a sulfonic acid group means a sulfo group or a salt thereof, and a carboxylic acid group means a carboxyl group or a salt thereof. Examples of salts include alkali metal salts such as Na and K, ammonium salts, and organic ammonium salts such as triethylamine, tributylamine, and pyridine. L represents a substituted or unsubstituted methine group, and X represents an anion. Specific examples of the anion represented by X include halogen ions (Cl, Br), p-toluenesulfonic acid ions, ethyl sulfate ions, and the like. n is 1
or 2, and 1 when the dye forms an inner salt.
It is. The general formulas (V) and (VI
) and (VIII) are shown below, but the scope of the present invention is not limited thereto.

[0087]

[C52]

[0088]

[C53]

[0089]

[C54]

[0090]

[C55]

[0091]

[C56]

[0092]

[C57]

[0093]

[C58]

[0094]

[C59]

[0095]

[C60]

[0096]

[C61]

[0097]

[C62]

[0098] The specific amount of dye used is generally 0.00
A range of 0.01 to 2 g/m2, particularly 0.001 to 1 g/m2 is preferred. These dyes may be used alone or in combination. Furthermore, it may be used in combination with dyes other than those of the above general formula.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
benzothiazoles, nitrobenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1, 3,
3a, 7) tetrazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can. In particular, polyhydroxybenzene compounds
This is preferable in that it improves pressure resistance without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having one of the following structures.

[0100]

[C63]

X and Y are respectively -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 alkyl group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group, alkyl ether group, alkylphenyl group, alkylthioether or phenylthioether group. More preferably, -H, -OH, -Cl, -Br, -COO
H, -CH2 CH2 COOH, -CH3, -CH
2 CH3, -CH(CH3)2, -C(CH3
)3, -OCH3, -CHO, -SO3Na,
-SO3H, -SCH3,

[0102]

[C64]

[0103] etc. X and Y may be the same or different. Particularly preferred representative compound examples are shown below.

[0104]

[C65]

[0105]

[C66]

[0106]

[C67]

[0107]

[C68]

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 photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for the purpose of increasing sensitivity, increasing contrast, or promoting development,
For example, polyalkylene oxide or its ether,
Derivatives such as esters and amines, thioether compounds,
It may also contain developing agents such as thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and aminophenols. Among them, 3-pyrazolidones (1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferred,
Usually used at 5g/m2 or less, 0.01-0.2g/
m2 is more preferred. The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, N,N-methylenebis-[β-(vinylsulfonyl)propionamide], etc.), active halides (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts (
1-morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1-(1-
Chloro-1-pyridinomethylene)pyrrolidinium, 2-
naphthalene sulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-412
No. 20, No. 53-57257, No. 59-162546
Preferred are the active vinyl compounds described in No. 60-80846 and the active halides described in U.S. Pat. No. 3,325,287. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention includes coating aids,
Various surfactants may be included for various purposes such as antistatic, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, promoting development, increasing contrast, and sensitizing). For example, saponins (steroids), alkylene oxide derivatives (
For example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, addition of silicone to polyethylene oxide products), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides)
, fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc.; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl Phosphate esters, N
-carboxy groups, sulfo groups, such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as phospho groups, sulfate ester groups, and phosphate ester groups; amphoteric interfaces such as amino acid salts, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, and amine oxides. Activators: Cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. can be used. Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example alkyl (meta)
Polymers containing as monomer components acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, etc. alone or in combination, or a combination of these and acrylic acid, methacrylic acid, etc. can be used. Gelatin is advantageously used as a condensing agent or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., single or copolymers thereof. Can be done. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used. The silver halide emulsion layer used in the present invention can contain a polymer latex such as an alkyl acrylate. As the support for the photosensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, etc. can be used.

[0112] There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable to include dihydroxybenzenes, since it is easy to obtain good halftone dot quality, and as the dihydroxybenzene developing agent, hydroquinone is preferred. ,
Chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3
Examples include -dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred. Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
These include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount of sulfite is preferably 0.25 mol/liter or more, particularly 0.4 mol/liter or more. Also, the upper limit is 2.
Preferably it is up to 5 mol/l, in particular up to 1.2.

[0113] Alkaline agents used for setting pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Contains pH regulators and buffers such as potassium carbonate. Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-
Antifoggants such as mercapto compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, benztriazole compounds such as 5-methylbenztriazole, or Black pot (b)
(lack pepper) inhibitors: and, if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, JP-A-56-106244, JP-A-61
-267,759 and the amino compounds described in Japanese Patent Application No. 1-29418. The developing solution used in the present invention contains JP-A No. 56-24347 as a silver stain preventive agent.
The compound described in JP-A No. 1983-1983 as a developing unevenness preventive agent
212,651, and the compound described in JP-A No. 61-267,759 can be used as a solubilizing agent.

[0114] The developer used in the present invention contains boric acid as described in Japanese Patent Application No. 61-28708 and Japanese Patent Application Laid-open No. 61-28708 as a buffering agent.
0-93433 (e.g. saccharose),
Oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), and the like are used. The processing method of the present invention can be carried out in the presence of polyalkylene oxide, but in order to contain polyalkylene oxide in the developer, polyethylene glycol with an average molecular weight of 1000 to 6000 is used in the range of 0.1 to 10 g/liter. It is preferable to do so.

In addition to the fixing agent, the fixing solution may also contain a water-soluble aluminum compound as a hardening agent. Furthermore, if necessary, an acidic aqueous solution containing acetic acid and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof), preferably at a pH of 3.
8 or more, more preferably 4.0 to 6.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, with ammonium thiosulfate being particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to about 5 mol/liter. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, and includes, for example, aluminum chloride, aluminum sulfate, and potassium alum.

As the aforementioned dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more kinds. It is effective to use these compounds in a content of 0.005 mol or more per liter of the fixing solution, particularly 0.01 mol/liter to 0.03 mol/liter. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, and the like. Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, and potassium citrate.

It is preferable to use a meso ion compound represented by the following general formula in the fixer used in the present invention.

[0118]

[C69]

In the formula, Z represents a 5- or 6-membered ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and X- represents -O-, -S-, or -N-R (Here, X represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group). Among these, compounds represented by the following general formula (X) are more preferred.

[0120]

[C70]

In the formula, R1 and R2 represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. However, R2
may be a hydrogen atom. Y is -O-, -S-, -
N(R3)-, R3 represents an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, amino group, acylamino group, sulfonamido group, ureido group or sulfamoylamino group . R1 and R2, R2 and R3 may be bonded to each other to form a ring.

The compound represented by the above general formula (X) will be explained in detail. In the formula, R1 and R2 are substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, n
-Propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylaminoethylthioethyl group, diethylaminoethyl group, aminoethyl group, methylthiomethyl group, trimethylammonioethyl group , carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group, etc.), substituted or unsubstituted cycloalkyl group (e.g. cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group) , etc.), substituted or unsubstituted alkenyl groups (e.g. allyl group, 2-methylallyl group, etc.), substituted or unsubstituted alkynyl groups (e.g. propargyl group, etc.), substituted or unsubstituted aralkyl groups (e.g. benzyl group, etc.) phenyl group, 4-methoxybenzyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 4-sulfophenyl group, etc.) or a substituted or unsubstituted heterocyclic group (
For example, it represents a 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, etc.).

[0123] However, R2 may be a hydrogen atom. R3 is a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, n-propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylaminoethylthioethyl group) , diethylaminoethyl group, aminoethyl group, methylthiomethyl group, trimethylammonioethyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfomethyl group, phosphonomethyl group, phosphonoethyl group, etc.), substituted or unsubstituted cycloalkyl groups (e.g., cyclohexyl group, cyclopentyl group, 2-methylcyclohexyl group, etc.), substituted or unsubstituted alkenyl groups (e.g., allyl group, 2-methylallyl group, etc.), substituted or unsubstituted alkynyl groups ( For example, propargyl group, etc.), substituted or unsubstituted aralkyl group (for example, benzyl group, phenethyl group, 4-methoxybenzyl group, etc.), aryl group (for example, phenyl group, naphthyl group, 4-methylphenyl group, 4- methoxyphenyl group, 4-carboxyphenyl group, 4-sulfophenyl group, etc.) or substituted or unsubstituted heterocyclic group (e.g. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, etc.),

Substituted or unsubstituted amino groups (for example, unsubstituted amino group, dimethylamino group, methylamino group, etc.), acylamino groups (for example, acetylamino group, benzoylamino group, methoxypropionylamino group, etc.),
Sulfonamide groups (e.g. methanesulfonamide group, benzenesulfonamide group, 4-toluenesulfonamide group, etc.), ureido groups (e.g. unsubstituted ureido group, 3
-methylureido group, etc.), sulfamoylamino group (
For example, it may be an unsubstituted sulfamoylamino group, 3-methylsulfamoylamino group, etc.). General formula (X
), preferably Y represents -N(R3)-, R1
, R3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group. R2 is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group. Specific examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.

[0125]

[C71]

The compounds of the invention can be used in amounts of 1 x 10-5 mol/l to 10 mol/l, especially 1 x 10-3 mol/l.
It is preferable to use it in the fixer or fixer replenisher in the range of liter to 3 mol/liter. Here, when the halogen composition of the silver halide emulsion in the photographic material to be processed is silver iodobromide, it is preferable to use it at 0.5 to 2 mol/liter; In the case of a silver chloride emulsion (silver halide containing 80 mol % or more of silver chloride), it is preferably used in a range of 0.05 to 1 mol/liter. The fixing solution further contains preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), pH adjusters (e.g. ammonia, sulfuric acid), image preservation improving agents (e.g. (potassium iodide), a chelating agent. Here, since the pH of the developer is high, the pH buffering agent is 10 to 40 g/liter, more preferably 18 to 25 g/liter.
Use approximately g/liter.

[0127] In addition, a mold inhibitor (for example, "Chemistry of Bacterial and Bacterial Prevention" by Horiguchi, Japanese Patent Application Laid-Open No. 115154/1986) is added to the washing water.
(compounds described in this issue), water washing accelerators (such as sulfites), chelating agents, etc. According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out to almost completely remove the silver salt dissolved during fixing, and is preferably carried out at about 20° C. to about 50° C. for 10 seconds to 3 minutes. Drying is carried out at a temperature of about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to
3 minutes and 30 seconds is enough.

Regarding the roller conveyance type automatic developing machine, see US Pat. No. 3,025,779 and US Pat. No. 3,545,971.
In this specification, it is simply referred to as a roller conveyance type processor. A roller conveyance type processor consists of four steps: development, fixing, washing, and drying, and although the method of the present invention does not exclude other steps (for example, a stopping step), it is most preferable to follow these four steps. . Replenishment amount of washing water is 1200ml/
It may be less than m2 (including 0). The case where the replenishment amount of washing water (or stabilizing liquid) is 0 means a washing method using a so-called accumulated water washing method. As a method to reduce the amount of replenishment, the multi-stage countercurrent method (for example, 2 stages, 3 stages, etc.) has been used since ancient times.
It has been known.

[0129] To solve the problem that occurs when the amount of replenishment of washing water is small, good treatment performance can be obtained by combining the following techniques. For the washing bath or stabilization bath, R.
T. Kreiman, J. Image. T
ech. Vol. 10 No. 6 242 (1
984), Research Disclosure (R.D.) Vol. 205, No.
Isothiazoline compounds described in 20526 (May 1981 issue), Volume 228, No. 22845
(April issue, 1983), JP-A-61-115,154, JP-A-62-
The compounds described in No. 209,532, etc. are used as antibacterial agents (
It can also be used in combination as Microbiocide. In addition, "Chemistry of antibacterial and antifungal" by Hiroshi Horiguchi, Sankyo Publishing (
1982), “Handbook of Antibacterial and Antifungal Technology” Japanese Society of Antibacterial and Antifungal Research, Hakuhodo (1987), L. E. West “W
ater Quality Criteria ”P
hoto Sci & Eng. Vol. 9N
o. 6 (1965), M. W. Beach “M
icrobiological Growths in
Motion Picture Processin
g”SMPTE Journal Vol.85(19
76), R. O. Deegan “Photo Pr
ocessing Wash Water Bioci
des”J. Imaging Tech. Vol.
10 No. 6 (1984).

[0130] When washing with a small amount of washing water in the method of the present invention, Japanese Patent Application Laid-open No. 63-18,350 and Japanese Patent Application Laid-Open No. 62-2
It is more preferable to provide a squeeze roller and a crossover rack cleaning tank as described in No. 87,252. Further, part or all of the overflow liquid from the washing or stabilizing bath of the present invention, which is generated by replenishing the washing or stabilizing bath with water treated with anti-mold means according to the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-1999.
As described in No. 235,133 and JP-A No. 63-129,343, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. Furthermore, water-soluble surfactants and antifoaming agents are added to prevent uneven blisters that tend to occur when washing with a small amount of water and/or to prevent the processing agent components that adhere to the squeeze roller from being transferred to the processed film. May be added. Further, a dye adsorbent described in JP-A-63-163-456 may be installed in the washing tank to prevent staining due to dyes eluted from the sensitive material. The developer used in the present invention is preferably stored in a packaging material with low oxygen and moisture permeability as described in JP-A-61-73147. Further, for the developer used in the present invention, a replenishment system described in JP-A-62-91939 can be preferably used.

Since the silver halide photographic light-sensitive material of the present invention provides a high Dmax, it maintains a high density even if the halftone dot area is reduced when subjected to power reduction treatment after image formation. There are no particular limitations on the reducing fluid used in the present invention; for example, as described in "The Theory of
the Photographic Process
” pages 738-744 (1954, Macmill
an), “Photo Processing Theory and Practice” by Tetsuo Yano 1
In addition to published works such as pages 66-169 (1978, Kyoritsu Shuppan), Japanese Patent Publication No. 50-27543, 52-68429, 55-17123, 55-79444, 5
No. 7-10140, No. 57-142639, No. 61-
61155, JP-A-1-282551, JP-A-2-
Those described in No. 25846 can be used. That is, permanganates, persulfates, ferric salts, cupric salts, cerium salts, red blood salts, dichromates, etc. are used alone or in combination as oxidizing agents, and if necessary, Inorganic acids such as sulfuric acid, reducing fluids containing alcohols, or oxidizing agents such as red blood salts and ferric ethylenediaminetetraacetic acid salts,
A reducing solution containing a silver halide solvent such as thiosulfate, rhodan salt, thiourea or a derivative thereof and, if necessary, an inorganic acid such as sulfuric acid, is used.

Typical examples of the reducing liquid used in the present invention include so-called Farmer reducing liquid, ferric salt of ethylenediaminetetraacetic acid, potassium permanganate, ammonium persulfate reducing liquid (Kodak R-5), Examples include ceric reducing fluid. The conditions for force reduction treatment are generally 10°C to 40°C,
In particular, it is preferable that the process can be completed at a temperature of 15°C to 30°C within several seconds to several tens of minutes, particularly within several minutes. By using the photosensitive material for plate making of the present invention, a sufficiently wide reduction width can be obtained within the range of these conditions. The reducing liquid is applied to the recorded image formed in the emulsion layer through the non-photosensitive upper layer containing the compound of the present invention. Specifically, there are various methods, such as immersing the photosensitive material for plate making in a reducing liquid and stirring the liquid, or applying the reducing liquid to the surface of the sensitive material for plate making with a brush, roller, etc. is available.

[0133] 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 the present invention, the developed, fixed, and water-washed photosensitive material is dried using a squeeze roller. Drying at 40°C to 80°C for 4 seconds to 30 minutes
Done in seconds. The total processing time in the present invention is defined as the time from when the leading edge of the film is inserted into the insertion slot of the automatic processor, to the developer tank,
This is the total time it takes for the film to pass through the transfer section, fixing tank, transfer section, washing tank, transfer section, and drying section until the leading edge of the film emerges from the drying outlet. Since the silver halide photosensitive material of the present invention can reduce the amount of gelatin used as a binder in the emulsion layer and protective layer without impairing pressure fog, development is possible even in rapid processing with a total processing time of 15 to 60 seconds. Development processing can be performed without impairing speed, fixing speed, or drying speed. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[0134]

【Example】

Example 1 Emulsions A and B were prepared by the following method. 0.5M silver nitrate aqueous solution, 0.1M potassium bromide and 0.44M
Sodium chloride, hexachloroiridium(III)
A halogen salt aqueous solution containing potassium acid, ammonium hexabromorodium (III) acid, and gelatin aqueous solution containing sodium chloride, 1,3-dimethylimidazolidine-2-thione and benzenethiosulfonic acid and adjusted to pH 4.0, Added by double jet method for 10 minutes at 38°C with stirring, average particle size 0.16 μm,
Nucleation was performed by obtaining silver chlorobromide grains with a silver chloride content of 70 mol%. Subsequently, a 0.5M silver nitrate aqueous solution, a halogen salt aqueous solution containing 0.1M potassium bromide, 0.44M sodium chloride, and potassium ferrocyanide were similarly added for 10 minutes by the double jet method to complete particle formation. . The obtained particles have an average particle size of 0.2μ
m, silver chloride content 70 mol%, 3 Ir per mol silver
．． 8 x 10-7 mol, Rh 6.1 x 10-8 mol, F
The silver chlorobromide cubic grains contained 2.3×10 −5 moles of e (coefficient of variation 10%). Thereafter, it was washed with water by flocculation according to a conventional method, and 30 g of gelatin was added. This emulsion was divided into two equal parts, and emulsions A and B were divided by the following method.
was prepared.

Emulsion A: Emulsion pH 5.6, pAg 7
．． 5, 3.2 mg of sodium thiosulfate and 4.3 mg of chloroauric acid were added, and chemical sensitization was performed at 65°C to obtain the optimum sensitivity. 75 mg of methyl-1,3,3a,7-tetraazaindene was added. Emulsion B: Adjust the pH of the emulsion to 5.1 and pAg to 7.5, and add 2.2 mg of sodium thiosulfate, 0.85 mg of N,N-dimethylselenourea, 3.4 mg of sodium benzenethiosulfonate, and benzene. By adding 0.85 mg of sodium sulfinate and 4.3 mg of chloroauric acid, 55
The aging time was adjusted so that the emulsion sensitivity would be the same as determined by the evaluation method described later, chemical sensitization was performed, and 4-hydroxy-6-methyl-1,3,3a,7- was added as a stabilizer.
75 mg of tetraazaindene was added.

In the obtained emulsions A and B, a dye having the following structure and D
ye1 and Dye2 were added as shown in Table 1. Furthermore, 4,4'-bis(4,6-dinaphthoxy-pyrimidine-
2-ylamino)-stilbenedisulfonic acid disodium salt, 234 mg per mole of silver, 1-phenyl-5-
25 mg of mercaptotetrazole was added. Furthermore, hydroquinone 150mg/m2, polyethyl acrylate latex, gelatin binder ratio 30%, 0.01μ
m colloidal silica to gelatin binder ratio of 30%,
70 mg/m2 of 2-bis(vinylsulfonylacetamido)ethane was added as a hardening agent, and the amount of silver coated was 3.2 g/m2 and the amount of gelatin coated was 1.4 on the polyester support.
It was coated so that the amount was g/m2. At this time, 0.5 g/m2 of gelatin was added to the upper layer of the emulsion layer as a protective layer, 70 mg/m2 of a dye having the following structural formula, and a particle size of 2.0 g/m2 as a matting agent.
60mg/m2 of 5μm polymethyl methacrylate,
70 mg/m2 of colloidal silica with a particle size of 10 μm, and 1.5 mg/m2 of dodecylbenzenesulfonic acid sodium salt and a fluorine-containing surfactant with the following structural formula as coating aids.
2 and chelating agent 20mg/m2, pH 5.5
It was coated at the same time as the emulsion layer.

[0137]

[C72]

The base 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

[0139]

[C73]

1,3-Divinylsulfone-2-propanol
60mg/m2 (back protective layer) gelatin

0.5g/m2 polymethyl methacrylate (particle size 4.7μm)
30mg/m2 Sodium dodecylbenzenesulfonate
20mg/m2 Fluorine-containing surfactant (above)

2mg/m2 silicone oil
100mg/m
2

Evaluation of Photographic Performance The obtained sample was exposed to xenon flash light with an emission time of 10-5 seconds through an interference filter having a peak at 633 nm and a continuous wedge.
Sensitometry was carried out at the temperature and time shown below using an automatic processor FG-710NH manufactured by Co., Ltd.

Development 38°C 14 seconds fixing 37°C 9.7 seconds washing with water
26℃ 9 seconds squeeze 2.4 seconds dry
55℃ 8.3 seconds total
43.4 seconds linear velocity
The developer and fixer used at 2800 mm/min had the following composition. (Developer formulation) Potassium hydroxide

10g 1-hydroxyethylidene-1,1-diphosphonic acid
2.6g potassium bromide

3.3g 5-methylbenzotriazole
0.08g 2
-Mercaptobenzimidazole-5-sulfonic acid
sodium

0.3g potassium sulfite

83g
hydroquinone

35g 4-hydroxymethyl-4-
Methyl-1-phenyl-3-pyrazolidone

1.3g diethylene glycol

Add 30g water

1 liter (Add sodium hydroxide to adjust pH to 10.7) (Fixer formulation) Ammonium thiosulfate

150g 1,4,5-trimethyl-1,2
,4-triazolium-3-thiolate

0.25mol sodium bisulfite

30g Ethylenediaminetetraacetic acid disodium dihydrate 0.025g
add water

1 liter (pH with sodium hydroxide =
Evaluation of sensitivity and gradation (adjusted to 6.0) The logarithm of the exposure amount giving a density of 3.0 was taken as the sensitivity, and the relative sensitivity was evaluated. Further, the slope of the straight line connecting the points of density 0.1 and 3.0 on the characteristic curve was evaluated as the gradation. At this time, 63
633 when exposed using a 3 nm interference filter
nm sensitivity, and when exposed using a 380 nm interference filter, Blue sensitivity was used. Evaluation of running suitability The automatic processor FG-710NH used for sensitivity evaluation was coated with a silver coating amount of 3.6 g/m2 and a silver chloride content of 70 per mole of silver.
A film coated with a silver chlorobromide emulsion of mol % was processed at 180 cc/m2 with a blackening rate of 50% and replenishment of developer, fixer, and mother solution.
A 150 m2 running process was carried out while replenishing with water. Using this liquid, the sensitivity at 633 nm and gradation were evaluated based on the difference from the Fr liquid. Evaluation of residual color The samples were processed in the same manner as in the sensitivity evaluation except that the unexposed sample and the washing water temperature were 5° C., and the color of the samples was visually evaluated on a five-point scale. 5 means the least residual color, 1 means the most residual color, and 3 means the practical limit. Table 1 shows the evaluation results for each sample.

[0143]

[Table 1]

[0144] As is clear from Table 1, sample No. 1 corresponds to the present invention. It is understood that samples No. 6 and No. 10 are excellent in sensitivity, gradation, running suitability, and residual color.

Example 2 The amounts of heavy metals contained in the emulsion grains were set to 5.0 x 10-7 mol of Ir and 1.5 x 10-7 mol of Rh per mol of silver.
Chlorobromide with an average particle size of 0.2 μm and a silver chloride content of 70 mol% was prepared in the same manner as in Example 1, except that the amount of each heavy metal compound added was adjusted so that Fe was 7 mol and Fe was 0.0. Silver cubic particles were made (coefficient of variation 10%). Thereafter, the flocculation method was followed by washing with water according to a conventional method, and 30 g of gelatin was added. This emulsion was divided into two equal parts, and emulsions C and D were prepared by the following method. Emulsion A: Adjust the pH of the emulsion to 5.9 and pAg to 7.5, add 2.8 mg of sodium thiosulfate, and 4 mg of chloroauric acid.
4-hydroxy-6- as a stabilizer.
Methyl-1,3,3a,7-tetraazaindene 75m
g was added. Emulsion B: Adjust the pH of the emulsion to 5.3 and pAg to 7.5, and add 1.9 mg of sodium thiosulfate, 0.74 mg of N,N-dimethylselenourea, 3.4 mg of sodium benzenethiosulfonate, and benzene. Chemical sensitization was performed by adding 0.85 mg of sodium sulfinate and 4 mg of chloroauric acid, and 4-hydroxy-6-methyl-1,3,3a,7-tetra was added as a stabilizer. 75 mg of azaindene was added. The procedure of Example 1 was repeated except that dyes Dye3 and Dye4 having the following structures were added to the obtained emulsions C and D as shown in Table 2, and the dyes added to the protective layer and back layer were changed to those of the following structural formula. Similarly, sample No.
．． Samples Nos. 11 to 16 were prepared, and their photographic performance was evaluated in the same manner as in Example 1, except that the 633 nm interference filter was changed to 780 nm. The results are shown in Table 2.

[0146]

[C74]

[0147]

[C75]

[0148] As can be seen from Table 2, No. It is understood that No. 14 and No. 16 are excellent in sensitivity, gradation, and running suitability.

[0149]

[Table 2]

[0150]

Effects of the Invention The present invention provides an emulsion in which the silver chloride content is 50 mol% or more, the iridium compound is contained in an amount of 10-9 mol per mol of silver, the emulsion is chemically sensitized with a selenium sensitizer, and the emulsion is chemically sensitized with a selenium sensitizer. By combining with dyes and compounds, it was possible to create a sensitive material for high-intensity, short-time exposure with high sensitivity, high contrast, and excellent running suitability.

Claims (5)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer, the silver halide emulsion containing at least 50 mol % of silver chloride and 10 −9 mol or more of an iridium compound per mol of silver. In a silver halide photographic light-sensitive material comprising silver halide grains containing a silver halide emulsion, the silver halide emulsion is spectrally sensitized with a compound having a structure of the general formula (I), (II), or (III); (I
A silver halide photographic material containing the compound V) and further chemically sensitized with a selenium sensitizer. [Image Omitted] [Image Omitted] [Image Omitted] In the general formula (II), R1 and R2 may be the same or different, and each represents an alkyl group. R3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z1 represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X1 represents an acid anion. m, p and q
each independently represents 1 or 2. However, when the dye forms an inner salt, q is 1. embedded image In the formula, R1' and R2' may be the same or different, and each represents an alkyl group. R3' and R4' each independently represent a hydrogen atom, a lower alkyl group,
Represents a lower alkoxy group, phenyl group, benzyl group or phenethyl group. R5' and R6' each represent a hydrogen atom, or R5' and R6' are linked to form a divalent alkylene group. R7' is a hydrogen atom,
Represents a lower alkyl group, lower alkoxy group, phenyl group, benzyl group, or -NW1'(W2'). However, W1' and W2' each independently represent an alkyl group or an aryl group, and W1' and W2' can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Further, R3' and R7' or R4' and R7' can be linked to form a divalent alkylene group. Z' and Z1' each independently represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X1 represents an acid anion, m' is 1 or 2
represents. However, when the dye forms an inner salt, m'
is 1. embedded image Here, A represents a divalent aromatic residue. R21, 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, a substituted or unsubstituted alkylamino group, It represents a substituted 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
represents -CH= or -N=. However, at least W
Either one of 3 and W4 represents -N=. Claim 2: Formulas (V), (VI) and (VII)
2. The silver halide photographic material according to claim 1, containing at least one compound represented by the following formula. embedded image In the formula, R1 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, and R2 and R3 are each a hydrogen atom, a halogen atom, Substituted or unsubstituted carbon number 1-6
represents an alkyl group, substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, hydroxy group, carboxyl group or a salt thereof, sulfonic acid or a salt thereof,
At least one of 3 represents a sulfonic acid group or a salt thereof. R4 and R5 each represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R6 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms. and R7 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms. [Chemical 6] Q is pyrazolone, barbituric acid, thiobarbituric acid, isoxazolone, 3-oxythionaphthene, 1,3
-Represents the atomic group necessary to form the heterocyclic nucleus of indandione. n represents 0 or 1. embedded image In the formula, R1 , R2 , R3 , R4 , R5 and R
6 may be the same or different and represent a substituted or unsubstituted alkyl group, and Z1 and Z2 represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring, respectively. show. however,
R1, R2, R3, R4, R5, R6, Z
1 and Z2 denote groups that allow the dye molecule to have at least 3 acid groups. L represents a substituted or unsubstituted methine group, and X represents an anion. n is 1 or 2, and is 1 when the dye forms an internal salt. 3. Claim 1 or 2, characterized in that the process is carried out using an automatic developing machine whose total processing time is 15 seconds to 60 seconds.
A method for developing a silver halide photographic material as described in . [Claim 4] Line speed is 1000mm/mi
4. The method of developing a silver halide photographic material according to claim 1, wherein the processing is carried out using an automatic developing machine of n or more. Claim 5: The developer and fixer replenishment amounts are each 200c.
5. The method for developing a silver halide photographic material according to claim 1, wherein the processing is carried out using an automatic developing machine having a developing temperature of not more than c/m2.