JPH05303159A - Silver halide photographic sensitive material and method for processing same - Google Patents

Abstract

PURPOSE:To enhance sensitivity and contrast and running characteristics in the photographic sensitive material used for high-illumination short-time exposure by incorporating an iridium compound and chemically sensitizing a silver halide emulsion with a tellurium compound in combination with a specified sensitizing dye stuff. CONSTITUTION:A silver halide emulsion containing the iridium compound in an amount of >=10<-9> mol is spectral sensitized with the compound represented by formula I or II or the like and chemically sensitized with the tellurium compound. In formulae I and II, each of Z and Z1 is a nonmetallic atomic group necessary to form a 5- or 6-membered N-containing hetero ring, each of R and R1 is alkyl group, substituted alkyl; each of Q and Q1 is a nonmetallic atomic group necessary to form a 4- or 5-thiazolidinone ring, each of L, L1, L2 is methine or optionally substituted methine, X is anion and X1 is an acid anion; each of R1 and R2 is alkyl, R3 is H or lower alkyl, V is H, alkoxy, or the like, and Z1 is anonmetallic atomic group necessary to form a 5- or 6-membered N-containing hetero ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, more specifically, in high-intensity short-time exposure,
The present invention relates to a silver halide photographic light-sensitive material having high sensitivity and suitability for rapid processing, and a development processing method thereof.

[0002]

2. Description of the Related Art In recent years, a scanner method has been widely used in the field of printing plate making. There are various types of recording devices that use the image forming method using the scanner system, and the light source for recording of these scanner type recording devices is a glow lamp, a xenon lamp, a tungsten lamp, an LED, a He-Ne laser, an argon laser. And semiconductor lasers. Various characteristics are required for the light-sensitive materials used in these scanners, but especially 10 ⁻³
Since exposure is performed in a short exposure time of -10 ^-7 seconds, even under such conditions, high sensitivity and high contrast are essential conditions. Further, in order to have wavelength suitability for various laser light sources, spectral sensitization is usually performed. For example, the compound represented by the general formula (I) of the present invention is mainly He-N
It has a suitable spectral sensitivity for e-laser, and has the general formula (II),
The compound represented by (III) has a suitable spectral sensitivity mainly to a semiconductor laser. The compounds represented by these general formulas are superior to other sensitizing dyes in terms of sensitivity and residual color, but they cannot be said to have sufficiently high spectral sensitization efficiency, and further, depending on the addition amount, intrinsic desensitization is caused. It may happen. As a method for improving the efficiency of spectral sensitization, for example, He
-For use as a Ne laser light source, Japanese Patent Publication No.
No. 500, Japanese Patent Application Laid-Open No. 59-
No. 19032, No. 59-192242, etc., but there are cases in which deterioration of UV transmittance in the post-exposure returning step, residual color and the like become problems. Further, in recent years, there has been a strong demand in the printing industry for work efficiency and speedup, and there is a widespread need for speeding up scanning and shortening the processing time of photosensitive materials. To meet the needs of these printing fields, exposure machines (scanners,
For plotters), it is desired to increase scanning speed and increase the number of lines and squeeze the beam for higher image quality. For silver halide photographic light-sensitive materials, high sensitivity, excellent processing stability, and rapid processing are required. It is desired to be able to be developed. The rapid development process referred to here is that after the leading edge of the film is inserted into the automatic processor, the leading edge of the film goes out of the drying section after passing through the developing tank, crossover section, fixing tank, crossover section, washing tank and drying section. Time to come 1
A process that is 5 to 60 seconds.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to have an appropriate spectral sensitivity to a laser light source used for exposure, and to provide high sensitivity, high contrast and processing dependence in high-illuminance short-time exposure. It is an object of the present invention to provide a silver halide photographic light-sensitive material having a small size and capable of rapid processing, and a processing method thereof. Another object of the present invention is to provide a silver halide photographic light-sensitive material and a method for processing the same, which have little fluctuation in photographic property in long-term operation even when the replenishment amounts of a developing solution and a fixing solution in an automatic processor are reduced. is there.

[0004]

These objects of the present invention are to have at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion contains 10 ^-9 mol or more of an iridium compound. In a silver halide photographic light-sensitive material comprising silver halide grains containing, the silver halide emulsion is spectrally sensitized with a compound having the structure of the general formula (I), (II) or (III), and a tellurium compound It was achieved by a silver halide photographic light-sensitive material characterized by being chemically sensitized by.

[0005]

[Chemical 5]

In the formula, Z and Z ₁ each represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R and R ₁ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q and Q ₁ together represent the non-metallic atomic group necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus. L, L ₁ and L ₂ each represent a methine group or a substituted methine group. n ₁ and n ₂ each represent 0 or 1. X represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt.

[0007]

[Chemical 6]

In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group. R ₃ 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. Z ₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle.
X ₁ represents an acid anion. m, p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt.

[0009]

[Chemical 7]

In the formula, R ₁ 'and R ₂ ' may be the same or different and each represents an alkyl group. R
₃ ′ and R ₄ ′ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₅ ′ and R ₆ ′ each represent a hydrogen atom, or R ₅ ′ and R ₆ ′ are linked to each other to form a divalent alkylene group. R ₇ 'is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or -NW _1' represents a (W ₂ '). However, W ₁ ′ and W ₂ ′ each independently represent an alkyl group or an aryl group, and W ₁ ′ and W ₂ ′ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. it can. Further, R ₃ ′ and R ₇ ′ or R ₄ ′ and R ₇ ′ may be linked to each other to form a divalent alkylene group. Z'and Z
₁ 'represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic ring each independently a 5- or 6-membered. X ₁ represents an acid anion, and m ′ represents 1 or 2. However, m'is 1 when the dye forms an inner salt.

The specific constitution of the present invention will be described in detail below. The silver halide emulsion used in the present invention may have any halogen composition, but for silver iodobromide or silver chloroiodobromide, the silver iodide content is 10 mol% or less, particularly 5 mol% or less. With respect to silver chlorobromide and silver chloroiodobromide, the silver chloride content is preferably 50 mol%, particularly preferably 70 mol% or more. The average grain size of silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The shape of the silver halide grains used in the present invention is a cube,
It may be an octahedron, a tetradecahedron, a plate or a sphere,
A mixture of these various shapes may be used, but cubic particles, tetradecahedral particles and tabular particles are preferable. The particle size distribution is preferably monodisperse. The monodisperse particles referred to herein have a coefficient of variation of 20% or less, particularly preferably 1
It refers to a silver halide emulsion having a grain size distribution of 5% or less. The coefficient of variation (%) is represented by the value obtained by dividing the standard deviation of the grain size of silver halide grains by the average grain size and multiplying by 100.

The photographic emulsion used in the present invention is P. Glaf.
Kides Chimie et Physique Photographique (Paul M
ontel, 1967), GF Duffin Photogr
aphic Emulsion Chemistry (Published by The Focal Press, 19
66), by VL Zelikman et al Making and Coatin
g Photographic Emulsion (The Focal Press, 196
4 years) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method for reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Further, in order to make the grain size uniform, the addition rate of silver nitrate or an alkali halide is adjusted according to the grain size as described in British Patent Nos. 1,535,016, Japanese Patent Publication Nos. 48-36890 and 52-16364. The critical saturation is not exceeded by using a method of changing the concentration according to the growth rate or a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124. It is preferable to grow faster in the range. The silver halide grains may have a so-called core / shell structure in which the inside and the surface have different halogen compositions.

As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, iridium (III) halide compounds, iridium (IV) halide compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III) or (IV)
Complex salts, hexaammineiridium (III) or (IV) complex salts, trioxalatoiridium (III) or (IV) complex salts and the like can be mentioned. In the present invention, any of these compounds may be used in any combination of a trivalent compound and a trivalent compound. These iridium compounds are used by dissolving them in water or a suitable solvent, and a method commonly used for stabilizing the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) , Or an alkali halide (eg KC
1, NaCl, NaBr, etc.) can be used. Instead of using the water-soluble iridium, it is also possible to add and dissolve another silver halide grain which is previously doped with iridium at the time of preparing the silver halide grain. The total addition amount of the iridium compound according to the present invention is appropriately 5 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol, and preferably 1 × 10 ⁻⁸ to 1 per 1 mol of finally formed silver halide. × 10 ^-5 mol, most preferably 5 × 10
^{-8 to} 5 × 10 ^-6 mol. The addition of these compounds is
It can be appropriately carried out during the production of the silver halide emulsion and before each step of coating the emulsion, but it is particularly preferably added during the grain formation and incorporated into the silver halide grains. Further, a compound containing a Group VIII atom other than the iridium compound may be used in combination with the iridium compound. The combination of two or three kinds of rhodium salt and iron salt can be advantageously carried out.

The grain formation of the silver halide emulsion of the present invention comprises
It is preferably carried out in the presence of a silver halide solvent such as a tetra-substituted thiourea or an organic thioether compound. The preferred tetra-substituted thiourea silver halide solvent used in the present invention is
It is a compound represented by the following general formula described in JP-A-53-82408, JP-A-55-77737 and the like.

[0015]

[Chemical 8]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group) or a substituted or unsubstituted aryl, which are the same as each other. Or may be different, and R _{1 to} R
The total number of carbon atoms of ₄ is preferably 30 or less. In addition, R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ are combined to form a 5- to 6-membered heterocyclic imidazolidinethione, piperidine,
You can also make morpholine. Both straight-chain and branched alkyl groups are used. Examples of the substituent of the alkyl group include a hydroxy group (—OH), a carboxy group, a sulfonic acid group, an amino group, and an alkyl residue.
An alkoxy group (o-alkyl) having 5 to 5 carbon atoms, a phenyl group or a 5- to 6-membered heterocycle (such as furan). The substituent of the aryl group is a hydroxy group, a carboxy group or a sulfonic acid group. Here, particularly preferably, among R _{1 to} R ₄ , there are 3 or more alkyl groups, the number of carbon atoms in each alkyl group is 1 to 5, the aryl group is a phenyl group, and the number of carbon atoms in R _{1 to} R ₄ is Total is 2
It is 0 or less. The following can be mentioned as examples of compounds that can be used in the present invention.

[0017]

[Chemical 9]

The organic thioether silver halide solvent preferably used in the present invention is, for example, Japanese Patent Publication No. 47-11386.
No. (U.S. Patent No. 3,574,628) comprising at least one compound group wherein oxygen atom and a sulfur atom are separated by an ethylene (e.g. -O-CH ₂ CH ₂ -S-) in the like, especially Alkyl groups at both ends described in JP-A-54-155828 (US Pat. No. 4,276,374) (wherein each alkyl group is at least 2 selected from hydroxy, amino, carboxy, amido or sulfone).
It is a chain thioether compound having one substituent). Specifically, the following examples can be given.

[0019]

[Chemical 10]

The amount of the silver halide solvent added varies depending on the kind of the compound used, the intended grain size, the halogen composition, etc., but is 10 ^-5 to 1 mol per mol of the silver halide.
10 ^-2 mol is preferred. If the grain size becomes larger than intended by using a silver halide solvent, the temperature during grain formation,
A desired particle size can be obtained by changing the addition time of the silver salt solution or the halogen salt solution.

The tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499 and 3,320.
069, 3,772,031, British Patent No. 23
No. 5,211, No. 1,121,496, No. 1,29
5,462, 1,396,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemical Communication (J. Chem.
Soc. Chem. Commun.) 635 (1980), ibid110
2 (1979), ibid645 (1979), Journal of Chemical Society Perkin Trans. (J. Chem. Soc. Perkin Trans.) 1,219
1 (1980) and the like are preferably used. Specific tellurium sensitizers include colloidal tellurium and telluroureas (eg, allyl tellurourea, N, N-).
Dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ', N'-dimethyl tellurourea,
N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isotellocyanates (for example, allyl isotellurocyanate), telluroketones (for example, telluroacetone, telluroacetophenone), telluroamides (for example, telluroacetamide). ,
N, N-dimethyl tellurobenzamide), tellurohydrazide (eg N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg t-butyl-t)
-Hexyl telluroester), phosphine tellurides (e.g. tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diylpropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (e.g. Examples thereof include negatively charged telluride ion-containing gelatin described in British Patent 1,295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, and allyl tellurocyanate). Of these tellurium compounds, the following general formulas (V) and (VI) are preferable. General formula (V)

[0022]

[Chemical 11]

Wherein R ₁ , R ₂ and R ₃ are aliphatic groups,
Aromatic group, heterocyclic group, OR ₄ , (NR ₅ (R ₆ ), SR
₇ , OSiR ₈ (R ₉ ) (R ₁₀ ), X or a hydrogen atom. R ₄ and R ₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₅ and R ₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom,
R ₈ , R ₉ and R ₁₀ represent an aliphatic group, and X represents a halogen atom. General formula (VI)

[0024]

[Chemical 12]

In the formula, R ₁₁ represents an aliphatic group, an aromatic group, a heterocyclic group or --NR ₁₃ (R ₁₄ ), and R ₁₂ represents --NR ₁₅ (R
_16), - represents a _{N (R 17) N (R} 18) R 19 or -OR _20. R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Here, R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁
And R ₁₈ , R ₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R _18, and R ₁₃ and R ₂₀ may combine to form a ring.
Specific examples of the compounds represented by formulas (III) and (IV) of the present invention are shown below, but the present invention is not limited thereto.

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

[0033]

[Chemical 20]

[0034]

[Chemical 21]

The compounds represented by the general formulas (V) and (VI) of the present invention can be synthesized according to a known method. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969. 2927; Journal of Organometallic Chemistry (J. Or.
ganomet. Chem.) 4,320 (1965); ibid. 1,
200 (1963); ibid, 113, C35 (197).
6); Phosphorus Sulfu
r) 15, 155 (1983); Hemische Berichte
(Chem. Ber.) 109, 2996 (1976); Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635.
(1980); ibid, 1102 (1979); ibid, 6
45 (1979); ibid, 820 (1987); Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 21
29 (1980); The Chemistry of Organo Selenium and Tellurium Campounds (The
Chemistry of Organo Selenium and Tellurinm Compou
nds) 2 volumes 216-267 (1987).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide emulsion grain. The following test can be conducted for the rate of silver telluride formation in a silver halide emulsion. When a large amount is added (for example, 1 × 10 ⁻³ mol / mol Ag), the formed silver telluride has absorption in the visible region. Therefore, regarding sulfur sensitizers, E. Moisar
, Journal of Photographic Science, Vol. 14, pp. 181 (1966) and pp. 16, 102 (1968).
Year) can be applied. The amount of silver sulfide produced in a silver halide emulsion can be determined from the infinite reflectivity of the emulsion in the visible range (520 nm) by Kubelka-M
The relative silver telluride formation rate can be easily obtained by the same method as that obtained using the unk equation. Also,
Since this reaction is apparently close to the first-order reaction, the pseudo-first-order reaction rate constant can also be obtained.

How to obtain the pseudo first-order reaction rate constant. A silver bromide octahedron emulsion having an average grain size of 0.5 μm (1 kg emulsion containing 0.75 mol of AgBr and 80 g of gelatin) was added.
While keeping H = 6.3 and pAg = 8.3, the temperature is kept at 50 ° C., and 1 × 10 ⁻³ mol / mol Ag of a tellurium compound dissolved in an organic solvent (methanol or the like) is added. Using a spectrophotometer with an integrating sphere, put the emulsion in a 1 cm thick cell and measure the reflectance (R) at 520 nm over time with reference to the blank emulsion. The reflectance is expressed by the Kubelka-Munk equation (1
-R) Substitute for ² / 2R and obtain the pseudo first-order reaction rate constant k (min ^-1 ) from the time until the value becomes 0.01. Kubelka-M because R is always 1 unless silver telluride is produced
The value of unk is the same as that without tellurium compound and remains 0. A compound having an apparent first-order reaction rate constant k of 1 × 10 ⁻⁸ to 1 × 10 ⁰ min ⁻¹ under exactly the same conditions as in this test method is preferable. The pseudo first-order reaction rate constant of the tellurium sensitizer of the present invention by this test method was as follows. Compound Example-7; k≈4 × 10 ⁻³ min ⁻¹ Compound Example-10; k≈2 × 10 ⁻³ min ⁻¹ Compound Example-12; k≈8 × 10 ⁻⁴ min ⁻¹ Compound Example-18; k≈2 × 10 ⁻⁴ min ⁻¹ Compound Example-4; k≈7 × 10 ⁻⁵ min ^{−1 Further} , in a smaller addition amount range where absorption in the visible region is difficult to detect, the produced silver telluride is not added. It can be quantified by separating it from the reaction tellurium sensitizer. For example, after separation by immersion in an aqueous solution of a halogen salt or an aqueous solution of a water-soluble mercapto compound, a trace amount of Te is quantitatively analyzed by an atomic absorption method or the like. This reaction rate greatly varies in the range of several digits depending on the type of compound, the silver halide composition of the emulsion to be tested, the temperature to be tested, pAg and pH. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and crystal habit to be used. Generally speaking,
For silver bromide emulsion, temperature 40-95 ° C, pH 3-1
Compounds capable of forming silver telluride in the range of 0 or pAg6 to 11 are preferably used in the present invention, and in this range, the pseudo first-order reaction rate constant k according to the above test method is 1 × 10. ^A compound falling within the range of ^-7 to 1 x 10 ^-1 min ^-1 is more preferable as the tellurium sensitizer.

The silver halide emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of selenium sensitization and / or sulfur sensitization and / or gold sensitization in chemical sensitization. Selenium sensitization or sulfur sensitization is
It is usually carried out by adding a sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. The gold sensitization is usually carried out at a high temperature, preferably 4 by adding a gold sensitizer.
It is carried out by stirring the emulsion at 0 ° C. or higher for a certain period of time. For sulfur sensitization, known sulfur sensitizers can be used. Examples thereof include thiosulfates, thioureas, allyl isothiocyanates, cystines, p-toluene thiosulfonates, and rhodanines. Other US Pat. Nos. 1,574,944 and 2,41
0,689, 2,278,947, 2,7
No. 28,668, No. 3,501,313, No. 3,
656,955 specifications, German Patent 1,422,8
No. 69, Japanese Patent Publication No. 56-24937, Japanese Patent Laid-Open No. 55-45.
The sulfur sensitizers described in JP-A No. 016, etc. can also be used. As the selenium sensitizer, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added at a high temperature, preferably 40
It is used by stirring the emulsion at a temperature of not less than 0 ° C for a certain period of time. As the unstable selenium compound, Japanese Patent Publication No. 44-157
No. 48, Japanese Patent Publication No. 43-13489, Japanese Patent Application No. 2-130
It is preferable to use the compounds described in Japanese Patent Application No. 976 and Japanese Patent Application No. 2-229300. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allylisoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. Can be given. The selenium sensitizer and the sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but it is 1 × 10 ^-7 mol or more per mol of silver halide, 5 or more.
It is preferably × 10 ^-4 mol or less.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, there are particular restrictions on the timing and order of addition of tellurium sensitizers or selenium sensitizers and / or sulfur sensitizers and / or gold sensitizers that can be used in combination with tellurium sensitizers. There is no need, and for example, the above compounds can be added simultaneously at the initial stage (preferably) of the chemical ripening or during the progress of the chemical ripening or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

The sensitizing dye preferably used in the silver halide emulsion of the present invention has optimum spectral sensitivity to He-Ne lasers and semiconductor lasers, and has the general formulas (I), (II), ( III). However, when these sensitizing dyes are used alone, the efficiency of spectral sensitization cannot be said to be sufficient, and the intrinsic desensitization tends to increase as the amount of addition increases. As a countermeasure against this, the general formula (I
It is known to use the compound (V) in combination, for example, JP-B-60-45414, JP-A-46-10473, and JP-A-5-45143.
9-192242 and the like. However, it is not expected by a person skilled in the art that the efficiency of spectral sensitization is further increased by combining with the emulsion of the present invention, and the sensitivity when using He-Ne or a semiconductor laser light source is further enhanced than the conventional one. It was an effect. Each general formula will be described in detail below.

In the general formula (I) of the sensitizing dye used in the present invention, the following can be used as the nitrogen-containing heterocyclic nucleus completed by Z or Z ₁ . Thiazole nucleus {eg thiazole, 4-methylthiazole, 4-
Phenylthiazole, 4,5-dimethylthiazole,
4,5-di-phenylthiazole and the like}, benzothiazole nucleus {for example, 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 nucleus {eg 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 {eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole nucleus {eg, benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-methoxybenzoselena Sol, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole and the like}, naphthoselenazoles {for example, naphtho [2,1-d] selenazole, naphtho [1,2]
-D] selenazole etc.}, oxazole nucleus {eg oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole etc.), benzoxazole nucleus {eg benzoxazole, 5-fluorobenzoxazole, 5-chlorobenz Oxazole, 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, etc., naphthoxazole nucleus {for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,2]
3-d] oxazole and the like}, 2-quinoline nucleus, imidazole nucleus, benzimidazole nucleus, 3,3′-dialkylindolenine nucleus, 2-pyridine nucleus, thiazoline nucleus and the like can be used. Particularly preferably Z and Z
_At least one of 1 is a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus or a benzoxazole nucleus.

As the alkyl group represented by R or R ₁ in the above general formula, an alkyl group having 5 or less carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), substituted As the alkyl group, a substituted alkyl group having 5 or less carbon atoms in the alkyl radical (eg, a hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, etc.), carboxyalkyl group (eg, carboxymethyl group) Group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2- (2-carboxyethoxy) ethyl group, etc.), sulfoalkyl group (for example, 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 of the alkyl radical is 1 to
5 is preferable, and the aryl group is preferably a phenyl group, for example, 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), aryloxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, aryl group of aryloxy group is preferably phenyl group, for example, phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, p -Methylphenoxyethyl group, p-
Methoxyphenoxypropyl group, etc.), vinylmethyl group, etc.}, etc., and an aryl group such as a phenyl group. L, L ₁ and L ₂ are methine groups or substituted methine groups =
Represents C (R ')-. R'is an alkyl group (such as a methyl group or an ethyl group), a substituted alkyl group (such as an alkoxyalkyl group (such as a 2-ethoxyethyl group)),
Carboxyalkyl group (for example, 2-carboxyethyl group), alkoxycarbonylalkyl group (for example, 2-carboxyethyl group)
Methoxycarbonylethyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), etc.}, aryl group (eg phenyl group, p-methoxyphenyl group, p
-Chlorophenyl group, o-carboxyphenyl group, etc.)
And so on. Further, L and R, and L ₁ and R ₁ may be bonded to each other by a methine chain to form a nitrogen-containing heterocycle. Q
Examples of the substituent attached to the nitrogen atom at the 3-position of the thiazolinone nucleus or imidazolinone nucleus formed by Q and Q ₁ include an alkyl group (preferably having a carbon number of 1 to 8 such as a methyl group, an ethyl group, a propyl group). , Allyl group, aralkyl group (alkyl group, radical preferably has 1 to 5 carbon atoms, for example, benzyl group, p-carboxyphenylmethyl group, etc.), aryl group (total carbon number is preferably 6 to 9, eg phenyl group) , P-carboxyphenyl group, etc.), hydroxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, for example, 2-hydroxyethyl group), carboxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, For example, carboxymethyl group, etc., alkoxycarbonylalkyl group (alkyl radical of alkoxy part) Preferably 1 to 3 carbon atoms, also the number of carbon atoms in the alkyl moiety preferably 1 to 5, for example, a methoxycarbonylethyl group) and the like.

Examples of the anion represented by X include halogen ions (iodine ion, bromine ion, chlorine ion, etc.), perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, Examples thereof include methylsulfate ion and ethylsulfate ion.

Next, the general formula (II) will be described. In the formula,
R ₁ and R ₂ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably, it has 1 to 8 carbon atoms. For example methyl,
Ethyl, propyl, butyl, pentyl, heptyl, octyl. Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms, eg, methoxycarbonyl, ethoxy). Carbonyl, benzyloxycarbonyl, etc.), alkoxy group (preferably having 7 or less carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy group (eg phenoxy, p-tolyloxy), acyloxy group (preferably carbon). C3 or less, such as acetyloxy, propionyloxy), acyl group (preferably having 8 carbon atoms)
Hereinafter, for example, acetyl, propionyl, benzoyl, mesyl), carbamoyl group (eg, carbamoyl, N, N)
-Dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl group (eg sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), aryl group (eg phenyl, p
-Hydroxyphenyl, p-carboxyphenyl, p-
Alkyl group substituted with sulfophenyl, α-naphthyl, etc. (preferably having 6 or less carbon atoms in the alkyl portion)
Is mentioned. However, two or more of these substituents may be combined and substituted with an alkyl group.

R ₃ is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, Propoxy, butoxy), phenyl group, benzyl group or phenethyl group. Particularly, a lower alkyl group and a benzyl group are advantageously used. V is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl),
Alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, butoxy), halogen atom (for example, fluorine atom, chlorine atom), substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl, carboxy) Represents methyl).

Z ₁ represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus [eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorobenzothiazole, 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-methoxy Naphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,2]
3-d] thiazole], selenazole nucleus [eg, 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 [eg 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 nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl- 5-chlorobenzimidazole, 1-ethyl-5
Chlorbenzimidazole, 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). Of these, a thiazole nucleus and an oxazole nucleus are preferably used advantageously. 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, q is 1 when the dye forms an inner salt.

X ₁ is an acid anion (for example, chloride, bromide, iodide, tetrafluorobollard, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4-nitrobenzene sulfonate, trifluoromethane sulfonate, perchlorate).

Next, the general formula (III) will be described. In the formula, R ₁ ′ and R ₂ ′ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably, it has 1 to 8 carbon atoms. For example, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl. As a substituent, for example, a carboxyl group,
Sulfo group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms, eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy Group (preferably having 7 or less carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy group (for example, phenoxy, p-tolyloxy), acyloxy group (preferably having 3 or less carbon atoms, for example, acetyloxy, Propionyloxy), an acyl group (preferably having 8 or less carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinoca). Vamoyl), a sulfamoyl group (eg sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), an aryl group (eg phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) and the like. And an alkyl group (preferably having 6 or less carbon atoms in the alkyl portion). However, two or more of these substituents may be combined and substituted with an alkyl group.

R ₃ 'and R ₄ ' are a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms, For example, methoxy, ethoxy, propoxy, butoxy), phenyl group, benzyl group or phenethyl group. Particularly, a lower alkyl group and a benzyl group are advantageously used. R ₅ ′ and R ₆ ′ each represent a hydrogen atom, or R ₅ ′ and R ₆ ′ are linked to each other to form a divalent alkylene group (eg ethylene or trimethylene). The alkylene group may be one, two or more suitable groups such as alkyl groups (preferably having 1 carbon atom).
To 4, for example, methyl, ethyl, propyl, isopropyl, butyl), halogen atom (for example, chlorine atom, bromine atom), or alkoxy group (preferably having 1 carbon atom).
~ 4, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy) and the like. R
₇ 'is a hydrogen atom, a lower alkyl group (preferably having from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, etc.), lower alkoxy group (preferably having from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, etc. ), Phenyl, a benzyl group, or —N (W ₁ ′) (W ₂ ′). Here, W ₁ ′ and W ₂ ′ are each independently an alkyl group (including a substituted alkyl group. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 4, for example, methyl, ethyl, propyl, butyl, Benzyl, phenylethyl), or an aryl group (including a substituted phenyl group, for example, phenyl, naphthyl, tolyl, p-chlorophenyl, etc.), wherein W ₁ ′ and W ₂ ′ are linked to each other to form a 5- or 6-membered group. It is also possible to form a nitrogen-containing heterocycle. Provided that R ₃ ′ and R ₇ ′ or R ₄ ′ and R ₇ ′ are linked to form a divalent alkylene group (synonymous with the divalent alkylene group formed by linking R ₅ ′ and R ₆ ′ above). ) Can also be formed.

Z'and Z ₁ 'represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus [eg benzothiazole, 4-chlorobenzothiazole, 5-chloro]. Benzothiazole, 6-
Chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzo Thiazole, 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 nucleus [eg 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-methyl Benzoxazole, 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 [eg 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 (eg 3,3-dimethylindolenine, 3,3-diethylindolenine,
3,3-dimethyl-5-cyanoindolenin, 3,3-
Dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-
Chlorindolenine), imidazole nucleus (eg 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-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) , Pyridine nuclei (eg pyridine, 5-methyl-2-pyridine, 3-methyl-4-)
Pyridine). Of these, a thiazole nucleus and an oxazole nucleus are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X ₁ ′ is an acid anion (eg chloride, bromide, iodide, tetrafluorobollard, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate). , 4-
Nitrobenzene sulfonate, trifluoromethane sulfonate, perchlorate). m'represents 0 or 1, and is 1 when the dye forms an intramolecular salt. Specific examples of compounds are shown below. However, the present invention is not limited to these.

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

[0056]

[Chemical formula 26]

[0057]

[Chemical 27]

[0058]

[Chemical 28]

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur
e) Volume 176, 17643 (issued in December 1978) No. 23
Item J on page IV, or Japanese Patent Publication No. Sho 49-25500,
43-4933, JP-A-59-19032, and 59-
19242 and the like. 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 kind of the antifoggant compound, etc. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art. Usually, preferably 10 ^{-7 to} 1 mol per mol of silver halide.
It is used in an amount of × 10 ^-2 mol, particularly 10 ^-6 to 5 × 10 ^-3 mol.

Compounds represented by the following general formula (IV) can be used as the compounds exhibiting a better effect when used in combination with the sensitizing dyes represented by the general formulas (I), (II) and (III) of the present invention. Can be mentioned.

[0061]

[Chemical 29]

The compound represented by formula (IV) will be described. Wherein, -A- represents a divalent aromatic residue, which -SO ₃ M group [wherein M represents a cation to give a hydrogen atom or a water-soluble (for example, sodium, potassium, etc.). ] May be included. -A- is, for example, the following -A
₁ - or -A ₂ - those selected from are useful. However R _21, R _22, when the R ₂₃ or R ₂₄ do not contain -SO ₃ M is, -A- is -A ₁ - is selected from the group consisting of.

[0063]

[Chemical 30]

[0064]

[Chemical 31]

[0065]

[Chemical 32]

R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each a hydrogen atom, a hydroxy group or a lower alkyl group (the number of carbon atoms is preferably 1 to 8, for example, methyl group, ethyl group, n-group).
Propyl group, n-butyl group, etc., alkoxy group (number of carbon atoms is preferably 1 to 8. For example, methoxy group,
Ethoxy group, propoxy group, butoxy group etc.), aryloxy group (eg phenoxy group, naphthoxy group, o-troxy group, p-sulfophenoxy group etc.), halogen atom (eg chlorine atom, bromine atom etc.), heterocyclic nucleus (eg For example, morpholinyl group, piperidyl group, etc., alkylthio group (eg, methylthio group, ethylthio group, etc.), heterocyclylthio group (eg, benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (eg, phenylthio group) , Tolylthio group), amino group, alkylamino group or substituted alkylamino group (eg, methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxy group) Chiruamino group, di - (beta-hydroxyethyl) amino group, beta-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-anisino group, m-anisino group, p-anisino group, o-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group ( For example, 2-benzothiazolylamino group, 2-pyridyl-amino group, etc.), a substituted or unsubstituted aralkylamino group (eg, benzylamino group, o-anisylamino group,
m-anisylamino group, p-anisylamino group, etc.),
It represents an aryl group (eg, a phenyl group) or a mercapto group. R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ may be the same or different from each other. -A- is -A ₂ - when selected from the group consisting of, R _21, at least one of R _22, R _23, R ₂₄ may be with one or more sulfo groups (free acid groups, to form a salt May be required). W ₃ and W
₄ represents -CH = or -N =, and at least one of them is -N =. Next, specific examples of the compound included in the general formula (IV) will be given. However, the compounds are not limited to these compounds.

(IV-1) 4,4'-bis [4,6-
Di (benzothiazolyl-2-thio) pyrimidin-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 (IV-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- Lolo-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 ) Pyrimidin-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'-
Disulphonic acid disodium salt (IV-13) 4,4'-bis (4-anilino-6-hydroxy-triazin-2-ylamino) stilbene-
2,2'-Disulfonic acid disodium salt (IV-14) 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 known or can be easily produced according to known methods.

The compound represented by the general formula (IV) used in the present invention may be a mixture of two or more kinds thereof.
The compound represented by general formula (IV) is advantageously used in an amount of about 0.01 to 5 grams per mol of silver halide in the emulsion. The compound represented by the general formula (IV) used in the present invention can be directly dispersed in an emulsion, and a suitable solvent (eg, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof is used. It can also be dissolved in the emulsion and added to the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. Further, it can be dispersed and added to the emulsion by the method described in JP-A-50-80119.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item Applicable place 1) Surfactant JP-A-2-12236, first right column, line 7 to the same right Antistatic agent, lower column, line 7 and JP-A-2-18542, page 2, left lower column, the line 13 to the same Page 4, lower right column, line 18. 2) Antifoggant JP-A-2-103526, page 17, lower right column, line 19 Stabilizer, from page 18 to upper right column, line 4 and lower right column, line 1 to line 5. 3) Polymer latex JP-A-2-103526, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103526, page 18, lower right column, line 6 to page 19, upper left column, line 1 and JP-A-2-55349, page 8, lower right column, line 13 To page 11, upper left column, line 8 of the same. 5) Polyhydroxyben JP-A-2-55349, page 11, upper left column, page 9 to zens, lower right column, line 17 6) Matting agent, slipping agent JP-A-2-103526, page 19, upper left column, line 15 Plasticizer to page 19 upper right column, line 15 7) Hardener JP-A-2-103526, page 18, upper right column, line 5 to line 17 8) Dyes, JP-A-2-103526, page 17, lower right column, line 1 to line 18, and JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Developer and developing method JP-A-2-55349, page 13, lower right column, line 1 to 16th upper left column, line 10 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

[0070]

【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
Of sodium chloride, potassium hexachloroiridium (III), ammonium hexabromorhodium (III), an aqueous solution of halogen salt containing sodium chloride, 1,3-dimethylimidazolidine-2-thione and benzenethiosulfonic acid, and a pH of 4 Nucleation by adding to a gelatin aqueous solution adjusted to 0.0 with stirring by a double jet method at 38 ° C. for 10 minutes to obtain silver chlorobromide grains having an average grain size of 0.16 μm and a silver chloride content of 70 mol%. I went. Then, similarly, with a 0.5 M silver nitrate aqueous solution,
A halogen salt aqueous solution containing 0.1 M potassium bromide, 0.44 M sodium chloride and potassium ferrocyanide was added by the double jet method for 10 minutes to complete the grain formation. The obtained grains have an average grain size of 0.2 μm, a silver chloride content of 70 mol%, and an Ir of 3.8 × 1 per mol of silver.
0 ^-7 mol, Rh 6.1 x 10 ^-8 mol, Fe 2.3 x
It was a silver chlorobromide cubic grain containing 10 ⁻⁵ mol (variation coefficient: 10%). Then, it was washed with water by the flocculation method 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 prepared by the following method.

Emulsion A: The pH of the emulsion was adjusted to 5.6 and the pAg was adjusted to 7.5, 3.2 mg of sodium thiosulfate and 4.3 mg of chloroauric acid were added to obtain the optimum sensitivity at 65 ° C. Was chemically sensitized, and 75 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added as a stabilizer. Emulsion B: The pH of the emulsion was adjusted to 5.1 and the pAg was adjusted to 7.5, 2.2 mg of sodium thiosulfate, 0.96 mg of tellurium sensitizer (Compound Example-13), and sodium benzenethiosulfonate of 3. 4 mg, sodium benzenesulfinate (0.85 mg) and chloroauric acid (4.3 mg) were added, and the ripening time was adjusted so that the emulsion sensitivity at 55 ° C was about the same as in the evaluation method described later, and the chemical sensitization treatment was performed. As a stabilizer,
75 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene were added.

Emulsions A and B thus obtained were dyed with the following structure, D
Ye1 and Dye2 were added as shown in Table 1. Furthermore, 4,4'-bis (4,6-dinaphthoxy-pyrimidine-
234 mg of 2-ylamino) -stilbenedisulfonic acid disodium salt and 25 mg of 1-phenyl-5-mercaptotetrazole were added per mol of silver. Further, hydroquinone 150 mg / m ² , polyethyl acrylate latex 30% gelatin binder ratio, 0.01 μm colloidal silica 30% gelatin binder ratio, and 2-bis (vinylsulfonylacetamide) ethane 70 mg / m ² hardener added. Then, it was coated on a polyester support so that the coating amount of silver was 3.2 g / m ² and the coating gelatin amount was 1.4 g / m ² . At this time, 0.5 g / m ^{2 of} gelatin was added to the upper layer of the emulsion layer as a protective layer, 70 mg / m ^{2 of} a dye having the following structural formula was added,
Then, as a matting agent, polymethyl methacrylate having a particle diameter of 2.5 μm is 60 mg / m ² , colloidal silica having a particle diameter of 10 μm is 70 mg / m ² , and dodecylbenzenesulfonic acid sodium salt as a coating aid and a fluorine-containing interface having the following structural formula. An activator (1.5 mg / m ²⁾ and a chelating agent (20 mg / m ²⁾ were added to adjust the pH to 5.5 and the emulsion layer was coated at the same time.

[0073]

[Chemical 33]

The base used in this example has a back layer and a back protective layer having the following compositions. (Back layer) Gelatin 2.0 g / m ² Sodium dodecylbenzene sulfonate 80 mg / m ²

[0075]

[Chemical 34]

1,3-divinylsulfone-2-propanol 60 mg / m ² (back protective layer) gelatin 0.5 g / m ² polymethylmethacrylate (particle size 4.7 μm) 30 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² fluorine-containing surfactant (above) 2 mg / m ² silicone oil 100 mg / 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, and was then developed by Fuji Photo Film Co., Ltd. Sensitometry was performed using FG-710NH at the temperature and time shown below.

Development 38 ° C. 14 sec Fixing 37 ° C. 9.7 sec Washing 26 ° C. 9 sec Squeeze 2.4 sec Dry 55 ° C. 8.3 sec Total 43.4 sec Linear velocity 2800 mm / min , Has the following composition.

(Developer formulation) 1,2-dihydroxybenzene-3,5-disulfonic acid sodium salt 0.5 g diethylenetriamine-pentaacetic acid 2.0 g sodium carbonate 5.0 g boric acid 10.0 g potassium sulfite 85.0 g sodium bromide 6.0 g Diethylene glycol 40.0 g 5-Methylbenzotriazole 0.2 g Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 2,3,5,6,7,8- Hexahydro-2-thioxo-4- (1H) -quinazolinone 0.05 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g Potassium hydroxide is added, water is added to 1 liter and the pH is adjusted to 10.7. To match. 1 liter

(Fixer Solution Formulation) Sodium thiosulfate (anhydrous) 150 g Compound-1 0.1 mol Sodium bisulfite 30 g Ethylenediaminetetraacetic acid disodium dihydrate 25 mg Sodium hydroxide is added, and water is added to make 1 liter and pH. To 6.0. 1 liter

[0081]

[Chemical 35]

Evaluation of sensitivity and gradation: The relative sensitivity was evaluated using the logarithm of the exposure amount giving a density of 3.0 as the sensitivity. Also, the slope of the straight line connecting the points of density 0.1 and 3.0 on the characteristic curve was evaluated as gradation. At this time, 63
633 when exposed using a 3 nm interference filter
When the exposure was performed using a 380 nm interference filter, the blue sensitivity was used. Evaluation of running suitability A film coated with a silver chlorobromide emulsion having an amount of coated silver of 3.6 g / m ² and a silver chloride content of 70 mol% per mol of silver was applied to an automatic processor FG-710NH used for evaluation of sensitivity. , Blackening rate 5
A 150 m ² running process was carried out while replenishing with 0%, 180 cc / m ² by replenishing the developing solution and the fixing solution with the mother solution. Using this solution, the 633 nm sensitivity and gradation were evaluated, and the difference with the Fr solution was evaluated. Evaluation of residual color The unexposed sample was processed in the same manner as in the evaluation of sensitivity except that the washing water temperature was set to 5 ° C., and the tint of the sample was visually evaluated in five levels. 5 means the least residual color, 1 means the most residual color, and 3 means the practical limit. The evaluation results of each sample are shown in Table 1.

[0083]

[Table 1]

As is clear from Table 1, Sample Nos. 6 and 10 which correspond to the present invention have sensitivity, gradation, running suitability,
It is understood that the residual color is excellent.

Example 2 The heavy metal contained in the emulsion grains was added such that Ir was 5.0 × 10 ^-7 mol and Rh was 1.5 × 10 ^-7 mol per mol of silver. Adjust the amount of compound added,
Silver chlorobromide cubic grains having an average grain size of 0.2 μm and a silver chloride content of 70 mol% were prepared in the same manner as in Example 1 except that the Fe compound was removed (variation coefficient: 10%). Then, in accordance with the usual method, washed with water by the flocculation method,
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 C: pH of the emulsion was adjusted to 5.9, pAg was adjusted to 7.5, 2.8 mg of sodium thiosulfate and 4 mg of chloroauric acid were added, and chemical sensitization treatment was performed at 60 ° C. to obtain optimum sensitivity. Then, 75 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added as a stabilizer. Emulsion D: pH of emulsion was adjusted to 5.3, pAg was adjusted to 7.5, sodium thiosulfate 1.9 mg, N, N-dimethylselenourea 0.35 mg, tellurium sensitizer (Compound Example 13).
0.76 mg, sodium benzenethiosulfonate 3.4 mg and sodium benzenesulfinate 0.85
mg and chloroauric acid (4 mg) were added, and chemical sensitization was performed to obtain optimum sensitivity, and 4-hydroxy-6- as a stabilizer.
Methyl-1,3,3a, 7-tetraazaindene 75 mg
Was added. The obtained emulsions C and D were mixed with dyes Dye3 and Dy having the following structures.
Sample Nos. 11 to 16 were prepared in the same manner as in Example 1 except that e4 was added as shown in Table 2 and the dyes added to the protective layer and the back layer were changed to those having the following structural formulas.
nm interference filter changed to 780 nm,
Photographic performance was evaluated in the same manner as in Example 1 except that the fixing solution was changed to the following composition. The results are shown in Table 2.

[0086]

[Chemical 36]

[0087]

[Chemical 37]

(Developer Formulation) Potassium Hydroxide 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.6 g Potassium bromide 3.3 g 5-Methylbenzotriazole 0.08 g 2-Mercaptobenzimidazole-5-sulfonic acid Sodium 0.3 g Potassium sulfite 83 g Hydroquinone 35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.3 g Diethylene glycol 30 g Water was added to 1 liter (sodium hydroxide was added to adjust pH = 10.7). ) (Fixing solution formulation) Ammonium thiosulfate 150 g 1,4,5-Trimethyl-1,2,4-triazolium-3-thiolate 0.25 mol Sodium bisulfite 30 g Ethylenediaminetetraacetic acid disodium dihydrate 0.025 g Water In addition 1 Liter (adjusted to pH = 6.0 with sodium hydroxide)

As can be seen from Table 2, Nos. 14 and 16, which correspond to the present invention, are excellent in sensitivity, gradation and running suitability.

[0090]

[Table 2]

[0091]

INDUSTRIAL APPLICABILITY In the present invention, the emulsion contains 10 ^-9 mol or more of iridium compound per 1 mol of silver, is chemically sensitized with a tellurium sensitizer, and is combined with the sensitizing dye of the present invention to obtain a high illuminance. The light-sensitive material for short-time exposure could have high sensitivity, high contrast, and excellent running suitability.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Chemical 14]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0088

[Correction method] Change

[Correction content]

(Developer formulation) Potassium hydroxide 10 g Diethylenetriaminetetraacetic acid 2.0 g Potassium bromide 3.3 g 5-Methylbenzotriazole 0.08 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 0.3 g Potassium sulfite 83 g Hydroquinone 35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.3 g Diethylene glycol 30 g Water was added to 1 liter (sodium hydroxide was added to adjust pH = 10.7) (fixing solution formulation) Ammonium thiosulfate 150 g 1,4,5-Trimethyl-1,2,4-triazolium-3-thiolate 0.25 mol Sodium bisulfite 30 g Ethylenediaminetetraacetic acid disodium dihydrate 0.025 g Water was added to 1 liter (sodium hydroxide) Adjusted to pH = 6.0 with helium)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

[0090]

[Table 2]

Claims (5)

[Claims] 1. A silver halide grain having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion contains 10 ⁻⁹ mol or more of an iridium compound per mol of silver. In the silver halide photographic light-sensitive material, the silver halide emulsion is spectrally sensitized with at least one compound having a structure represented by the general formula (I), (II) or (III), and with a tellurium compound. A silver halide photographic light-sensitive material characterized by being chemically sensitized. [Chemical 1] In the formula, Z and Z ₁ each represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R and R ₁ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q and Q ₁ together represent the non-metallic atomic group necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus.
L, L ₁ and L ₂ each represent a methine group or a substituted methine group. n ₁ and n ₂ each represent 0 or 1.
X represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt. [Chemical 2] In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group. R ₃ 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. Z ₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion. m, p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt. [Chemical 3] In the formula, R ₁ ′ and R ₂ ′ may be the same or different and each represents an alkyl group. R ₃ 'and R
Each ₄ ′ independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₅ ′ and R ₆ ′ each represent a hydrogen atom, or R ₅ ′ and R ₆ ′ are linked to each other to form a divalent alkylene group. R ₇ 'is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or -N,
It represents W ₁ ′ (W ₂ ′). However, W ₁ ′ and W ₂ ′ each independently represent an alkyl group or an aryl group, and W ₁ ′ and W ₂ ′ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. it can. Also R ₃ ′ and R
₇ ′ or R ₄ ′ and R ₇ ′ may be linked to each other to form a divalent alkylene group. Z ′ and Z ₁ ′ each independently represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion, and m ′
Represents 1 or 2. However, m'is 1 when the dye forms an inner salt. 2. The silver halide photographic light-sensitive material according to claim 1, containing at least one compound selected from the compounds represented by formula (IV). [Chemical 4] Here, A represents a divalent aromatic residue. R ₂₁ , R ₂₂ , R
₂₃ and R ₂₄ 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 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, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ has a sulfo group. W ₃ and W ₄ represents -CH =, or -N =. However, at least one of W ₃ and W ₄ represents -N =. 3. The method for developing and processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out by an automatic processor having a total processing time of 15 to 60 seconds. 4. The method for developing a silver halide photographic light-sensitive material according to claim 3, wherein the processing is carried out by using an automatic processor having a line speed of 1000 mm / min or more. 5. A developer and a fixer replenishing amount of each is 200 cc /
5. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the processing is carried out using an automatic processor having a m ² or less.