JPH05197060A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To improve development performance and rapid processing aptitude and covering power by spectrally sensitizing silver grains to a specified value with a sensitizing dye chemically sensitizing it with tellurium and gold compounds. CONSTITUTION:Photosensitive silver halide emulsion in at least one layer formed on a support contains <=50mol% silver chloride and an iridium compound in an amount of >=10<8>mol/mol of silver halide. The silver halide emulsion is spectrally sensitized to >=600nm wavelength with a sensitizing dye and chemically sensitized with the tellurium compound and the gold compound. The support is coated with the silver halide in an amount of <=2.8g/m<2> in terms of silver on one side and gelatin on the same side as the silver halide-coated side to the support in an amount of <=3.5g/m<2> in terms of the total gelatin.

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, and more particularly to a silver halide photographic light-sensitive material which is suitable for rapid processing, has high covering power and high sensitivity, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, in the medical field, X-ray CT, MRI
2. Description of the Related Art As an image recording system for a diagnostic device such as (nuclear magnetic resonance device), a laser imager which scans a laser beam and records it on a photographic light-sensitive material has been widely used. This laser imager system is desired to be recorded and developed in a shorter time for quick diagnosis. The recording laser of the laser imager is He-N
There are e-lasers and semiconductor lasers.

The exposure wavelength of a laser imager includes He-Ne laser, AlGaP (semiconductor) laser and the like in the range of 600 to 700 nm, and the infrared region of the semiconductor.

Various characteristics are required for the light-sensitive materials used in these laser imagers, but in particular 10 ⁻³
Since exposure is performed in a short time of about 10 ⁻⁷ seconds, high sensitivity is an essential condition even under such conditions.

Further, it is known that the output image from the laser imager has adjacent portions in the image where the difference in density is clearly different, and that portion causes uneven processing when rapidly processed by an automatic processor. ing. Since this can be improved by accelerating the development progress of the light-sensitive material, it is necessary that the sensitivity of the light-sensitive material varies little with the development time.

On the other hand, in order to achieve rapid processing, it is necessary to have a light-sensitive material which gives a sufficient blackening density in a short time, and a property in which fixing, washing and drying are completed in a short time. In particular, various methods for rapidly completing the drying have been studied so far, but as a method often used for improving the drying property of a light-sensitive material, a sufficient amount of a hard material is previously prepared in the step of applying the light-sensitive material. A method of reducing the water content in the light-sensitive material before the start of drying by adding a filming agent (gelatin cross-linking agent) and reducing the swelling amount of the emulsion layer and the surface protective layer in the developing, fixing and washing steps. is there. In this method, if a large amount of hardener is used, the drying time can be shortened by that much, but the swelling becomes small. As a result, the development is delayed, the soft feeling is lowered, and the covering power is lowered. Further, a method of rapid high-temperature processing with a processing agent in which the developing solution and the fixing solution have substantially no gelatin hardening action is disclosed in, for example, JP-A-63-
136043 and the like. These methods are not sufficiently effective methods because they accelerate development progress and improve fixability, but eventually slow dryness.

On the other hand, it is known to use various additives to silver halide as a method for accelerating the development and increasing the covering power. For example, polyacrylamides as polymers include U.S. Pat. No. 3,271,15.
No. 8, No. 3,514, 289, No. 3, 514, 2
89, etc., and dextran compounds as sugars are disclosed in U.S. Pat. Nos. 3,063,838 and 3,272,631.
No., etc. However, if these compounds are used in an amount sufficient to achieve their purpose, they have the drawbacks of slow drying and poor film strength.

Further, apart from the point of view of rapid processing, further enhancement of the sensitivity of the sensitive material and improvement of the covering power are issues that have been continuously sought. Generally, the covering power decreases if the sensitivity is increased by increasing the particle size. It is meaningless unless the particles of the same size achieve higher sensitization or the same sensitivity and higher covering power.

As described above, as a photographic light-sensitive material for a laser imager, a photographic light-sensitive material having high sensitivity, high covering power, excellent development progress and rapid processing suitability has been desired.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to provide rapid processing which has excellent development progress and sensitivity with particles of the same size (projected area diameter), high covering power, and excellent fixing property. An object is to provide a suitable silver halide photographic light-sensitive material having a spectral sensitivity of 600 nm or more and a processing method thereof.

[0011]

The object of the present invention is to provide at least one photosensitive silver halide emulsion on the support in an amount of 50 mol% or less of silver chloride and 10 ^-8 mol or more of iridium per mol of silver halide. In a silver halide photographic light-sensitive material composed of silver halide grains containing a compound, the silver halide emulsion is spectrally sensitized to 600 nm or more by a sensitizing dye, and further chemically sensitized with a tellurium compound and a gold compound. And a silver halide photographic light-sensitive material.

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 composition such as silver bromide, silver chlorobromide and silver iodochlorobromide as long as the content of silver chloride is 50 mol% or less.
It is preferably 0 mol% or less, and particularly preferably 40 mol% or less and 5 mol% or more silver chlorobromide. The reason for this is that, as described in Japanese Patent Application No. 3-266934, the silver chloride content may be increased in order to improve the fixing property, but the sensitivity is lowered when the silver chloride content is increased. 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 may be any of a cube, an octahedron, a tetradecahedron, a plate and a sphere, and may be a mixture of these various shapes. , Tetradecahedral and tabular grains are preferred.

The photographic emulsion used in the present invention is P. Glafki.
des by Chimie et Physique Photographique (Paul Mont
published by el, 1967), by GF Duffin Photographic
Emulsion Chemistry (The Focal Press, 1966
,) By VL Zelikman et al Making and Coating Ph
otographic Emulsion (Published by The Focal Press, 1964
Year) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as the formation of reacting the soluble silver salt and the 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. A method of keeping pAg constant in a liquid phase in which silver halide is produced, as one form of the simultaneous mixing method,
That is, the so-called controlled double jet method can also 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 particle size uniform, British Patent No. 1,535,016 and Japanese Patent Publication No. 48-36890, 5
No. 2-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent 4,242,445 and JP-A-55-158124. As described above, it is preferable to use the method of changing the concentration of the aqueous solution to grow the growth rapidly within a range not exceeding the critical saturation. The silver halide grains may have a so-called core / shell structure in which the inside and the surface have different halogen compositions.

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
The compounds described in JP-A Nos. 53-82408 and 55-77737. The organic thioether silver halide solvent preferably used in the present invention is, for example, JP-B-47-
Compounds containing at least one group described in 11386 (US Pat. No. 3,574,628) in which an oxygen atom and a sulfur atom are deprotected by ethylene (for example, —O—CH ₂ CH ₂ —S—), An alkyl group at both ends described in JP-A-54-155828 (US Pat. No. 4,276,374) (wherein each alkyl group is at least two substituents selected from hydroxy, amino, carboxy, amido or sulfone) Chain thioether compound having a group). The addition amount of the silver halide solvent varies depending on the kind of the compound used, the intended grain size, the halogen composition, etc., but is preferably 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide. When the grain size becomes larger than the intended size by using the silver halide solvent, the grain size can be made desired by changing the temperature during grain formation, the addition time of the silver salt solution, the halogen salt solution and the like.

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 (I
V) complex salt, hexaammineiridium (III) or (I
V) complex salt, trioxalatoiridium (III) or (I
V) Complex salts and the like. 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 are generally used for stabilizing the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid,
A method of adding bromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, 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 10 ^-8 mol or more, preferably 1 ×, per 1 mol of silver halide finally formed.
10 ⁻⁸ to 1 × 10 ⁻⁵ mol, most preferably 5 × 10 ⁻⁸ to
It is 5 × 10 ⁻⁶ mol. The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion and at each stage before coating the emulsion, but in particular, it can be added at the time of grain formation and incorporated into the silver halide grains. preferable. 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 reason for using the iridium compound is to accelerate the development progress in short-time exposure (10 ^-3 to 10 ^-7 seconds) as described in Japanese Patent Application No. 3-266934. However, the use of an iridium compound lowers the sensitivity, and a method for increasing the sensitivity has been required. It was an unexpected effect that when the tellurium compound of the present invention was used, the sensitivity when using He—Ne or a semiconductor laser light source was further enhanced than that of the conventional one.

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 800,958, Journal of Chemical Society Chemical Communication (J. Chem.S.
oc.Chem.Commun.) 635 (1980), ibid 110
2 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Transaction (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 (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (eg United Kingdom Examples thereof include negatively charged telluride ion-containing gelatin described in Japanese Patent No. 1,295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, and allyl tellurocyanate). Among these tellurium compounds, the following general formulas (A) and (B) are preferable. General formula (A)

[0018]

[Chemical 1]

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

[0020]

[Chemical 2]

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 (A) and (B) of the present invention are shown below, but the present invention is not limited thereto.

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

The compounds represented by the general formulas (A) and (B) of the present invention can be synthesized according to the already known methods. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969, 2927; Journal of Organometallic Chemistry (J.
Organomet.Chem.) 4, 320 (1965); ibid.
1, 200 (1963); ibid, 113, C35 (19
76); Phosphorus Sul
fur) 15, 155 (1983); Hemische Berichte (Chem.Ber.) 109, 2996 (1976); Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 635 ( 19
80); ibid, 1102 (1979); ibid, 645
(1979); ibid, 820 (1987); Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2129.
(1980); The Chemistry of Organo Selenium and Tellurium Companies (The Ch
emistry of Organo Selenium and Tellurium Compound
s) It can be synthesized by the method described in Volume 2 216 to 267 (1987).

Tellurium sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include US Pat.
271,157, 3,531,289, 3,574,628, and JP-A-54-1019, 5
(A) Organic thioethers described in JP-A-4-158917, JP-A-53-82408 and JP-A-55-7773.
No. 7, 55-2982 and the like (b) thiourea derivatives, and (c) the thiocarbonyl group described in JP-A No. 53-144319 (c) sandwiched between an oxygen or sulfur atom and a nitrogen atom. Silver halide solvent having
No. 100717 (d) imidazoles,
(E) Sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

The silver halide photographic emulsion of the present invention has high sensitivity,
In order to achieve low fog, it is chemically sensitized with a gold compound (hereinafter referred to as gold sensitization). 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. As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Typical examples are chloroaurate, potassium chloroaurate,
Auric trichloride, potassium auriothiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate,
Pyridyl trichloro gold etc. are mentioned. The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 mol or more and 5 × 10 ^-4 mol or more per mol of silver halide.
It is preferably not more than mol.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization in chemical sensitization. Sulfur sensitization is
Usually, a sulfur sensitizer is added to the mixture at a high temperature, preferably 40
It is carried out by stirring the emulsion at a temperature of not less than 0 ° C 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 U.S. Pat. Nos. 1,574,944 and 2,410,68
No. 9, No. 2,278, 947, No. 2,728, 6
No. 68, No. 3,501,313, No. 3,656.
955 specifications, German Patent 1,422,869,
The sulfur sensitizers described in JP-B-56-24937 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount will vary over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but will be 1 per mole of silver halide.
It is preferably from 10 ^-7 mol to 5 10 ^-4 mol.

In chemical ripening, it is not necessary to place restrictions on the timing and order of addition of tellurium sensitizers, sulfur sensitizers, gold sensitizers, etc., such as the initial (preferably) chemical ripening or The above compounds can be added at the same time or at different addition points during the aging process. 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 combined effect of sulfur sensitization, selenium sensitization, and gold sensitization with thiosulfate can effectively exert the effect of the present invention.

As the selenium sensitizer effective in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, by adding an unstable selenium compound and / or a non-unstable selenium compound,
It is preferably used by stirring the emulsion at 40 ° C. or higher for a certain period of time. As the unstable selenium compound, it is preferable to use the compounds described in JP-B-41-15748, JP-B-43-13489, Japanese Patent Application Nos. 2-130976 and 2-229300. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, and 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, and the like. The preferred types of labile selenium compounds are described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and play no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. As the non-labile selenium compound used in the present invention, compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

The sensitizing dye having a wavelength of 600 nm or more, which is 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) and (II ), (III), and (IV). However, when these sensitizing dyes are used alone, the efficiency of spectral sensitization cannot be said to be sufficient,
Inherent desensitization tends to increase as the amount of addition increases. As a countermeasure against this, it is known to use a compound of the general formula (IV) in combination, for example, Japanese Patent Publication No. 60-45414,
No. 46-10473 and JP-A-59-192242. However, by combining with the emulsion of the present invention, the efficiency of spectral sensitization is further increased, and He-
It was an unexpected effect for a person skilled in the art that the sensitivity when using Ne or a semiconductor laser light source was further enhanced than that of the conventional one.

General formula (I)

[Chemical 9]

General formula (II)

[Chemical 10]

General formula (III)

[Chemical 11]

General formula (IV)

[Chemical formula 12]

Each general formula will be described in detail below. First, general formulas (I) and (II) will be described. In formulas (I) and (II), R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group. Z ₁ , Z ₂ , Z ₃ and Z ₄ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Q and Q'represent together an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. L ₁ ,
L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , L ₉ , L
₁₀ , L ₁₁ , L ₁₂ , L ₁₃ and L ₁₄ represent a methine group.
n ₁ , n ₂ , n ₃ and n ₄ represent 0 or 1. M
₁ and M ₂ represent a charge-neutralizing counterion, and m ₁ and m ₂ are a number of 0 or more necessary for neutralizing the charge in the molecule.

The general formulas (I) and (II) will be described in more detail. R ₁ , R ₂ , R ₃ and R ₄ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or substituted alkyl groups { As a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine,
It is bromine. ), A hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (for example, methoxy, ethoxy, benzyloxy, phenethyloxy) ), A monocyclic aryloxy group having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), an acyloxy group having 3 or less carbon atoms (eg, acetyloxy, propionyloxy), an acyl group having 8 or less carbon atoms (eg, acetyl,
Propionyl, benzoyl, mesyl), carbamoyl groups (eg carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl),
A sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl group having 10 or less carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-aftyl) A substituted alkyl group having 18 or less carbon atoms}. Preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-
Butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group) Group, 3-sulfobutyl group).

The nuclei formed by Z ₁ , Z ₂ , Z ₃ and Z ₄ include thiazole nuclei {thiazole nuclei (for example, thiazole, 4-methylazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4, 5-diphenylthiazole), benzothiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5
-Nitrobenzothiazole, 4-methylbenzothiazole, 5-methylthiobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5
-Iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5
-Ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole,
5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethylthiobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy -6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, 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 [2,2] 3-d] thiazole)}, a thiazoline nucleus (eg, thiazoline, 4-methyi) Thiazoline, 4-Nitorochiazorin), an oxazole nucleus {oxazole nucleus (e.g., oxazole, 4-methyloxazole, 4-nitro Toki Sasol, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4
-Ethyloxazole), a benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzotoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole,
6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-
Dimethylbenzothiazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-
Nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (eg, 4,4-dimethyloxazoline),
Selenazole nucleus (selenazole nucleus (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-
Nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole Nuclear (eg naphtho [2,1
-D] selenazole, naphtho [1,2-d] selenazole)}, selenazole nucleus (eg selenazoline, 4-
Methyl selenazoline), tellurazole nucleus {terrazole nucleus (eg, tellurazole, 4-methylterrazole,
4-phenylterrazole), a benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzoterrazole), naphtho Tellurazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)}, tellrazoline nucleus (for example, tellrazoline, 4-methylterrazoline), 3,3-dialkylindolenine nucleus (For example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dityl-5. -Nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethyl Ndrenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (indazole nucleus (eg, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (eg, 1 -Alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5
-Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-
Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1- Aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (for example, -alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole) The above-mentioned alkyl groups are those having 1 to 8 carbon atoms, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, and hydroxyalkyl groups (eg 2-hydroxyethyl, 3-hydroxypropyl). preferable. Particularly preferred are methyl group and ethyl group. The above aryl group is
Represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, A pyridine nucleus (eg, 2-pyridine, 4-pyridine, 5-methyl-
2-pyridine, 3-methyl-4-pyridine), quinoline nucleus {quinoline nucleus (eg, 2-quinoline, 3-methyl-
2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6
-Hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-
Nitro-4-quinoline, 8-chloro-4-quinoline, 8
-Fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4
-Quinoline), isoquinoline nuclei (eg 6-nitro-
1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (eg 1,3-diethylimidazo [4,5-b]) Examples thereof include quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

The nucleus formed by Z ₁ , Z ₂ , Z ₃ and Z ₄ is preferably thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, 2
A quinoline nucleus and a 4-quinoline nucleus. The 5- or 6-membered nitrogen-containing heterocycle formed by Q and Q'is the acid nucleus with the oxo or thioxo group at the appropriate position removed. The acidic nucleus is a resonance terminal of a general merocyanine dye, and is, for example, "The Theory of the" by TH James.
The Theory of th
e Photographic Process) ", 4th Edition, Chapter 8, 198-
200 pages, those described in Macmillan 1977, etc. may be mentioned.

The acid nucleus will be described in more detail. The substituent that participates in the resonance of the acidic nucleus is preferably, for example, a carbonyl group, a cyano group, a sulfonyl group or a sulfinyl group. The acidic nucleus forms a 5- or 6-membered heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. The following nuclei are preferred. 2-pyrazolin-5-one,
Pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2
-Iminooxazolidin-4-one, 2-oxazolin-5-one, 2-thiooxazolidin-2,4-dione, isoxazolin-5-one, 2-thiazoline-4
-One, thiazolidin-4-one, thiazolidine-2,
4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-
Dioxide, indoline-2-one, indoline-3-
On, idanzolin-3-one, 2-oxoindazolinium, 3-oxaindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3- Dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,
6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, or pyrido [1,2-a] pyrimidine-1,3-
Zion's nucleus. More preferred are rhodamine, 2-thiooxazolidine-2,4-dione and 2-thiohydantoin.

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl,
Hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (eg aralkyl groups (eg benzyl, 2
-Phenylethyl), a hydroxyalkyl group (for example,
2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-
Methoxyethyl, 2- (2-methoxyethoxy) ethyl), sulfoalkyl group (for example, 2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (for example, 3-
Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (eg 2- (pyrrolidin-2-one-
1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl}, allyl group, aryl group (for example, phenyl, 2-naphthyl),
A substituted aryl group (eg, 4-carboxyphenyl, 4
-Sulfophenyl, 3-chlorophenyl, 3-methylphenyl) and a heterocyclic group (for example, 2-pyridyl, 2-thiazolyl) are preferable. More preferably, an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl), a carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, a sulfoalkyl group (for example, 2-sulfoethyl).

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
₇ , L ₈ , L ₉ , L ₁₀ , L ₁₁ , L ₁₂ , L ₁₃ and L ₁₄ are methine groups or substituted methine groups {eg substituted or unsubstituted alkyl groups (eg methyl group, ethyl group, 2-carboxyethyl Group), a substituted or unsubstituted aryl group (for example, a phenyl group, an o-carboxyphenyl group),
Heterocyclic group (eg barbituric acid), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy group, ethoxy group), amino group (eg N, N-diphenylamino group, N-methyl-N) -Phenylamino group, N-methylpiperazino group), alkylthio group (eg, methylthio group, ethylthio group), and the like} and may form a ring with another methine group, or It is also possible to form a ring with the chromophore.
L ₃ , L ₅ , L ₁₀ , and L ₁₂ are preferably unsubstituted methine groups. L ₄ is preferably an unsubstituted methine group or an unsubstituted alkyl (eg methyl group, ethyl group) substituted methine group. L ₁₁ is preferably an unsubstituted methine group, a substituted methine group (lower alkyl group (preferably having a carbon number of 1 to 4, for example, methyl group, ethyl group, propyl group,
Butyl group), a lower alkoxy group (preferably having a carbon number of 1 to 4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group), a phenyl group, a benzyl group, a phenethyl group, and the like}, More preferably, it is a substituted methine group (those substituted with a methyl group, an ethyl group, a propyl group, a benzyl group or a phenyl group).

(M ₁ ) _m1 and (M ₂ ) _m2 are included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye. It is included. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium ions (eg triethylammonium ion, pyridinium ion) and alkali metal ions (eg sodium ion, potassium ion), while anions are specifically inorganic or organic anions. It may be any of ions such as a halogen anion (eg, fluorine ion, chlorine ion,
Bromide ion, iodine ion), substituted aryl sulfonate ion (eg p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (eg 1,3-benzene sulfonate ion,
1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion,
Examples thereof include picrate ion, acetate ion, and trifluoromethanesulfonate ion.

Preferred are ammonium ion (eg, triethylammonium ion, pyridinium ion), alkali metal ion (eg, sodium ion, potassium ion), iodine ion, and p-toluenesulfonate ion.

Next, the general formula (III) will be described. In the formula, R ₁ and R ₂ may be the same or different and each is an alkyl group (including a substituted alkyl group).
Represents. 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), an acyl group (preferably C8 or less, such as acetyl, propionyl, benzoyl,
Mesyl), carbamoyl groups (eg carbamoyl, N,
N-dimethylcarbamoyl, morpholinocarbamoyl,
Piperidinocarbamoyl), 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 are substituted with 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 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 (IV) 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 'and R ₄ ' are 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. 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.

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

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 600 nm or more 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, and the antifoggant compound. It is desirable to select the optimal amount according to the type,
The method of testing for that choice is well known to those skilled in the art. Usually preferably 10 per mole of silver halide
^-7 mol to 1 × 10 ^-2 mol, especially 10 ^-6 mol to 5
It is used in the range of × 10 ^-3 mol.

In the present invention, the compound represented by the general formula (V) can also be used as a supersensitizer.

[0070]

[Chemical 25]

In the formula, -A- represents a divalent aromatic residue, and these represent a -SO ₃ M group (where M represents a hydrogen atom or a cation imparting water solubility (eg sodium, potassium, etc.). ] May be included. As -A-, those selected from the following -A ₁ -or -A _2- 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.

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

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, a methyl group, an ethyl group, n-).
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-anisidino group, m-anisidino group, p-anisidino 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 contained in the general formula (V) will be given. However, the compounds are not limited to these compounds.

(V-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (V-2) 4,4'-bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino)]
Stilbene-2,2'-disulfonic acid disodium salt (V-3) 4,4'-bis [4,6-di (naphthyl-
2-oxy) pyrimidin-2-ylamino] stilbene-2,2′-disulfonic acid disodium salt (V-4) 4,4′-bis [4,6-di (naphthyl-
2-Oxy) pyrimidin-2-ylamino] bibenzyl-2,2′-disulfonic acid disodium salt (V-5) 4,4′-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2, 2'-Disulfonic acid disodium salt (V-6) 4,4'-bis [4-chloro-6- (2-
Naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt (V-7) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5-thio) Pyrimidin-2-ylamino] stilbene-2,2′-disulfonic acid disodium salt (V-8) 4,4′-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene- 2,2'-Disulfonic acid disodium salt (V-9) 4,4'-bis [4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-10) ) 4,4'-Bis [4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-
Disulfonic acid disodium salt (V-11) 4,4'-bis [4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2'-disulfonic acid disodium salt (V-12) 4,4 ' -Bis [4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-13) 4,4'-bis (4-anilino-6-hydroxy-triazine-2 -Ilamino) stilbene-
2,2'-Disulfonic acid disodium salt (V-14) 4,4'-bis [4-naphthylamino-6
-Anilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-15) 4,4'-bis [2,6-di (2-naphthoxy) pyrimidin-4-ylamino] stilbene -2
2'-Disulfonic acid (V-16) 4,4'-bis [2,6-di (2-naphthylamino) pyrimidin-4-ylamino] stilbene-
2,2'-Disulfonic acid disodium salt (V-17) 4,4'-bis [2,6-dianilinopyrimidin-4-ylamino) stilbene-2,2'-disulfonic acid disodium salt (V-18) ) 4,4'-Bis [2-naphthylamino)-
6-anilinopyrimidin-4-ylamino] stilbene-2,2′-disulfonic acid (V-19) 4,4′-bis [2,6-diphenoxypyrimidin-4-ylamino] stilbene-2,2′- Disulfonic acid ditriethylammonium salt (V-20) 4,4'-bis [2,6-di (benzimidazolyl-2-thio) pyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt General formula The compound represented by (V) is known or can be easily produced according to known methods.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to. Particularly, a polyhydroxybenzene compound is preferable because it improves pressure resistance without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having any of the following structures.

[0078]

[Chemical 29]

X and Y are --H, --OH, halogen atom --OM (M is an alkali metal ion), --alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl, respectively. Group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group,
It is an alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group. More preferably, -H, -OH, -Cl, -Br, -C.
_{OOH, -CH 2 CH 2 COOH,} -CH 3, -CH 2
_{CH 3, -CH (CH 3)} 2, -C (CH 3) 3, -O
_{CH 3, -CHO, -SO 3 Na} , -SO 3 H, -SC
H ₃ ,

[0080]

[Chemical 30]

And so on. X and Y may be the same or different.

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

The light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, 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,
Developers such as thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and aminophenols may be included. Among them, 3-pyrazolidones (1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like) are preferable,
Usually used at 5 g / m ² or less, 0.01 to 0.2 g / m ²
Is more preferable. The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis-
[Β- (vinylsulfonyl) propionamide] and the like), active halides (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid and the like), N-carbamoylpyridinium salts (1- Morpholi) carbonyl-3-pyridinio) methanesulfonate, etc.), haloamidinium salts (1- (1
-Chloro-1-pyridinomethylene) pyrrolidinium, 2
-Naphthalene sulfonate, etc.) alone or in combination. Among them, JP-A-53-41
220, 53-57257, 59-16254.
Active vinyl compounds described in JP-A Nos. 6 and 80-8046 and active halides described in US Pat. No. 3,325,287 are preferable. For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement of slipperiness, an emulsion dispersion, an adhesion prevention and an improvement of photographic characteristics (for example, development acceleration, tone increase For various purposes such as sensitization), various surfactants may be included. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing acidic groups such as carboxy group, sulfo group, phospho group, sulfuric acid ester group, phosphoric acid ester group such as acid esters; amino acid salts, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid Amphoteric surfactants such as esters, alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Further, in order to prevent electrification, JP-A-60-80849 is used.
It is preferable to use the fluorine-containing surfactants described in Japanese Patent No.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethylmethacrylate 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 (meth)
A polymer having a monomer component of acrylate, alkoxyacrylic (meth) acrylate, glycidyl (meth) acrylate, etc., alone or in combination, or a combination of these with acrylic acid, methacrylic acid, or the like can be used. As the condensing agent or protective colloid for the photographic emulsion, it is advantageous to use gelatin, 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, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper and the like can be used.

The developing agent used in the developing solution for use in the present invention is a dihydroxybenzene or a trihydroxybenzene, since it gives a high feeling.
-Pyrazolidones are preferable, and hydroquinone, 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are particularly preferable. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is 0.25 mol / liter or more,
Particularly, 0.4 mol / liter or more is preferable. The upper limit is preferably 2.5 mol / liter, and particularly preferably 1.2.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains a pH adjuster such as potassium carbonate and a buffer. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Hexylene glycol, ethanol, methanol and other organic solvents: 1-phenyl-
Antifoggants such as 5-mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, benztriazole-based compounds such as 5-methylbenztriazole, or the like. Black pot (bla
ck pepper) inhibitor: If necessary, a toning agent, a surfactant, a defoaming agent, a water softener, a film hardener, JP-A-56-106244, JP-A-61-267, 75
9 and amino compounds described in Japanese Patent Application No. 1-291818 may be included. In the developer used in the present invention, the compounds described in JP-A-56-24347 are used as silver stain preventing agents, and the development unevenness preventing agents are JP-A-62-212,651.
JP-A-61-26 as a compound and a dissolution aid
The compounds described in No. 7,759 can be used.

In the developing solution used in the present invention, boric acid described in Japanese Patent Application No. 61-28708 is used as a buffer, and JP
0-93433 sugars (eg 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 developing solution, polyethylene glycol having an average molecular weight of 1000 to 6000 is used in the range of 0.1 to 10 g / liter. Preferably.

The fixing solution may contain a water-soluble aluminum compound as a hardening agent in addition to the fixing agent. Further, if necessary, an acidic aqueous solution containing acetic acid and a dibasic acid (eg tartaric acid, citric acid or a salt thereof), preferably pH 3.
It has 8 or more, more preferably 4.0 to 6.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 5 mol / liter. The water-soluble aluminum salt that mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. The fixer may further contain a preservative (eg, sulfite, bisulfite), if desired.
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably 18 to 25 g / liter.

For washing water, an antifungal agent (see, for example, Horiguchi, "Chemistry of Antibacterial and Antifungal", JP-A-62-115154).
Compound), a water washing accelerator (such as sulfite), and a chelating agent. According to the above method, the developed and fixed photographic material is washed with water and dried.
Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and preferably at about 20 ° C to about 50 ° C for 10 seconds to 3 minutes. Drying is performed at about 40 ° C to about 100 ° C, and the drying time is appropriately changed depending on the ambient conditions, but is usually about 5 seconds to
3 minutes and 30 seconds are enough.

Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 3,545,971.
And the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .. Replenishing amount of washing water is 1200 ml / m ²
The following may be included (including 0). The case where the replenishment amount of the washing water (or the stabilizing solution) is 0 means a washing method by a so-called accumulated water washing method. As a method for reducing the replenishment amount, a multi-stage countercurrent system (for example, two-stage, three-stage, etc.) has long been known.

Good processing performance can be obtained by combining the following techniques with the problems that occur when the replenishing amount of washing water is small. For washing bath or stabilizing bath, R.
T. Kreiman J. Image. Tech. Vol. 10 No.6 2
42 (1984), Research Disclosure (RD) No. 205, an isothiazoline compound.
Vol., No. 20526 (May, 1981), isothiazoline compounds, Vol. 228, No. 228.
45 (April, 1983), isothiazoline compounds, JP-A-61-115154, JP-A-6-115.
The compounds described in 2-209,532 and the like can also be used together as a bacteriostatic agent (Microbiocide). Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Sho 5
7), "Antibacterial and Antifungal Technology Handbook", Japan Antibacterial and Antifungal Society, Hakuhodo (Showa 61), L.S. E. West “Water Qual
lity Criteria "Photo Sci & Eng. vol. 9 No. 6
(1965), M.A. W. Beach “MicrobiologicalGrowt
hs in Motion Picture Processing ”SMPTE Journal Vo
l.85 (1976), RO. Deegan “Photo Processing
Wash Water Biocides "J. Imaging Tech. Vol. 1
0 No. 6 (1984).

When washing with a small amount of washing water in the method of the present invention, JP-A-63-18350 and JP-A-62-2 are used.
It is more preferable to provide a squeeze roller and a crossover rack cleaning tank described in No. 87,252. Further, a part or all of the overflow liquid from the washing or stabilizing bath of the present invention, which is produced by replenishing the washing or stabilizing bath with antifungal water depending on the treatment, is disclosed in JP-A-60-
No. 235,133 and JP-A No. 63-129,343, it can also be used for a processing solution having a fixing ability which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent is added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of washing water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. You may add. Further, the dye adsorbent described in JP-A-63-163,456 may be installed in a water washing tank to prevent contamination by the dye eluted from the light-sensitive material.

The photosensitive material of the present invention has a total processing time of 15 seconds to
It shows excellent performance in rapid development processing by an automatic processor which is 60 seconds. In the rapid development processing of the present invention, the temperature and time of development and fixing are each 25 seconds or less at about 25 ° C. to 50 ° C., and preferably 4 seconds to 15 seconds at 30 ° C. to 40 ° C. In the present invention, the light-sensitive material is subjected to washing or stabilizing treatment after being developed and fixed. Here, in the water washing step, a water saving treatment can be performed by using a countercurrent water washing method of two or three stages. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Further, a part or the whole of the overflow solution from the washing bath or the stabilizing bath can be used as the fixing solution as described in JP-A-60-235133. This is more preferable because the amount of waste liquid is reduced. In the present invention, the photosensitive material which has been developed, fixed and washed with water is dried through a squeeze roller. Drying at 40 ° C to 80 ° C for 4 seconds to 3
It takes 0 seconds. With the total processing time in the present invention, after inserting the tip of the film into the insertion port of the automatic developing machine, a developing tank, a transition portion, a fixing tank, a transition portion, a washing tank, a transition portion,
It is the total time for the leading edge of the film to come out of the drying outlet after passing through the drying section. Since the silver halide light-sensitive material of the present invention can reduce the amount of gelatin used as a binder for the emulsion layer and the protective layer without impairing the pressure fog, the total processing time is 15 to 60 seconds. Development processing can be carried out without impairing the speed, fixing speed, and drying speed. Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

[0096]

EXAMPLES Example 1 1. Preparation of silver halide emulsions A to F: 32 g of gelatin was dissolved in 1 liter of H ₂ O, and the mixture was heated to 53 ° C.
In a heated container, 0.3 g of potassium bromide, 5 g of sodium chloride and compound (A)

[0097]

[Chemical 31]

After adding 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate and 452 ml of an aqueous solution containing 45 g of potassium bromide and 5.5 g of sodium chloride were added by the double jet method over about 20 minutes, and then 80 g of silver nitrate was added. Aqueous solution containing 400 ml, potassium bromide 44.8 g, sodium chloride 5.5 g and hexachloroiridium (III)
An average particle size (projected area diameter) was obtained by adding 415 ml of an aqueous solution containing potassium acid (10 ^-7 mol / mol of completed silver halide) by the double jet method over about 25 minutes.
0.34 μm cubic monodisperse silver chlorobromide grains (variation coefficient of projected area diameter: 10%) were prepared.

After desalting this emulsion, 62 g of gelatin,
1.75 g of phenoxyethanol was added to adjust the pH to 6.5,
Matched to pAg 8.5. Then, the temperature was raised to 65 ° C., 12.6 × 10 ⁻⁶ mol of sodium thiosulfate was added, 2 minutes after that, 5 mg of chloroauric acid was added, and 80 minutes later, 4-hydroxy-6-methyl-1,3,3a. Then, 512 mg of 7,7-tetrazaindene was added and then rapidly cooled to solidify to obtain Emulsion A.

Furthermore, sodium thiosulfate 12.6 × 10
^-6 moles instead of the tellurium sensitizer exemplified compound 24,
Emulsions B to F were prepared in exactly the same manner as Emulsion A except that N, N dimethylselenourea and sodium thiosulfate were added in the amounts shown in Table 1. 2. Preparation of emulsion coating solution The following chemicals were added to each emulsion per mol of silver halide to prepare emulsion coating solutions.

A. Spectral sensitizing dye (A) 138 mg b. Spectral sensitizing dye (B) 42.5 mg c. Polyacrylamide (molecular weight 40,000) 8.54 g d. Trimethylolpropane 1.2 g e. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.46 g f. Latex of poly (ethyl acrylate / methacrylic acid) 32.8 g g. 1,2-bis (vinylsulfonylacetamide) ethane 2g

Spectral sensitizing dye (A)

[0103]

[Chemical 32]

Spectral sensitizing dye (B)

[0105]

[Chemical 33]

3. Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer The container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. t-octylphenoxyethoxyethanesulfonic acid sodium salt 1.5 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.3g Ji. C ₈ F ₁₇ SO ₃ K 84 mg Re. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. NaOH 0.2 g. Methanol 78cc. 1,2-Bis (vinylsulfonylacetamide) ethane Prepared to be 2.3% by weight with respect to the total amount of gelatin in the emulsion layer and the surface protective layer. Wa. Compound [B] 52 mg

[0107]

[Chemical 34]

4. Preparation of back layer coating liquid

The container was heated to 40 ° C., and the following chemicals were added to prepare a back layer coating solution. I. Gelatin amount 100 g b. Dye [A] 2.39 g

[0110]

[Chemical 35]

C. Sodium polystyrene sulfonate 1.1 g d. Phosphoric acid 0.55 g E. Poly (ethyl acrylate / methacrylic acid) latex 2.9 g f. Compound [B] 46 mg

[0112]

[Chemical 36]

G. Oil dispersion of dye described in JP-A-61-285445. As dye itself, 246 mg Dye (B)

[0114]

[Chemical 37]

H. Oligomeric surfactant dispersion of dye described in JP-A-62-275639 46 mg as dye itself Dye (C)

[0116]

[Chemical 38]

5. Preparation of back surface protective layer coating liquid

The container was heated to 40 ° C., and the chemicals shown below were added to prepare a coating solution.

A. Gelatin 100 g b. Sodium polystyrene sulfonate 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.6g bets. C ₈ F ₁₇ SO ₃ K 268 mg h. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 45mg Li. NaOH 0.3 g Nu. 131 ml of methanol 1,2-bis (vinylsulfonylacetamide) ethane based on the total amount of gelatin in the back layer and surface protection layer; Prepared to be 2%. Wo. Compound (B) 45 mg

[0120]

[Chemical Formula 39]

6. Preparation of Photographic Material The coating solution for the back layer together with the coating solution for the surface protective layer for the back layer was coated on one side of a polyethylene terephthalate support colored in blue, and the gelatin coating amount for the back layer was 2.6.
The coating amount was 9 g / m ² , and the coating amount of the back surface protective layer was 1.13 g / m ² . Following this,
And opposite each emulsion coating solution described above to side and the surface protective layer coating solution of the support, coated Ag amount of emulsion coating solution 2.4 g / m ^2, the amount of gelatin of 1.85 g / m ² and a surface protective layer Photographic materials 1 to 6 were prepared by coating so that the amount of gelatin was 1.2 g / m ² . 7. Sensitometry Method The coated sample thus prepared was subjected to sensitometry by the following method to measure the photographic sensitivity. The coated sample at 25 ° C,
After being kept at 60% temperature and humidity for 7 days after coating, it was exposed using a 633 nm He-Ne laser exposure unit of AC-1 manufactured by Fuji Photo Film Co., Ltd.

The development processing was carried out as follows. Automatic developing machine ... The drive motor and gear of SRX501 manufactured by KONICA Co., Ltd. were modified to speed up the transfer speed. <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-Hydroxymethyl-4-methyl 1-phenyl-3-pyrazolidone 22.0 g 5-methylbenzotriazole 2 g

[0123]

[Chemical 40]

Make up to 1 liter with water (adjust to pH 10.60). <Fixing liquid concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid). When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 333 ml of the above concentrated developer solution, 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above-mentioned fixing liquid concentrate and 800 ml of water Processing speed ... Dry to Dry 35 seconds Development temperature ... 35 ° C. Fixing temperature ... 32 ° C. Drying temperature ... 55 ° C.

As the photographic sensitivity, the reciprocal of the exposure amount showing D = 1.0 was represented by a relative value, and the sensitivity of the photographic material 1 was set to 100. The fog value was shown by the difference between the density of the support and the density of the unexposed area. The results obtained are shown in Table 1.

[0126]

[Table 1]

From the results shown in Table 1, it is clear that the present invention using the tellurium compound has higher sensitivity than the comparative material. Further, it can be seen that the use of N, N dimethylselenourea (selenium sensitizer) in combination provides higher sensitivity. From the above, it is clear that the present invention is effective.

Example 2 1. Preparation of silver halide emulsion 40 g of gelatin was dissolved in 1 liter of H ₂ O and heated to 53 ° C.
5 g of sodium chloride, 0.4 g of potassium bromide, and the following compound (A) in a container heated to

[0129]

[Chemical 41]

After adding 60 mg of water, 1000 ml of water-soluble containing 200 g of silver nitrate, potassium hexachloroiridium (III) so that the molar ratio of iridium to the finished silver halide is 10 ⁻⁷ , 21 g of sodium chloride and potassium bromide. Water-soluble 1080 ml containing 100 g was added by the double jet method to give an average particle size of 0.35μ.
m cubic monodisperse silver chlorobromide grains were prepared. After desalting this emulsion, 40 g of gelatin was added, pH 6.0, pA
2.5 mg of sodium thiosulfate and 4 mg of chloroauric acid were added according to g8.5, and chemical sensitization was performed at 60 ° C.
Hydroxyl-6-methyl-1,3,3a, 7-tetrazaindene (0.2 g) was added and rapidly solidified (emulsion A). Next, 0.35 μm cubic monodispersed silver chlorobromide grains were prepared in the same manner as in Emulsion A, and after desalting, 40 g of gelatin was added to adjust to pH 6.0 and pAg 8.5. To this emulsion, 9.6 × 10 ^-6 mol of the tellurium sensitizer exemplified compound 24 and 4 mg of chloroauric acid were added, and after chemical sensitization at 60 ° C., 4-hydroxy-6-methyl-1,3,3a, 0.2 g of 7-tetrazaindene was added and rapidly solidified to prepare Emulsion B. Similarly to Emulsion A, except that 3.2 × 10 ⁻⁶ mol of tellurium sensitizer Exemplified Compound 24 and 1.5 mg of sodium thiosulfate were added in place of 2.5 mg of sodium thiosulfate of Emulsion A. To prepare Emulsion C.

2. Preparation of emulsion coating solution

A container in which 1000 g of each emulsion was weighed was placed at 40 ° C.
The mixture was heated to 1, and additives were added by the method described below to prepare an emulsion coating solution.

(Formulation of emulsion coating solution)

A. Emulsion 1000 g b. Spectral sensitizing dye [2] 1.2 × 10 ⁻⁴ mol c. Supersensitizer [3] 0.8 × 10 ⁻³ mol d. Shelf life improving agent [4] 1 × 10 ⁻³ Morpho. Polyacrylamide (molecular weight 40,000) 7.5 g f. Trimethylolpropane 1.6 g. Polystyrene sulfonate Na 1.2 g H. Poly (ethyl acrylate / methacrylic acid) latex 12 g Re. N, N'-ethylenebis- (vinyl sulfone acetamide) 3.0 g. 1-phenyl-5-mercapto-tetrazole 50mg

Spectral sensitizing dye [2]

[0136]

[Chemical 42]

Supersensitizer [3]

[0138]

[Chemical 43]

Storability improver [4]

[0140]

[Chemical 44]

3. Preparation of coating solution for surface protection layer of emulsion layer

The container was heated to 40 ° C., and additives were added in the formulation shown below to prepare a coating solution.

(Formulation of coating solution for emulsion layer surface protective layer)

A. Gelatin 100 g d. Polyacrylamide (molecular weight 40,000) 12 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g D, N, N'-ethylenebis- (vinyl sulfone acetamide) 2.2 g E. Polymethylmethacrylate fine particles (average particle size 2.0 μm) 2.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Ji. Sodium polyacrylate 6.0 g Re. C ₈ F ₁₇ SO ₃ K 70 mg Nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. 6 ml of NaOH (1N). Methanol 90 ml Wa. Compound [5] 0.06 g

[0145]

[Chemical 45]

4. Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added according to the formulation shown below to prepare a back layer coating liquid.

(Prescription of Back Layer Coating Liquid) a. Gelatin 100 g b. Dye [6] 4.2 g c. Polystyrene sodium sulfonate 1.2 g d. Poly (ethyl acrylate / methacrylic acid) latex 5 g e. N, N'-ethylenebis- (vinyl sulfone acetamide) 4.8 g f. Compound [5] 0.06 g g. Dye [7] 0.3 g h. Dye [8] 0.05g

Dye [6]

[0149]

[Chemical 46]

Dye [7]

[0151]

[Chemical 47]

Dye [8]

[0153]

[Chemical 48]

5. Preparation of back surface protective layer coating liquid

The container was heated to 40 ° C., and additives were added in the formulation shown below to prepare a coating solution.

(Prescription of coating solution for back surface protective layer)

B. Gelatin 100 g b. Polystyrene sulfonic acid soda 0.5 g c. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.9 g d. Polymethylmethacrylate fine particles (average particle size 4.0 μm) 4 g e. Sodium t-octylphenoxyethoxyethane sulfonate 2.0 g f. 6 ml of NaOH (1N). Sodium polyacrylate 2.4 g h. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Li. C ₈ F ₁₇ SO ₃ K 70 mg. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. 150 ml of methanol. Compound [5] 0.06 g

6. Creating photographic material

The above coating solution for the back layer was applied together with the coating solution for the surface protective layer of the back layer on the side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3 g / m ² . Subsequently, the emulsion coating solution and the surface protective layer coating solution described above were applied to the opposite side of the support at a coating Ag amount of 2.5 g / m ^2.
And the gelatin coating amount of the surface protective layer was 1 g / m ² (photographic material 7). Further, a photographic material 8 was prepared in exactly the same manner except that the emulsion B was used in place of the emulsion A. Further, a photographic material 9 was prepared by using the emulsion C in the same manner.

7. Sensitometric method

Sensitometry was carried out by the following method using Samples 1-1 to 3 thus prepared, and the sensitivity was measured. Samples 1-1 to 3 were kept at a temperature and humidity of 25 ° C. and 60%, left for 7 days after coating, and subjected to scanning exposure for 10 ⁻⁷ seconds using a semiconductor laser of 780 nm at room temperature. Development processing was performed with the fixing solution [I]. The development time was performed in two stages of 7 seconds and 15 seconds, and the rise of initial development and the arrival sensitivity were compared. For the sensitivity value, the reciprocal of the exposure amount giving D = 1.0 was expressed as a relative value. The fog value was measured in the same manner as in Example 1. The results are shown in Table 1.

Composition of developer [I]

Potassium hydroxide 29 g Sodium sulfite 31 g Potassium sulfite 44 g Ethylenetriaminetetraacetic acid 1.7 g Boric acid 1 g Hydroquinone 30 g Diethylene glycol 29 g 1-Phenyl-3-pyrazolidone 1.5 g Glutaraldehyde 4.9 g 5-Methylbenzotriazole 60 mg 5- Nitroindazole 0.25 g Potassium bromide 7.9 g Acetic acid 18 g upto 1000 ml pH 10.3 Fixer [I] composition

Ammonium thiosulfate 140 g sodium sulfite 15 g ethylenediaminetetraacetic acid disodium dihydrate 20 mg sodium hydroxide 7 g aluminum sulfate 10 g boric acid 10 g sulfuric acid 3.9 g acetic acid 15 g H ₂ O upto 1000 ml pH 4.30 The results obtained were obtained. It shows in Table 2.

[0165]

[Table 2]

From the results shown in Table 2, it is clear that the present invention is effective as in Example 1.

Claims (3)

[Claims] 1. A support comprising at least one photosensitive silver halide emulsion comprising silver halide grains containing 50 mol% or less of silver chloride and 10 ^-8 mol or more of an iridium compound per mol of silver halide. In a silver halide photographic light-sensitive material, the silver halide emulsion is mixed with a sensitizing dye at 6
A silver halide photographic light-sensitive material characterized by being spectrally sensitized to a wavelength of 00 nm or more and further chemically sensitized with a tellurium compound and a gold compound. 2. The silver coating amount on one side of the silver halide emulsion is 2.8 g / m ² or less, and the total coating amount of gelatin on the same side of the support as the silver halide emulsion is 3. 5 g
/ M ² or less, the silver halide photographic light-sensitive material according to claim 1. 3. The development processing method for a silver halide photographic light-sensitive material according to claim 2, wherein the processing is carried out by an automatic processor having a total processing time of 15 seconds to 60 seconds.