JP2002258427A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high contrast silver halide photosensitive material having low fog and high sensitivity, less liable to fog in long-term storage and causing a small sensitivity change with age after exposure. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on the base, the at least one silver halide emulsion layer contains at least one compound of the formula [Aux Chy Mz ]Wn [where Ch is S, Se or Te; M is an alkali metal; W is a counter ion required to neutralize an electric charge of the compound; (x), (y) and (n) are each an integer of >=1; and (z) is an integer of 0-2].

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 material. In particular, when the charge is neutralized by a counter salt, the composition of which is achieved by a complex consisting of only the gold and chalcogen elements, high sensitivity, less generation of fog, high contrast, and when the photosensitive material is aged for a long time. The present invention relates to a silver halide photographic light-sensitive material which has a small increase in fog and a small change in sensitivity with time after exposure.

[0002]

2. Description of the Related Art A silver halide emulsion used for a silver halide photographic light-sensitive material is usually subjected to chemical sensitization using various chemical substances in order to obtain desired sensitivity and gradation. As typical methods, sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals such as gold, reduction sensitization, and various sensitization methods using a combination thereof are known. In recent years, there has been a strong demand for high sensitivity, excellent graininess, high sharpness, and rapid processing in which development progress has been accelerated in silver halide photographic light-sensitive materials. Of these, the most widely used one is a gold-sulfur sensitization method using a so-called unstable sulfur compound and a gold compound which can generate silver sulfide by reacting with silver ions. By P. Grafkies, “Chimie et Physiqu
e Photographique ”(Paul Montel, 1987, 5th
Edition), edited by TH James, “The Theory of the Photogr
aphic Process ”(published by Macmillan, 1977, 4th edition),
H. Frieser, “Die Grundlagen der Photographische
n Prozesse mit Silber-halogeniden ”(Akademische V
erlagasgeselshaft, 1968).

As a method of sensitizing a silver halide emulsion with gold-sulfur, a method of separately adding an unstable sulfur compound capable of reacting with silver ions to form silver sulfide and a gold compound, The method is described in the above-mentioned reference materials, as well as the Journal of the Photographic Society of Japan, Vol. 50, No. 2, p. 108 et seq. (1987);
ournal of the Optical Society of America, 39
Vol. 6, No. 6, 494 et seq. (1949). In these methods, chloroauric acid has been used as a gold compound, and thiourea compounds and thiosulfates have been used as unstable sulfur compounds. However, when these compounds are used, the degree of increase in sensitivity obtained is insufficient, fogging is likely to occur, the gradation is softened, and fog occurs when the photosensitive material is stored for a long period of time. There are various problems such as remarkable, and a solution to the problem has been strongly demanded.

On the other hand, gold sulfur sensitization using a gold compound other than chloroauric acid is described in JP-B-38-6447, JP-A-62-85239, and gold complexes of thioethers.
Gold complexes of rhodanines described in JP-A-1-47537, gold complexes of mesoions described in JP-A-4-267249, and golds of hydantoins disclosed in JP-A-4-268550 and the like Methods using a complex have been known. However, none of these compounds was sufficient to solve the above problems.

JP-A-4-67032, JP-A-4-75053, JP-A-4-8664
No. 9 describes a gold complex compound which is described as having an effect of improving fog when a photosensitive material is aged for a long period of time and accompanying deterioration of granularity, but all these compounds are also described. It did not show sufficient action to solve the above problem.

Further, JP-A-4-204724 discloses a method of sensitizing a silver halide emulsion to gold selenium by separately adding an unstable selenium compound which can react with silver ions to form silver selenide and a gold compound. However, in this case as well, the rise in fog is remarkable, and the above problem has not been solved.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the use of a specific gold-chalcogen complex, whose charge is neutralized by a counter ion, enables low fog and high fog. Another object of the present invention is to provide a silver halide light-sensitive material which has a high sensitivity, has less fogging when stored for a long period of time, and has a small sensitivity fluctuation with time after exposure.

[0008]

The above object has been achieved by the following silver halide photographic materials. [1] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains at least one compound represented by the following general formula (1). A silver halide photographic material characterized by containing. In the general formula _{(1) [Au x Ch y} M z] W n [ Formula (1), Ch represents a sulfur atom, a selenium atom or tellurium atom, M represents an alkali metal. W represents a counter salt required to neutralize the charge of the compound, and x, y, n
Represents an integer of 1 or more, and z represents an integer of 0 to 2. [2] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has at least one kind represented by formula (1) above. A silver halide photographic material comprising a silver halide emulsion chemically sensitized with a compound. In the general formula _{(1) [Au x Ch y} M z] W n [ Formula (1), Ch represents a sulfur atom, a selenium atom or tellurium atom, M represents an alkali metal. W represents a counter salt required to neutralize the charge of the compound, and x, y, n
Represents an integer of 1 or more, and z represents an integer of 0 to 2. [3] The silver halide photographic material as described in [1] or [2], wherein in the general formula (1), Ch is a sulfur atom. [4] The silver halide photographic material as described in [1] or [2], wherein in the general formula (1), Ch is a selenium atom. [5] The silver halide photographic material as described in [1] or [2], wherein in the general formula (1), Ch is a tellurium atom. [6] The silver halide photographic material as described in any one of the above items, wherein in the general formula (1), x + y is 4 or more and 40 or less. [7] The silver halide photographic material as described in any of the above items, wherein in the general formula (1), Au is a monovalent ion. [8] In the above general formula _{(1), [Au x Ch} y M z] The silver halide photographic light-sensitive material according to any one of the terms structure ions characterized in that it is a cyclic or cage-like structure .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (1) used in the present invention will be described below in detail. Complex ion structures of the general formula _{(1) [Au x Ch y} M z] a compound represented by W _n Formula (1) is a chain-like structure, can be represented by the cyclic structure or cage structure, a cyclic structure or cage Those represented by an independent molecular structure such as a ring-like structure are preferable, and a case of a cyclic structure is more preferable.

In the formula (1), Au is preferably an ion, and more preferably a monovalent ion.

In the formula (1), Ch represents a sulfur atom, a selenium atom or a tellurium atom. In the present invention, Ch is preferably a sulfur atom or a selenium atom, particularly preferably a sulfur atom. Ch is may be atomic in ion has a charge as a whole [Au _x Ch _y]. M may be contained in the annular or cage structure.

In the formula (1), M represents an alkali metal, such as a lithium cation, a sodium cation, and a potassium cation.

In the formula (1), W represents a counter ion necessary for neutralizing the charge of the compound. When the counter ion represented by W is an anion, a halogenium ion (for example, F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a tetrafluoroboronate ion (BF ₄ ⁻ ), and a hexafluorophosphonate ion (PF ₆ ⁻⁾ ), Sulfate ion (SO ₄ ²⁻ ), arylsulfonate ion (eg, p-toluenesulfonate ion, naphthalene-2,5-disulfonate ion, etc.), carboxy ion (eg, acetate ion, trifluoroacetate ion, oxalate ion, benzoic acid ion) Acid ion). When the counter ion represented by W is a cation, an alkali metal ion (for example, lithium cation,
Sodium cation, potassium cation, rubidium cation, cesium cation, etc.), alkaline earth metal ion (eg, magnesium ion, calcium ion, etc.), substituted or unsubstituted ammonium ion (eg, ammonium, triethylammonium, tetraethylammonium, etc.), Unsubstituted pyridinium ions (eg, pyridinium, 4-phenylpyridinium, etc.), substituted arsenium ions (eg, tetraphenylarsenium, etc.), substituted phosphonium ions (eg, tetraphenylphosphonium, etc.), (R ₃ P) ₂ N
^{+ And the} like. R represents an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group; An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl,
2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably Is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms.
2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl), and also includes a tricyclo structure having many ring structures. An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o
-Hexadecanoylaminophenyl) or a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound). And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl).

In the formula (1), x and y represent an integer of 1 or more. In the present invention, x is preferably 1 to 20
And more preferably 1 to 12. In the present invention, y is preferably 1 to 20, more preferably 1
~ 13. Further, in the present invention, x + y is 4 to 4
It is preferably 0, more preferably 5 to 25, and even more preferably 7 to 20. In the present invention, it is preferable that x ≦ y.

In the formula (1), n is the number of W for neutralizing the charge of the compound, and represents an integer of 1 or more.
In the present invention, n is preferably 1 to 8.

In the present invention, the compound represented by the general formula (1) is preferably such that Ch is a sulfur atom or a selenium atom, x + y is 4 to 40, more preferably Ch is a sulfur atom or a selenium atom, and x + y Is 5 to 25, and more preferably, Ch is a sulfur atom and x + y is 7 to 20.
It is. In the present invention, the compound represented by the general formula (1) is preferably used together with an unstable sulfur compound, an unstable selenium compound or an unstable tellurium compound known as a chalcogen sensitizer, and is preferably used together with an unstable selenium compound. Is particularly preferred.

Next, specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to these.

[0018]

[Table 1]

The compounds represented by the general formula (1) of the present invention can be prepared by the following known literatures, for example, Angew. Chem. Int. Ed. 1984, 23, 246. Inorg. Chim. Acta 1984, 85 Chem. Int. Ed. 1984, 23, 715. Inorg. Chem. 1991, 30, 3572. Angew. Chem. Int. Ed. 1992, 31, 787. Angew. Chem. Int. Ed. 1985, L39. , 24, 432. Inorg. Chim. Acta 1985, 102, L37. Kristallogr. 1998, 213, 18. J. Less-Common. Met. 1988, 137, 13. J. Less-Common. Met. 1987, 132, 173. J. Alloys Comp. 1996, 243, 1. Angew. Chem. Int. Ed. 1990, 29, 914.

The addition amount of the compound represented by the general formula (1) of the present invention can vary widely depending on the case, but it is 1 × 10 ^{-6 to} 5 × 10 ^-3 mol, preferably 1 mol per mol of silver halide. It is from 5 × 10 ^{-6 to} 5 × 10 ^-4 mol.

The compounds represented by the general formula (1) of the present invention include water, alcohols (eg, methanol and ethanol), ketones (eg, acetone), amides (eg, dimethylformamide), and glycols (eg, methylpropylene). Glycol and the like, and esters (such as ethyl acetate) may be added as a solvent. Further, as for the compound insoluble in various solvents, the solid itself can be used as fine particles. With regard to micronization, a ball mill,
It can be used after being pulverized with a grinding agent such as salt using a kneader such as a sand mill or a kneader to form fine particles, or formed into fine particles by a well-known precipitation method or a synthetic precipitation method. Such micronization can be carried out, for example, by the method described in "Latest Pigment Dispersion Technology" (Technical Information Association, 1995).

The compound of the present invention represented by the general formula (1) can be added at any stage during the production of the emulsion, but is added after the formation of silver halide grains and before the completion of the chemical sensitization step. Are preferred.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochloride and silver iodobromide are used. However, an emulsion containing bromide ions or iodide ions is more preferable. The size of silver halide grains is not limited, but is equivalent to 0.01 to 3 μm
Is preferred. The shape of silver halide grains is
A regular crystal system (normal crystal grains) or an irregular crystal system may be used. Normal crystal grains include cubic, octahedral, dodecahedral, tetradecahedral, icosahedral, and forty-octahedral. Irregular crystal forms include spherical and potato-like. In addition, grains having one or more twin planes may be used, and hexagonal tabular grains and triangular tabular grains having two or three parallel twin planes are preferably used. Further, in the case of tabular grains, it is more preferable that the grain size distribution be monodisperse (coefficient of variation: 10 to 20%). For the preparation of monodisperse tabular grains, see JP-A-63-11928.
There is a description in the publication. Monodisperse hexagonal tabular grains are described in JP-A-63-151618. Circular monodisperse tabular grain emulsions are described in JP-A-1-131.
No. 541. JP-A-2-838 discloses that at least 95% of the total projected area is occupied by tabular grains having two twin planes parallel to the main plane, and the size distribution of the tabular grains is small. Emulsions that are monodisperse are disclosed. EP 514 742 A discloses a tabular grain emulsion prepared using a polyalkylene oxide block polymer and having a grain size variation coefficient of 10% or less. By using these techniques, it is possible to prepare monodisperse particles preferred in the present invention. Further, the coefficient of variation of the particle thickness is preferably 20% or less, particularly preferably 5 to 15%.

The main surface of the tabular grains is (10)
Nos. 0) and (111) are known, and the former is described in U.S. Pat. No. 4,063,951 and JP-A-5-281640 regarding silver bromide.
Silver chloride is described in EP 0534395 A1 and US Pat. No. 5,264,337. The latter tabular grains are grains having various shapes having one or more twin planes described above. Silver chloride is disclosed in U.S. Pat. Nos. 4,399,215, 4,983,508 and 5,183. 732, JP-A-3-13763.
Nos. 2 and 3-116113 can be referred to. The present invention can be preferably applied to both (100) and (111) tabular grains. The tabular emulsion preferably used in the invention has an aspect ratio (equivalent circle diameter / grain thickness) of 2 or more and 1 or more.
An emulsion in which silver halide grains of not more than 00 exist in an amount of 50% or more (area) of all silver halide grains in the emulsion. The emulsion is preferably one in which silver halide grains having an aspect ratio of 5 or more, more preferably 8 or more, are present in an amount of 50% (area) or more of all silver halide grains in the emulsion, preferably 60% or more, and particularly preferably. Is an emulsion present in 85% or more. The equivalent circle diameter of the tabular grains is 0.2 to 5.
0 μm, preferably 0.5 to 3.0 μm, particularly preferably 0.6 to 2.0 μm. The thickness of the tabular grains is preferably 0.02 to 0.3 μm, and 0.03 to 0.2 μm.
m is particularly preferred. In the case of an internal latent image type direct positive silver halide emulsion, the same range as that of the above-mentioned tabular emulsion is preferable, but the average grain diameter (equivalent circle diameter) is 0.3.
μm or more (preferably 0.3 to 10 μm, more preferably 0.5 to 5.0 μm, and still more preferably 0.5 to 3.
0 μm) and an aspect ratio of 2 or more, more preferably 5 or more, and still more preferably 8 or more (preferably 100 or less).
Is 5% of the total silver halide grains in the emulsion.
Emulsions having 0% (area) or more (preferably 70% or more, more preferably 85% or more) are preferable.

The silver halide grains may have dislocation lines in the grains. With respect to the technique of introducing dislocations into silver halide grains while controlling the dislocations, see JP-A-63-22023.
No. 8 can be referred to. Dislocation can be introduced by providing a specific high iodine phase inside a tabular grain having an average aspect ratio of 2 or more and covering the outside thereof with a phase having a lower iodine content than the high iodine phase. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in latent image stability, and a reduction in pressure fog can be obtained. Thereby, dislocations are mainly introduced at the edge portions of the tabular grains. The tabular grains having dislocations introduced at the center are described in US Pat. No. 5,238,796. The present invention
The effect is obtained when 50% or more of the silver halide grains contain 10 or more dislocation lines per grain.

In the preparation of the silver halide emulsion, there are no particular restrictions on the additives that can be added from the time of grain formation to the time of coating. A silver halide solvent can be used to promote growth during the crystal formation process, and to effectively enhance chemical sensitization during grain formation and / or chemical sensitization. As preferred silver halide solvents, water-soluble thiocyanates, ammonia, thioethers and thioureas can be used. Examples of silver halide solvents include thiocyanates (U.S. Pat. No. 2,222,264).
No. 2,448,534 and No. 332,069), ammonia, thioether compound (US Pat.
No. 271157, No. 3574628, No. 370413
0, 4297439 and 4276347), thione compounds (JP-A-53-144319,
JP-A-53-82408 and JP-A-55-77737, amine compounds (described in JP-A-54-100717), thiourea derivatives (described in JP-A-55-2982), imidazoles (described in JP-A-55-2982). 54-100717) and substituted mercaptotetrazole (Japanese Unexamined Patent Publication No.
2020531).

There is no particular limitation on the method for producing a silver halide emulsion. Generally, a silver salt aqueous solution and a halogen salt aqueous solution are added to a reaction solution having an aqueous gelatin solution with efficient stirring. As a specific method, P. Glafk
by ides Chimie et PhysiquePhtographique (Paul Mont
el, 1967), GF Dufin, PhotographicEmu
lsion Chemistry (The Forcal Press, 1966), V.
Making and Coating Photographic by L. Zelikman etal
It can be prepared using the method described in Emulsion (The Forcal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used.
The method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, a combination thereof, and the like. Further, a method of changing the addition rate of silver nitrate or an aqueous solution of an alkali halide according to the grain growth rate (British Patent No. 153016, Japanese Patent Publication No.
36890 and 52-16364) and a method of changing the concentration of an aqueous solution (US Pat.
No. 445 and Japanese Patent Application Laid-Open No. 55-158124), it is preferable to grow quickly within a range not exceeding the critical supersaturation degree. Since these methods do not cause renucleation and the silver halide grains grow uniformly,
It can be preferably used.

Instead of adding a silver salt solution and a halogen solution to a reaction vessel, a method in which fine particles prepared in advance are added to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. It is also preferred to use This technique is disclosed in Japanese Patent Laid-Open No. 1-183644.
Nos. 1-183645, 2-44335, and 2
References can be made to JP-A-43534 and JP-A-2-43535 and U.S. Pat. No. 4,879,208. According to this method, the distribution of halogen ions in the crystal of the emulsion grains can be made completely uniform, and favorable photographic characteristics can be obtained. Further, in the present invention, emulsion grains having various structures can be used. A so-called core / shell double-structured particle comprising a particle inside (core portion) and an outside (shell portion), and a triple structure particle (JP-A-60-2)
No. 22844) or a multi-layered particle having more than that is used. When giving a structure inside the emulsion grain,
Particles having not only the above-described wrapping structure but also a so-called bonding structure can be produced. Examples thereof are described in JP-A-58-108526, JP-A-59-16254, JP-A-59-133540, JP-B-58-24772, and European Patent 199290A2. The crystal to be bonded can be grown by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure. In the case of a joint structure,
Naturally, silver halides can be combined with each other, but any silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, may be used in combination with silver halide to form a bonding grain. In the present invention, it is most preferable to use core-shell type double structure particles.

In the case of silver iodobromide grains having these structures, for example, in core-shell type grains, even if the silver iodide content in the core is high and the silver iodide content in the shell is low, Conversely, grains having a low silver iodide content in the core portion and a high silver iodide content in the shell portion may be used. Similarly, particles having a bonding structure may be particles having a high silver iodide content in the host crystal and a relatively low silver iodide content in the bonding crystal, or vice versa. Further, in the grains having these structures, the boundary portion having different halogen composition may be a clear boundary, or may be an unclear boundary by forming a mixed crystal due to a composition difference, and may be continuously connected. It may have a structural change. The silver halide emulsion is preferably of a surface latent image type. However, JP-A-59-1335
As disclosed in JP-A-42, an internal latent image type emulsion can be used by selecting a developing solution or conditions for development. Also, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose. In the present invention, the chemical sensitization of at least one of the above-described core and shell chemical sensitizations is preferably performed using the compound of the above general formula (1), preferably with a pAg of 5 to 10, a pH of 4 to 8, and a temperature of 30 to 30. Performed at 80 ° C. A chalcogen sensitizer, a gold sensitizer, and another chemical sensitizer may be used in combination with the compound of the general formula (1). A typical example of the gold sensitizer is chloroauric acid or an alkali salt thereof. Preferably, chemical sensitization of the core is performed using a compound of the general formula (1). Further, both the core and the shell need not necessarily be chemically sensitized using the compound of the general formula (1). In such a case, chemical sensitization using a combination of a chalcogen sensitizer and a gold sensitizer, Alternatively, other chemical sensitizers are applied. Regarding the production method of the silver iodobromide tabular emulsion preferably used in the present invention, U.S. Pat.
No. 34226, No. 4433048, No. 44143
No. 10, No. 5,334,495 and the like can be referred to. Ultra thin tabular emulsions having a grain thickness of 0.1 μm or less are described in U.S. Pat.
Nos. 1853 and 5418125 can be referred to. When the present invention is applied to a high silver chloride tabular emulsion,
Emulsions preferably used include EP 7231
Nos. 87, 615517, 534395, and 584644 can be referred to.

[0030] Silver halide emulsions are usually spectrally sensitized. It is usually preferable to use a methine dye as the spectral sensitizing dye. Methine dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
Any of rings generally used for cyanine dyes as basic heterocycles can be applied to these dyes. Examples of the basic hetero ring include a pyrroline ring, an oxazoline ring, a thiazoline ring, a pyrrole ring, an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a tetrazole ring, and a pyridine ring. Also,
Rings in which a cyclic hydrocarbon ring or an aromatic hydrocarbon ring is fused to a hetero ring can also be used. Examples of the condensed ring include an indolenine ring, a benzindolenin ring, an indole ring, a benzoxadol ring, a naphthoxazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a benzimidazole ring and a quinoline ring. Can be done. Substituents may be bonded to carbon atoms of these rings. A 5- or 6-membered heterocycle having a ketomethylene structure can be applied to the merocyanine dye or the composite merocyanine dye. Examples of such heterocycles include pyrazolin-5-one ring, thiohydantoin ring, 2-thiooxazolidine-2,4-dione ring, thiazolidine-2,4-dione ring, rhodanine ring and thiobarbitur. Acid rings can be mentioned.

The sensitizing dye is preferably added in an amount of 0.001 to 100 mmol per mol of silver halide, preferably 0.1 to 100 mmol.
More preferably, it is from 01 to 10 mmol. The sensitizing dye is preferably added during or before chemical sensitization (for example, during grain formation or physical ripening).

A dye which does not exhibit spectral sensitization itself or a substance which does not substantially absorb visible light and exhibits supersensitization together with a sensitizing dye can be added to a silver halide emulsion. Good. Examples of such dyes or substances include aminostil compounds substituted with a nitrogen-containing heterocyclic group (US Pat. Nos. 2,933,390 and 3,635,721).
Described in each specification), an aromatic organic acid formaldehyde condensate (described in US Pat. No. 3,743,510), a cadmium salt and an azaindene compound. For the combination of a sensitizing dye and the above dye or substance, see US Pat. Nos. 3,615,613 and 3,61.
Nos. 5,641, 3,617,295 and 3,6
No. 35,721.

The silver halide emulsion is generally used after chemical sensitization. Chemical sensitization includes sensitization by a compound of the general formula (1), chalcogen sensitization (sulfur sensitization, selenium sensitization,
Tellurium sensitization), noble metal sensitization (eg, gold sensitization), and reduction sensitization are performed alone or in combination. In the present invention, sensitization by the compound of the general formula (1), chemical sensitization in which sulfur sensitization and gold-sulfur sensitization are combined, and selenium sensitization and tellurium sensitization are also preferably used. In sulfur sensitization, an unstable sulfur compound is used as a sensitizer. For unstable sulfur compounds, see P. Glafkides, Chimie e
t Physique Photographeque (Paul Montel, 1987
Year, 5th edition), Research Disclosure Magazine, Volume 307
No. 105, edited by THJames, The Theory of the Photog
raphic Process (published by Macmillan, 1977, 4th edition),
H. Frieser, Die GrundlagenderPhotographischen Pr
ozess mit Silver-halogeniden (Akademische Verlags-
geselbshaft, 1968). Examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate), thioureas (eg, diphenylthiourea, triethylthiourea, N-ethyl-N′-).
(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide, N-phenylthioacetamide), rhodanines (eg, rhodanine, N-ethylrhodanine, 5
-Benzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine, diethyl rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2-thiones, dipolysulfide (E.g., dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (e.g., cysteine), polythionates and elemental sulfur. Activated gelatin can also be used as a sulfur sensitizer.

In selenium sensitization, an unstable selenium compound is used as a sensitizer. Unstable selenium compounds are described in JP-B-43-13489 and JP-B-44-15748.
No., JP-A-4-25832, JP-A-4-109240,
It is described in JP-A-4-271341 and JP-A-5-40324. Examples of selenium sensitizers include colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenourea) Acetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-) Tolyl selenophosphate, tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone) isoselenocyanates, selenocarboxylic acids, selenoesters, and diacyl selenides. In addition, relatively stable selenium compounds such as selenous acid, potassium selenocyanide, selenazoles and selenides (Japanese Patent Publication No.
Nos. 4553 and 52-34492)
Can also be used as a selenium sensitizer.

In the tellurium sensitizer, an unstable tellurium compound is used as a sensitizer. Unstable tellurium compounds are described in Canadian Patent No. 800,958;
Nos. 295,462 and 1,396,696, JP-A-4-204640 and 4-271341.
No. 4,333,033 and 5-303157. Examples of tellurium sensitization include telluroureas (eg, tetramethyltellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylenetellurourea), phosphine tellurides (eg, butyl- Diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride,
Ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride , Bis (ethoxycarbonyl) telluride), isotellurocyanates (eg, allyl isotellurocyanate), telluroketones (eg, telluroacetone, telluroacetophenone), telluramides (eg, telluroacetamide, N, N-dimethyltellurobenzamide) , Tellurohydrazides (eg, N, N ', N'
-Trimethyltellurobenzhydrazide), telluroesters (eg, t-butyl-t-hexyltelluroester), colloidal tellurium, (di) tellurides and other tellurium compounds (eg, potassium telluride, sodium telluropentathionate) Salt).

In noble metal sensitization, a salt of a noble metal such as gold, platinum, palladium or iridium is used as a sensitizer. For precious metal salts, see P. Grafkides, Chimie et P
hysique Photographique (Paul Montel, 1987,
5th edition), Research Disclosure, Vol. 307, 307105
There is a description in the issue. Gold sensitization is particularly preferred. Examples of gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. In addition, U.S. Pat.
The gold compounds described in the specifications of JP-A-49,484 and JP-A-5,049,485 can also be used. As one form of gold sensitization, U.S. Pat.
No. 5,568,841 and JP-A-3-266828.
And gold complexes described in JP-A Nos. 4-67032 and 8-69074 can also be used.

In the present invention, reduction sensitization can be used in combination. In reduction sensitization, a reducing compound is used as a sensitizer. For reducing compounds, see P. Grafkides, Chi
mie et Physique Photographique (Paul Montel, 1
987, 5th edition), Research Disclosure 307, 30
No. 7105. Examples of reduction sensitizers include aminoiminomethanesulfinic acid (thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine), polyamine compounds (eg, diethylenetriamine, Triethylenetetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds and hydrogen. Further, reduction sensitization can be carried out in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).

Chemical sensitization may be performed in combination of two or more. As the combination, sensitization by the general formula (1),
Combinations of chalcogen sensitization and gold sensitization are particularly preferred. Further, reduction sensitization is preferably performed at the time of forming silver halide grains. The amount of the sensitizer used is determined depending on the type of silver halide grains generally used and the conditions of chemical sensitization. The amount of the chalcogen sensitizer to be used is generally from 10 ^-8 to 10 ^-2 mol, preferably from 10 ^{-7 to} 5 × 10 ^-3 mol, per mol of silver halide. The use amount of the noble metal sensitizer is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. There are no particular restrictions on the conditions for chemical sensitization. The pAg is from 6 to 11, preferably from 7 to 10. Preferably, the pH is between 4 and 10. Preferably the temperature is 40-95 ° C, 45
More preferably, it is -85 ° C.

The layer constitution of the silver halide photographic material is not particularly limited. However, in the case of color photographic materials, blue,
It has a multilayer structure to record green and red light separately. Each silver halide emulsion layer may be composed of two layers, a high-speed layer and a low-speed layer. Examples of practical layer configurations are listed in (1) to (6) below.

(1) BH / BL / GH / GL / RH / RL / S (2) BH / BM / BL / GH / GM / GL / RH / R
M / RL / S (3) BH / BL / GH / RH / GL / RL / S (4) BH / GH / RH / BL / GL / RL / S (5) BH / BL / CL / GH / GL / RH / RL / S (6) BH / BL / GH / GL / CL / RH / RL / S

B is a blue-sensitive layer, G is a green-sensitive layer, R is a red-sensitive layer, H is a highest-sensitivity layer, M is an intermediate-sensitivity layer, L is a low-sensitivity layer, S is a support, and CL is a layer effect. Layer. Non-photosensitive layers such as a protective layer, a filter layer, an intermediate layer, an antihalation layer and an undercoat layer are omitted. The high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse.
(3) is described in US Pat. No. 4,184,876. For (4), Research Disclos
ure, Vol. 225, No. 22534, JP-A-59-177551
And JP-A-59-177552.
Further, (5) and (6) are described in JP-A-61-345.
No. 41 discloses this. Preferred layer constitutions are (1)
(2) and (4). The silver halide photographic material of the present invention can be applied not only to color photographic materials but also to X-ray photographic materials, black-and-white photographic materials, plate-making photographic materials and photographic paper.

Various additives for the silver halide emulsion (eg, binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin, hardener, surfactant, antistatic agent, polymer latex, matting agent, color For couplers, ultraviolet absorbers, anti-fading agents, dyes), supports for photographic materials and processing methods for photographic materials (eg, coating methods, exposure methods, development processing methods), Research Disclosure, Vol. 176, No. 17643 (RD- 17643), 187, 18716 (RD-18716),
Reference can be made to the description of Vol. 225, No. 22534 (RD-22534). The following table shows the descriptions in these Research Disclosure magazines.

種類 Additive type RD-17643 RD-18716 RD-22534 ─ ───────────────────────────────── 1 Chemical sensitizer Page 23 648 Right column Page 24 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648, right column 24-28 page Supersensitizer 〜 page 649 right column 4 Brightening agent page 24 5 Anti-fogging agent, page 24-25 page 649 right column page 24 , Page 31 Stabilizer 6 Light absorber, page 25-26 page 649 right column Filter dye, ~ 650 page left column Ultraviolet absorber Stain inhibitor 25 page right column 650 page left column to right column 8 Dye image stabilizer 25 Page 32 9 Hardener 26 Page 651 Left column 32 Page 10 Binder 26 Same as above 28 Page 11 Plasticizers and lubricants 27 Page 650 Right column 12 Coating aids, pages 26 to 27 Same as above Surfactants 13 Static prevention Agent page 27 Same as above 14 Color coupler page 25 page 649 page 31 ───── ─────────────────────────────

As the gelatin hardener, for example, an active halogen compound (2,4-dichloro-6-hydroxy-
1,3,5-triazine and its sodium salt, etc.)
And active vinyl compounds (such as 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or a vinyl-based polymer having a vinylsulfonyl group in the chain) can rapidly convert hydrophilic colloids such as gelatin. It is preferred because it cures and provides stable photographic properties. N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) matansulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) can be preferably used because of their high curing rate.

The color photographic material is Research Disclosure
The development can be carried out by a usual method described in Journal Nos. 176, 17643 and 187, 18716.
The color photographic light-sensitive material is usually subjected to a washing treatment or a stabilizer treatment after development, bleach-fixing or fixing. In the rinsing step, two or more tanks are generally countercurrently washed to save water. A typical example of the stabilizing treatment is a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543, instead of the washing step.

In addition to the above, the color coupler used in the present invention is described in JP-A-11-65007, paragraphs 0019 to 0024, and the chemical sensitization is described in paragraphs 0041 to 0053 in JP-A-11-65007. For the agent, paragraph No. 0057 of the same publication, for sensitizing dyes and the like, paragraphs 0058 to 0060 of the same publication, for development processing, paragraphs 0080 to 999 of the same publication, and for the application to the APS system, paragraph No. 0100 to the same publication. 01
26 can be referred to.

The present invention can be preferably applied to a color diffusion transfer photosensitive material using an internal latent image type direct positive silver halide emulsion. As for the internal latent image type direct positive silver halide emulsion, there are a type fogged with light and a type fogged chemically using a nucleating agent, and the type fogged chemically is preferred. Examples of the nucleating agent include hydrazines, hydrazides, heterocyclic quaternary salt compounds, thiourea-bonded acylhydrazine compounds, and hydrazine compounds in which a heterocyclic group such as a thioamide ring or triazole or tetrazole is bonded as an adsorbing group. Compounds are preferred. Preferred internal latent image type direct positive silver halide emulsions are described in US Pat. No. 3,206,313.
Nos. 3761266, 4035185, 43
No. 95478, No. 4504570, No. 4434226
And Nos. 4,414,310 and 4,439,520.

The compound of the present invention represented by the general formula (1)
When used for internal latent image type direct positive silver halide emulsion
Is 5 × 10 5 per mol of silver halide in the core grains.^-Five
~ 1 × 10^-7It is preferably used in a molar ratio, more preferably
Or 1 × 10^-Five~ 1 × 10 ^-6Used in moles. General
Chalcogen sensitizer that may be used in combination with formula (1), gold sensitization
And the other chemical sensitizers are each represented by the general formula (I)
Used at 100 times to 1/100 times (molar ratio) the compound
Preferably, it is 10 times to 1/10 times (molar ratio)
More preferably it is used. Also, the shell particles are chemically
Even when sensitized, the silver halide of the shell grains
Preferably, the above amounts are used.

The color diffusion transfer photosensitive material to which the present invention can be preferably applied will be described. The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (which may be a dye precursor) in connection with silver development, or a substance which changes its diffusivity itself,
The Theory of the Photograp
hic Process) 4th edition. All of these compounds can be represented by the following general formula (3). General formula (3) (DYE-Y ^′ ) _p- Z ^′ {In formula (3), DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, and Y ^′ represents a simple bond or Represents a linking group, and Z ^′ is related to silver development (specifically,
(DYE-Y ^' ) The difference in diffusivity of the compound represented by _p- Z ^' or the release of DYE (corresponding to or inversely corresponding to a photosensitive silver salt having a latent image in an image form). Represents a group having a property that causes a difference in diffusivity between the released DYE and (DYE-Y ^′ ) _p -Z ^′, and p represents 1 or 2, and when p is 2, two DYE-Y ^'may be the same or different. {Circle around (2)} According to the function of Z ^{′ in} the general formula (3), the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion.

Specific examples of the negative type Z ^' include those which are oxidized as a result of development and are cleaved to release a diffusible dye. Specific examples of Z ^′ are U.S. Pat. No. 3,928,312,
4,055,428, 4,179,291, 4,149,892, 4,183,753, 4,142,891, 4,199,355, and 4 , 135,929, JP-A-53-50736, JP-A-57-4043, JP-A-54-130927, and JP-A-56-130927.
164342, 57-119345 and the like.

The negative dye-releasing redox compound Z ^′
Among them, a particularly preferred group is an N-substituted sulfamoyl group (an example of the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions but are oxidized by development to become non-diffusible. As the effective Z ^′ for this type of compound, those described in US Pat. No. 2,983,606 are representative.

Another type is a type in which a diffusible dye is released by, for example, self-ring closure under alkaline conditions, but the dye is substantially not released when oxidized during development. Specific examples of Z ^' having such a function are described in JP-A-53-69033 and JP-A-54-130927.
No. 3,421,964, 4,199,3
No. 55, etc.

Another type does not release the dye itself, but releases the dye when reduced.
Compounds of this type are used in combination with an electron donor,
The diffusible dye can be released imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, U.S. Patent Nos. 4,183,753 and 4,278,750.
No. 4,218,368, 4,358,535
JP-A-53-110827 and JP-A-54-13092.
7, No. 56-164342, published technical report 87-619
No. 9, EP-A-220746A2 and the like.

When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or a precursor (precursor) thereof. Examples of ED compounds include, for example, US Pat.
Nos. 63,393 and 4,278,750;
No. 138736. Specific examples of other types of dye image-forming substances include US Pat.
No. 89 and 4,098,783.

On the other hand, specific examples of the dye represented by DYE in the above general formula are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930 and JP-A-56-71072: Rese
arch Disclosure 17630 (1978), 164
75 (1977).

Examples of magenta dyes: US Pat.
No. 2,380, No. 4,233,237, No. 4,25
0,246, 4,207,104, 4,28
No. 7,292: JP-A-55-36804 and JP-A-56-7
Nos. 3057 and 55-134.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 4,171, 220, No. 4, 142, 89
Nos. 1 and 4,148,642; British Patent 1,551,
No. 138; JP-A-52-8827 and JP-A-53-4782.
Nos. 3 and 56-71061; European Patent (EP)
53,037, 53,040; Research Disclos
ure 17,630 (1978) and 16,475
(1977).

[0058]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 (Production method of Em-1) 1200 ml of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. 30 ml of an aqueous solution containing 1.9 g of AgNO ₃ , 1.5 g of KBr and a molecular weight of 15,000
30 ml of an aqueous solution containing 0.7 g of low molecular weight gelatin was added by a double jet method over 30 seconds to form nuclei.
At this time, the excess concentration of KBr was kept constant. 5 KBr
0 g was added, and the temperature was raised to 75 ° C. to ripen. After aging, 1
Molecular weight 10 containing 35 μmol methionine per gram
35 g of phthalated gelatin having a phthalation rate of 97% and 0000
Was added. The pH was adjusted to 5.6. AgNO ₃ 30
g of an aqueous solution containing g and a KBr aqueous solution were added over 16 minutes by a double jet method (growth step 1). At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of AgNO ₃ and 3.8 m
An aqueous solution of KBr (15% by mass) containing ol% of KI was added over 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate (growth step 2). At this time, the silver potential was kept at -20 mV. Further, the number of rotations of the stirring solution was returned to 132, and an aqueous solution 132 containing 35 g of AgNO ₃ was added.
ml and an aqueous KBr solution were added over 7 minutes by the double jet method. KB so that the potential at the end of addition becomes +20 mV
The addition of the r aqueous solution was adjusted. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to −20 mV, and an aqueous solution 1 containing 6.8 g of AgNO ₃ was added.
900 ml of an aqueous solution containing 00 ml and 7.1 g of KI were added by the double jet method over 10 minutes. Immediately after the addition, 250 ml of an aqueous solution containing 70 g of AgNO ₃ and KBr5
170 ml of an aqueous solution containing 0 g was added over 20 minutes. After washing with water, 45 g of gelatin was added and the mixture was adjusted to pH 5.
8, pAg was adjusted to 8.7.

According to transmission electron microscope observation of Em-1 at the temperature of liquid nitrogen, dislocation lines were observed at high density in the fringe portions of the particles, and the particles clearly had 20 or more dislocation lines. The proportion of particles of Em-1 having an aspect ratio of 8 or more occupied 61%, the average aspect ratio was 9.0, the coefficient of variation in iodine distribution between particles was 17, and the average iodine content was 4.3 mol%. .

(Chemical Sensitization and Spectral Sensitization) (Preparation of Solid Fine Dispersion of Sensitizing Dye) Solid fine dispersions of sensitizing dyes 1 to 3 were prepared as follows. As shown in Table 2, the inorganic salt was dissolved in ion-exchanged water, a sensitizing dye was added, and the mixture was dispersed at 2,000 rpm for 20 minutes using a dissolver blade at 60 ° C. as shown in Table 2.
Solid fine dispersions of sensitizing dyes 1 to 3 were prepared. Sensitizing dye 1

[0061]

Embedded image

Sensitizing dye 2

[0063]

Embedded image

Sensitizing dye 3

[0065]

Embedded image

[0066]

[Table 2]

(Preparation of Em-1AR to Em-12AR)
Em-1 was heated to 56 ° C. Sensitizing dyes 1, 2, and 3 were added in a molar ratio of 58: 36: 1, respectively, and in the form of a fine solid dispersion. Thereafter, 1800 ppm of calcium nitrate was added to the emulsion. Thereafter, the gold compound of the present invention, a sulfur sensitizer, potassium thiocyanate (1.5 × 10 ⁻³ mol / mol Ag), chloroauric acid, and N, N-dimethylselenourea shown in Table 3 were added, followed by aging. Optimal chemical sensitization.
1- (p-carboxyphenyl) -5 at the end of chemical sensitization
-Em-1AR to Em-12AR were prepared by adding the disodium salt of mercaptotetrazole.

[0068]

[Table 3]

[0069]

Embedded image

On the cellulose triacetate film support provided with an undercoat layer, the emulsion subjected to the above chemical sensitization under the coating conditions shown in Table 4 below was provided on the protective layer and coated to prepare a sample.

[0071]

[Table 4]

These samples were left under the conditions of 40 ° C. and 70% relative humidity for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge with a gelatin filter SC-50 manufactured by FUJIFILM Corporation. Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., the following method was used (the cumulative replenishment amount of the solution was 3% of the mother liquor tank capacity).
(Until doubled).

(Processing method) Process Processing time Processing temperature Replenishment amount Color development 3 min. 15 sec. 38 ° C. 45 ml Bleaching 1 min. 00 sec. 38 ° C. 20 ml. 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30 ml Stable 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ° C * The replenishment amount is 35mm width 1.1m per length (24Ex. 1 bottle).

Next, the composition of the processing solution will be described. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] 2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.10

(Bleaching solution) Common to tank solution and replenisher (unit: g) Ferric ammonium ammonium diaminetetraacetate dihydrate 20.0 Disodium ethylenediaminetetraacetic acid salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching Accelerator 0.005 mol (CH ₃ ) ₂ N-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -N (CH ₃ ) ₂ .2HCl Aqueous ammonia (27%) 15.0 ml Add water 1. 0 liter pH (adjusted with aqueous ammonia and nitric acid) 6.3

(Bleach-fixing solution) Tank solution (g) Replenisher (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0-Disodium ethylenediaminetetraacetate 5.0 2.0 2.0 Sodium sulfite 12.0 20 6. Ammonium thiosulfate aqueous solution (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 2 7.3

(Washing solution) Common to tank liquid and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stable liquid) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water 1.0 liter pH 8.5

The density of the treated sample was measured with a green filter. The sensitivity was indicated by a relative value of the reciprocal of the exposure required to give a density of fog plus 0.2. In addition, the following experiment was performed to evaluate the storage stability. Unexposed samples were stored at 50 ° C. and 60% relative humidity for 2 weeks. The same sample stored at 5 ° C. for 2 weeks was subjected to a color temperature of 4800 °
A sensitometric exposure was given for 1/100 second through a continuous wedge at K to perform the above color development processing. Next, the concentration was measured, and the difference (Δfog) between the fog value of the sample stored at 50 ° C. and the fog value of the sample stored at 5 ° C. was determined. The larger the plus value, the higher the density. The results are shown in Table 3 above.

Samples were prepared such that the amount of gold atoms contained in each sample was equal, and the above experiment was performed. Table 3
As is clear from the above, when the compound represented by the general formula (1) of the present invention is used, the sensitivity tends to be higher and the fog tends to be lower than when chloroauric acid is used. It was found that the increase in fog was significantly suppressed. Furthermore, it was found that when both the compound represented by the general formula (1) of the present invention and a chalcogen sensitizer, particularly an unstable selenium compound, were used, the fog remained the same and the sensitivity was increased. Also,
Compared with the present invention, when the compound HK-1 described in JP-A-4-267249 was used, an increase in fog during storage could not be suppressed.

Example 2 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: sensitizing dye ExF: dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion P Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020 Third layer (intermediate layer) Silver iodobromide emulsion O 0.020 ExC-2 0.022 Polyethyl acrylate latex 0.085 gelatin 0.294 4th layer (low-speed red-sensitive emulsion layer) silver iodobromide emulsion A silver ^{0.323 ExS-1 5.5 × 10 -4} ExS-2 1.0 × 1 ^{-5 ExS-3 2.4 × 10 -4} ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd- 4 0.025 HBS-1 0.17 Gelatin 0.80 Fifth layer (Medium sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion B Silver 0.28 Silver iodobromide emulsion C Silver 0.54 ExS-1 0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC -5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18 6th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.47 ExS-1 3.7 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 1.8 × 10 ^-4 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd-2 0.046 Cpd- 4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12 7th layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl Acrylate latex 0.83 Gelatin 0.84 Eighth layer (layer giving an overlay effect to red-sensitive layer) Silver iodobromide emulsion E Silver 0.560 ExS-6 1.7 × 10 ^-4 ExS-10 4.6 × 10 ^-4 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58 9th layer (low sensitivity green) Emulsion layer) Silver iodobromide emulsion F silver 0.39 silver iodobromide emulsion G silver 0.28 silver iodobromide emulsion H silver 0.35 ExS-4 2.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExS-7 7.7 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-2 0.36 ExM-3 0.045 HBS-1 0.28 HBS- 3 0.01 HSB-4 0.27 Gelatin 1.39 10th layer (Medium speed green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.45 ExS-4 5.3 × 10 ^-5 ExS-7 5 × 10 ^-4 ExS-8 6.3 × 10 ^-4 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 HBS-1 064 HBS-3 2.1 × 10 ^-3 gelatin 0.44 11th layer (high sensitivity green-sensitive emulsion layer) silver iodobromide emulsion I silver 0. 9 iodobromide emulsion J silver ^{0.80 ExS-4 4.1 × 10 -5} ExS-7 1.1 × 10 -4 ExS-8 4.9 × 10 -4 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-1 18 polyethyl acrylate latex 0.099 gelatin 1.11 12th layer (yellow filter layer) yellow colloidal silver silver 0.047 Cpd-1 0.16 solid disperse dye ExF-5 0.020 solid disperse dye ExF-6 020 Oil-soluble dye ExF-7 0.010 HBS-1 0.082 Gelatin 1.057 13th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K silver 0.18 Silver iodobromide emulsion L Silver 0.20 silver iodobromide emulsion M silver 0.07 ExS-9 4.4 × 10 ^-4 ExS-10 4.0 × 10 ^-4 ExC-1 0.041 ExC-8 0.012 ExY-1 035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.24 Gelatin 1.41 Layer 14 (high Sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion N silver 0.75 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91 15th layer (first protective layer) Silver iodobromide emulsion O silver 0.30 UV-1 21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-18 009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 Gelatin 2.3 16th layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.75 Furthermore, each layer may have a suitable storage property, processing property, pressure resistance, and antifungal property.
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-5, B-4 to B-6, F-1 to F
-18 and iron, lead, gold, platinum, palladium, iridium, ruthenium, and rhodium salts. The coating solution for the eighth layer was 8.5 × 10 ^-3 g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 10 ^-3 g / mol.
^A sample was prepared by adding ^-3 grams of calcium with an aqueous solution of calcium nitrate.

Table 5 below shows the AgI content, grain size, surface iodine content and the like of the emulsions indicated by the above-mentioned abbreviations. The surface iodine content can be determined by XPS as follows. The sample was transferred to -115 in a 1x10 torr transfer vacuum.
C., and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
2, measured for Br3d and I3d5 / 2 electrons, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio.

[0083]

[Table 5]

In Table 5, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to O are disclosed in JP-A-3-23745.
According to the example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer.

(3) Preparation of tabular grains is disclosed in
According to the example of 58 426, low molecular weight gelatin is used.

(4) JP-A-3-2374 for tabular grains
Dislocation lines as described in No. 50 have been observed using a high voltage electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were placed in a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 milliliters were added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The compounds used to form each of the above layers are as shown below.

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(Preparation of Samples 102 to 105) Em-1A prepared in Example 1 in place of the silver iodobromide emulsion D of the sixth layer
Samples using R, Em-2AR, Em-3AR, Em-4AR were prepared, and samples 102, 103, 10
4, 105.

Next, a method of developing each sample will be described.

(Processing method) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 3 minutes 00 seconds 38 ° C. Water washing 30 seconds 24 ° C. Fixing 3 minutes 00 seconds 38 ° C. Water washing (1) 30 seconds 24 ° C. Washing with water (2) 30 seconds 24 ° C. Stability 30 seconds 38 ° C. Drying 4 minutes 20 seconds 55 ° C. Next, the composition of the treatment liquid is described. (Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate 1.0 liter by adding water pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 (bleach-fix solution) (g) Ethylenediaminetetraacetic acid Ferric 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (ammonia Adjusted with water and nitric acid) 6.0 (Fixer) Ethylene Amine tetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Add water to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 (Stabilized solution) (Unit g) ) P-Nonylphenoxypolyglycidol (glycidol average degree of polymerization 10) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 Hydroxyethylcellulose 0.1 (Daicel Chemical HEC SP-2000) 1,2-benzisothiazolin-3-one 0.05 Add water and add 1.0 liter pH 8.5

The density of the processed sample was measured with a red filter, and the fogging value, sensitivity, and the increase in fogging during storage were evaluated in the same manner as in Example 1. Table 6 shows the results. Emulsion of the invention (E
m-3AR, Em-4AR), high sensitivity and low fogging were achieved even with a multilayer color light-sensitive material, and it was confirmed that the increase in fogging during storage was small.

[0112]

[Table 6]

Example 3 In the sample of Example 2, instead of the cellulose triacetate film of the support, the support used for the sample 104 in Example 1 of US Pat. The undercoat layer and the back layer are provided by the method described in column 21, line 54 to column 23, line 29,
A heat treated PEN support was used. Further, these samples were loaded into a packaging unit having a photographing function, and evaluated in the same manner as in Example 2.

As a result, the same result as in Example 2 was obtained. Example 4 Sample 102 of Example 1 in JP-A-7-333782
A color diffusion transfer photosensitive material was prepared in the same manner as described above.
However, Em-7AR which is the emulsion of Example 1 of the present application was used in place of Em-D7 of the eighth, fifteenth, and twenty-second layers of the same sample.
A cover sheet was prepared in the same manner as in the example of JP-A-7-337378, and treated in the same manner as in the example. The obtained photographic properties (highest density, gradation) were all good.

[0115]

By using the compound represented by the general formula (1) of the present invention, the sensitivity tends to be higher and the fog tends to be lower than in the case where another gold sensitizer is added. In this case, the fog increase can be suppressed. Further, in a photographic light-sensitive material using an internal latent image type direct positive silver halide emulsion, the compound represented by the general formula (1) of the present invention has a mid-point sensitivity higher than that obtained when another gold sensitizer is added. In addition, both the foot sensitivity and the foot sensitivity could be increased.

Claims (6)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has at least one kind represented by the following general formula (1). A silver halide photographic material characterized by containing a compound. In the general formula _{(1) [Au x Ch y} M z] W n [ Formula (1), Ch represents a sulfur atom, a selenium atom or tellurium atom, M represents an alkali metal. W represents a counter ion necessary to neutralize the charge of the compound, x,
y and n each represent an integer of 1 or more; z represents an integer of 0 to 2; ] 2. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has at least one kind represented by the following general formula (1). A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with the compound of the formula (1). In the general formula _{(1) [Au x Ch y} M z] W n [ Formula (1), Ch represents a sulfur atom, a selenium atom or tellurium atom, M represents an alkali metal. W represents a counter ion necessary to neutralize the charge of the compound, x,
y and n each represent an integer of 1 or more; z represents an integer of 0 to 2; ] 3. The silver halide photographic light-sensitive material according to claim 1, wherein in the general formula (1), Ch is a sulfur atom. 4. In the general formula (1), x + y is 4 or more and 40 or more.
The silver halide photographic material according to any one of claims 1 to 3, wherein: 5. The silver halide photographic material according to claim 1, wherein in the general formula (1), Au is a monovalent ion. During wherein said general formula _{(1), [Au x Ch} y M z] halogen according to claim 1, the structure of the ion characterized in that it is a cyclic or cage-like structure Silver halide photographic material.