JP2000056427A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having higher sensitivity without using cyanide ions by incorporating a metallic complex having one or more specified compds. as ligands into emulsion. SOLUTION: The silver halide photographic sensitive material contains a complex having an imidazole deriv. of the formula as a ligand in emulsion. In the formula, R1-R4 may be the same or different and are each a substituent selected from H, alkyl, alkenyl, alkynyl, aryl, halogen, cyano, nitro, mercapto, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, acyloxy, sulfonyloxy, amino, etc., a carboxylic acid and its salt, a sulfonic acid and its salt, a phosphonic acid and its salt and R2 and R3 may form a satd. carbon ring, an arom. carbon ring or a heteroarom. ring by cyclization.

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, the present invention relates to a high-sensitivity silver halide photographic material using a dopant technique.

[0002]

2. Description of the Related Art As one of the techniques for modifying silver halide grains to improve the performance of silver halide photographic materials as expected, substances other than silver ions and halide ions are used.
There is a technology (doping technology) that incorporates (dopant). In particular, much research has been made on the doping technology of transition metal ions. It is generally accepted that transition metal ions can effectively change photographic performance when they are introduced into silver halide grains as a dopant, even if the added amount is very small.

In order to enhance the sensitivity of a silver halide emulsion, it has been known to dope a silver halide grain with a Group VIII metal complex having a cyanide ion as a ligand. JP-B-48-35373 discloses the hexacyano complex of iron, yellow blood salt and red blood salt, as dopants containing cyanide ions, but the effect of the present invention is related to the type of ligand. And only when iron ions are contained. Sho 49-14265 discloses, as a silver halide emulsion is sensitive in a high illuminance, in the following silver halide grain particle size 0.9 .mu.m, silver ions per mole 10 ^{- 6} mol to 10 ^-3 mol No. VIII metal compound is added during grain formation, and the emulsion is spectrally sensitized with a merocyanine dye. According to this technique, a highly sensitive emulsion can be obtained. JP-A-1-121844 discloses that a photosensitive silver halide grain in which one grain is composed of two or more different halogen compositions has a portion of the halogen composition having the smallest bandgap energy and one mole of silver halide in that portion. Disclosed is a high-sensitivity emulsion containing 10 ^-7 mol or more of divalent iron ions per one.

[0004] Complexes doped by the doping technique are:
Not only iron complexes but also a wide variety of metal complexes, the effects brought by them are not only high sensitization, but also improvement of reciprocity failure and high contrast. U.S. Pat. No. 2,448,060 discloses that an emulsion doped with a platinum or palladium trivalent complex having a halogen ion as a ligand sensitizes. US Patent 3,7
No. 90,390 discloses a silver halide emulsion containing a cyano complex of iron (II), iron (III) and cobalt (III) and containing a spectral sensitizing dye. U.S. Pat. No. 4,847,191 discloses silver halide grains formed in the presence of a rhodium (III) complex having 3, 4, 5 or 6 cyano ligands. These patents report a reduction in high intensity failure with these dopants. European Patent 03
Nos. 36425 and 0336426, and JP-A-2-20853 and JP-A-2-20854,
Rhenium, ruthenium having more than one cyano ligand,
Osmium or iridium doped silver halide emulsions are disclosed. These documents describe that the sensitivity and the gradation stability over time are improved, and that low light failure is improved. EP 0 336 427 and JP-A-2-20852 disclose halogenation using hexacoordinate vanadium, chromium, manganese, iron, ruthenium, osmium, rhenium and iridium complexes containing a nitrosyl or thionitrosyl ligand. A silver emulsion is described which provides an improvement in low light reciprocity failure without reducing medium light sensitivity. In addition, European Patent 03
No. 36689 and JP-A-2-20855 disclose a hexacoordinate rhenium complex whose halogen is halogen,
A dopant based on a complex using nitrosyl, thionitrosyl, cyan, water, and thiocyan is disclosed. Japanese Patent Application Laid-Open No. 3-118535 discloses a transition metal in which one ligand of a six-coordinate metal complex is carbonyl. No. 3,118,536 discloses a six-coordinate metal complex.
Emulsions containing a transition metal complex in which two ligands are oxygen are disclosed as emulsions each having useful photographic performance. As dopants other than transition metal ions, emulsions doped with bismuth and lead ions are described in U.S. Pat. No. 3,690,888, and emulsions containing metal ions belonging to Groups 13 and 14 of the periodic table are described. JP-A-7-
No. 128778.

As disclosed in these examples, cyanide ions have been used most frequently as ligands of complexes doped into silver halide grains, but halide ions are also frequently used. For example, if M is any metal, [MCl
₆ ] Examples of doping with a complex having an ^n- structure include JP-A-63-184740 and JP-A-1-285941,
Hexachlororuthenium, hexachloroiridium, hexachlororhodium and hexachlororhenium described in JP-A-2-20852, JP-A-2-20855 and the like.

[0006] Nitrosyl, thionitrosyl, water and thiocyan are used as ligands of the complex to be doped in addition to cyanide and halide.
As described in 360,712, an example using a complex having a heterocyclic compound as a ligand as a dopant is also disclosed. However, an example in which a complex having an arbitrary imidazole derivative (L ') as a ligand is used as a dopant is described in the aforementioned U.S. Pat. No. 5,360,712 [Fe (CN) ₅ (L')].
^3- , [Ru (CN) ₅ (L ')] ^{3- and} only a complex such as [MCl ₅ (L')] or [MCl ₄ (L ') ₂ ] (M is There is no example of doping with any metal).

[0007] In order to obtain an emulsion having a high sensitivity, a silver halide emulsion is usually subjected to chemical sensitization. Among them, gold sensitization is a typical chemical sensitization. In a cyano complex-doped emulsion, for example, as described in JP-A-8-62761, cyanide ions released from the complex are adsorbed on the surface of silver halide grains, and gold ions added as a chemical sensitizer are added to the emulsion. It forms a gold cyano complex and inhibits the formation of a sensitizing nucleus by a gold sensitizer. Therefore, in order to sensitize gold with an emulsion using a cyano complex as a dopant, US Pat.
As described in JP-A-32,203 and European Patent 0508910, a cyano complex must be doped on the subsurface to keep the cyano group away from the surface of the silver halide grains. Further, in order to prevent the inhibition of the gold sensitization, JP-A-6-308
A method of adding ions such as zinc as disclosed in Japanese Patent No. 653 is also known.

As described above, the emulsion doped with a complex having a cyanide ion as a ligand brings about an improvement in photographic performance of sensitization, but also has a major drawback of inhibiting gold sensitization. In order to achieve both gold sensitization and gold sensitization, some other method must be taken. Also, even if the inhibition of gold sensitization by the cyano complex could be overcome, it is well known that compounds containing cyanide ions are highly toxic, so that a similar sensitized emulsion containing no cyanide ions was used. It is desired to obtain.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having a higher sensitivity without using cyanide ions.

[0010]

According to the present invention, there is provided a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein an imidazole derivative represented by the following general formula I is contained in the emulsion. It has been found that the above-mentioned problems can be achieved by using a silver halide photographic light-sensitive material characterized by containing a complex as a ligand. General formula I

[0011]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group , Halogen, cyano, nitro, mercapto, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, acyloxy, sulfonyloxy, amino, ammonium, carbonamido, sulfonamido, oxy Carbonylamino group, oxysulfonylamino group, ureido group, thioureido group, acyl group, oxycarbonyl group, carbamoyl group, thiocarbonyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group, sulfano Group, carboxylic acid and its salt Sulfonic acids and salts thereof, represent a substituent selected from phosphonic acids and salts thereof. Also, where R ₂
And R ₃ may be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring.

In order to achieve the above object, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a compound doped into silver halide grains contained in the emulsion is used. It is preferable to use a silver halide photographic material characterized by being a metal complex represented by the following general formula II. General formula II

[0014]

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In the formula, M represents any metal ion, L is a compound represented by the above general formula I, X is a halogen ion, n is 3, 4 or 5, m is -5, -4, -3, -2, -1,
0, +1 or +2.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Cyanide ions in a sensitizing dopant are ligands necessary for providing a shallow electron trap by a Coulomb field in silver halide grains. Aromatic heterocyclic compounds having the effect of providing electrons back from one of the t _2g orbitals of the electron-filled metal to the free orbital of the ligand have the same effect as cyanide ions Expected. Above all, imidazole was considered to be an anion by deprotonating the 1-position H atom, and even in this anionized state, it did not have as high a crosslinking ligand as pyrazole, so it was considered to be a suitable ligand for the purpose. .

In the present invention, the complex represented by the general formula II is used. In the general formula II, the central metal M is more preferably a metal ion selected from ruthenium, titanium, manganese, platinum, and tin. Preferably, especially in these complexes, n = 4 and X = Cl-.

In the above general formula I used as the ligand of the complex in the present invention, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, a substituted or unsubstituted alkyl group (methyl group, ethyl group, n -Propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, t-octyl, isodecyl, isostearyl, dodecyloxypropyl , Trifluoromethyl group, methanesulfonylaminomethyl group, etc.), alkenyl group, alkynyl group, aralkyl group, cycloalkyl group (cyclohexyl group, 4-t-butylcyclohexyl group, etc.), substituted or unsubstituted aryl group
(Phenyl, p-tolyl, p-anisyl, p-chlorophenyl, 4-t-butylphenyl, 2,4-di-t-aminophenyl, etc.), halogen (fluorine, chlorine, bromine, iodine) ), Cyano group, nitro group, mercapto group, hydroxy group, alkoxy group (methoxy group, butoxy group, methoxyethoxy group, dodecyloxy group, 2-ethylhexyloxy group, etc.), aryloxy group (phenoxy group, p-tolyloxy group , P-chlorophenoxy group, 4-t-butylphenoxy group, etc., alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, substituted or unsubstituted amino group
(Amino group, methylamino group, dimethylamino group, anilino group, N-methylanilino group, etc.), ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, substituted ureido group (3
-Methylureido, 3-phenylureido, 3,3-dibutylureido, etc., thioureido, acyl (formyl, acetyl, etc.), oxycarbonyl, substituted or unsubstituted carbamoyl (ethylcarbamoyl, dibutyi) Rucarbamoyl group, dodecyloxypropylcarbamoyl group, 3- (2,4-di-t-aminophenoxy) propylcarbamoyl group, piperidinocarbonyl group, morpholinocarbonyl group, etc.), thiocarbonyl group, thiocarbamoyl group, sulfonyl group, Sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group, sulfano group,
It is preferably a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof. Here, R ₂ and R ₃ may be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring. Among these, an alkyl group such as a methyl group, an ethyl group, and an n-propyl group is more preferable.

Specific examples of the complex of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[0020]

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[0021]

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[0022]

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The central metal of the metal complex preferably used in the present invention is ruthenium (III), titanium (IV), manganese
(II), platinum (IV) and tin (IV). In each complex, four Cl- bonds to the central metal, titanium
The (IV) complex, the platinum (IV) complex, and the tin (IV) complex are uncharged complex complexes. Each of these IV-valent complexes is an uncharged complex, but is soluble in water. Titanium (IV) complexes are highly deliquescent and are therefore desirably handled in non-aqueous solutions such as alcohols. In order to increase the solubility of the uncharged complex in water, the charge of the central metal may be made to have a charge other than the IV valence, such as making the charge of the central metal have a valence of three, so that the complex molecule may have a charge. The ruthenium (III) complex and the manganese (II) complex are monovalent and divalent complexes, respectively, and these charged complex molecules are completely dissociated from the counter ion in the aqueous solution and form an anion. Alternatively, the counterion is not important for photographic performance because it exists in the form of a cation. When the complex molecule becomes an anion and forms a salt with the cation, the counter cation is a sodium ion, potassium ion, rubidium ion, cesium which is easily dissolved in water and is suitable for the precipitation operation of the silver halide emulsion. Alkali metal ion such as ion, ammonium ion, the following general formula II
It is preferable to use an alkyl ammonium ion represented by I. General formula III

[0024]

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Wherein R ₅ , R ₆ , R ₇ and R ₈ are methyl groups,
It represents a substituent arbitrarily selected from an ethyl group, a propyl group, an iso-propyl group, and an n-butyl group. Among them, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n-butyl) in which R ₅ , R ₆ , R ₇ and R ₈ are all the same substituents
Ammonium ions are preferred. In addition, from the viewpoint of convenience in synthesizing the complex, it is also preferable to use, as a counter cation, an imidazolium cation in which an H ⁺ ion is added to the imine portion of the compound represented by the general formula I.

When the complex molecule becomes a cation and forms a salt with the anion, the counter anion is a halogen ion, a nitrate ion, a peroxide ion, which is easily dissolved in water and is suitable for the precipitation operation of a silver halide emulsion. Chlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylborate ion, hexafluorosilicate ion,
It is preferable to use trifluoromethanesulfonic acid or the like. When a counter anion such as a cyano ion, a thiocyano ion, a nitrite ion, or an oxalate ion having a strong coordination is used, a ligand exchange reaction with a halogen ion used as a ligand of the complex may occur. The use of these anions is not preferred because it is highly possible that the composition and structure of the complex of the present invention cannot be maintained.

The complex of the present invention can be synthesized by several methods. For example, a titanium complex and a tin complex can be obtained by reacting titanium tetrachloride or tin tetrachloride with an imidazole derivative under dry nitrogen while cooling. As a specific synthesis example, a method for synthesizing (bisimidazole) titanium tetrachloride and its tin complex is described in J. Gen. Chem. USSR 1967, 36, 1078.
And other titanium complexes and tin complexes can be synthesized by a similar method. Further, tetrachloromanganese complex, platinum complex, and ruthenium complex having imidazole as a ligand are respectively described in J. Inst. Chem. (India) 1989,
61, 129; Russ. J. Inorg. Chem. 1981, 26, 1179, Ino
rg. Chem. 1987, 26, 844, and the respective derivatives can be obtained in a similar manner.

The complex of the present invention may be added directly to the reaction solution at the time of forming silver halide grains, or may be added to an aqueous halide solution for forming silver halide grains, or to any other solution. It is preferable to add it to the reaction solution so that it is contained in the silver halide grains.
Further, these methods may be combined to dope silver halide grains. In the case of a titanium complex, it is most preferable to dissolve the complex in a small amount of a methanol solution or an ethanol solution separately from the silver nitrate aqueous solution and the halide aqueous solution, and to simultaneously add the silver nitrate aqueous solution and the halide aqueous solution to the reaction solution.

When the complex of the present invention is doped into silver halide grains, they may be uniformly present inside the grains, or may be incorporated in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188847. As disclosed in the gazette,
High concentration doping may be performed by the particle surface layer. Nos. 5,252,451 and 5,25.
As disclosed in US Pat. No. 6,530, the particle surface phase may be modified by physical ripening with doped fine particles. Further, a method in which fine particles doped with a complex are prepared, and the fine particles are added and physically ripened to dope the silver halide particles with the complex is also preferable. Further, the above doping methods may be used in combination.

The doping amount of the complex is suitably from 1 × 10 ⁻⁸ mol to 1 × 10 ⁻³ mol per mol of silver halide.
Preferably it is 1 × 10 ⁻⁷ or more and 1 × 10 ⁻⁴ mol or less.

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. be able to. Although the size of the silver halide grains is not limited, grains having a sphere equivalent diameter of 0.1 to 3 mm are preferred. The shape of the silver halide grains may be a regular crystal system (normal crystal grains), an irregular crystal system, or various shapes having one or more twin planes. Regular crystal systems include cubic, octahedral, dodecahedral, tetradecahedral, icosahedral and forty-octahedral. Irregular crystal forms include spherical and potato-like. Grains having one or more twin planes include hexagonal tabular grains and triangular tabular grains having two or three parallel twin planes. In the tabular grains, the grain size distribution is preferably monodispersed. The preparation of monodisperse tabular grains is described in JP-A-63-11928. Monodisperse hexagonal tabular grains are disclosed in
No. 151618. Circular monodisperse tabular grain emulsions are described in JP-A-1-131541. 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. European Patent 51
No. 4,742, A discloses a tabular grain emulsion having a grain size variation coefficient of 10% or less, prepared using a polyalkylene oxide block polymer.

The tabular grains whose major planes are (100) and (111) are known, and the technique of the present invention can be applied to both. The former is described in U.S. Pat. No. 4,063,951 and JP-A-5-281 regarding silver bromide.
No. 640, there is a description of silver chloride in European Patent 0
No. 534395A1 and US Pat. No. 5,264,337.
There is a description in each specification. The latter tabular grains are grains having various shapes having one or more twin planes described above,
Regarding silver chloride, U.S. Pat. Nos. 4,399,215, 4,983,508 and 5,183,732, JP-A-3-137632 and JP-A-3-11611.
No. 3 is described in each gazette.

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, there is a description. According to this publication, a specific high iodine phase is provided inside a tabular silver halide grain having an average grain diameter / grain thickness ratio of 2 or more, and the outside thereof is covered with a phase having a lower iodine content than the high iodine phase. Thereby, dislocations can be introduced. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in stability of a latent image, and a reduction in pressure fog can be obtained. According to the invention described in this publication,
Dislocations are mainly introduced at the edge of tabular grains. Also,
Tabular grains having dislocations introduced at the center are described in US Pat. No. 5,238,796. further,
Japanese Patent Application Laid-Open No. 4-348337 discloses a normal crystal grain having a dislocation therein, wherein the normal crystal grain is formed with silver chloride or silver chlorobromide epitaxy, and the epitaxy is subjected to physical ripening and It is disclosed that dislocations can be introduced by conversion by halogen and / or halogen. The introduction of such dislocations has the effect of increasing sensitivity and reducing pressure fog. Dislocation lines in silver halide grains are described, for example, in JF Hamilton, Photo.
Sci. Eng. 1967, 11, 57, T. Shinozawa, J. Soc. P
JAPAN, 1972, 35, 213, can be observed by a direct method using a transmission electron microscope at low temperature. That is, silver halide grains taken out with care not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for electron microscope observation, and the sample is cooled so as to prevent damage (printout) by electron beams. Observation is performed by a transmission method in a state where the state has been set. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate.
Using an electron microscope (200 kV or more with respect to a thickness of m) enables more clear observation. From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from a plane perpendicular to the main plane can be obtained. The present invention is effective 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 the silver halide solvent, water-soluble thiocyanates, ammonia, thioethers and thioureas can be used. Examples of the silver halide solvent include thiocyanates (U.S. Pat.
No. 448534 and No. 3320069).
Ammonia, thioether compound (US Pat.
Nos. 57, 3574628, 3704130, 4297439 and 4276347),
Thione compounds (JP-A Nos. 53-144319 and 53-143)
Nos. 82408 and 55-77737), amine compounds (described in JP-A-54-100717),
Thiourea derivatives (described in JP-A-55-2982), imidazoles (described in JP-A-54-100717) and substituted mercaptotetrazole (described in JP-A-57-2025)
No. 31).

The method for producing a silver halide emulsion is not particularly limited. 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), PhotographicEmul by GF Dufin
sion Chemistry (The Forcal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
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. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. 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 is preferably used.

Instead of adding a silver salt solution and a halogen solution to a reaction vessel, a method in which previously prepared fine particles are added to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. It is preferable to use Regarding this technology, JP-A-1-183644,
No. 1-183645, No. 2-44335, No. 2-4
No. 3,534, 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. Inside the particle (core)
So-called core / shell double-structured particles comprising an outer layer (shell portion) and triple-structured particles (JP-A-60-222)
No. 844) or a multi-layered particle having more than that. When a structure is provided inside the emulsion grain, not only the above-described wrapping structure but also a grain having a so-called junction structure can be produced. These examples are described in JP-A-58-108526, JP-A-59-16254 and JP-A-59-16254.
No. 133540, JP-B-58-24772 and EP 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 halogen composition or has a core-shell structure. In the case of a joint structure, it is naturally possible to combine silver halides. However, if it is possible to combine silver halide with a silver halide compound having no rock salt structure, such as silver rhodanate or silver carbonate, to form a joint grain, it is used. You may.

In the case of silver iodobromide particles having these structures, for example, in core-shell type particles, even if the silver iodide content in the core portion is high and the silver iodide content in the shell portion 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 a different halogen composition may be a clear boundary, or a mixed crystal may be formed due to a difference in composition to form an indefinite boundary. It may have a structural change. The silver halide emulsion used in the present invention may be subjected to a treatment for causing grain roundness (described in European Patent Nos. 0097727B1 and 0064412B1) or a surface modification treatment (German Patent 2).
No. 306447C2 and JP-A-60-2213
No. 20). The silver halide emulsion is preferably of a surface latent image type. However, JP-A-59-133
As disclosed in JP-A-542, an internal latent image type emulsion can also be used by selecting a developing solution or a developing condition. Also, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose.

[0038] Silver halide emulsions are usually spectrally sensitized. A methine dye is generally used 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 the rings usually 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. Further, a ring obtained by condensing a cyclic hydrocarbon ring or an aromatic hydrocarbon ring with a hetero ring can also be used. Examples of fused rings include indolenine ring, benzoindolenine ring, indole ring, benzoxadol ring,
Examples include a naphthoxazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a benzimidazole ring and a quinoline ring. 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-
Examples include a 2,4-dione ring, a rhodanine ring and a thiobarbituric acid ring.

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).

In the present invention, the sensitivity of silver halide grains to light having a wavelength of intrinsic absorption after chemical sensitization (intrinsic sensitivity) is improved. That is, the desensitization (specific desensitization by the sensitizing dye) caused by the adsorption of the spectral sensitizing dye for the light having a wavelength longer than about 450 nm to the surface of the silver halide grain,
It can be reduced by doping each complex of the present invention. The present invention has an effect that in addition to the effect of increasing the intrinsic sensitivity of silver halide, intrinsic desensitization by a sensitizing dye can be more effectively prevented.

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. Regarding the combination of a sensitizing dye and the above dye or substance, US Pat. Nos. 3,615,613 and 3,61.
Nos. 5,641, 3,617,295 and 3,6
It is described in each specification of JP-A No. 35,721.

The silver halide emulsion is generally used after chemical sensitization. As chemical sensitization, chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization), noble metal sensitization (eg, gold sensitization), and reduction sensitization are performed alone or in combination. In sulfur sensitization, an unstable sulfur compound is used as a sensitizer. For unstable sulfur compounds, see P.
Glafkides, Chimie et Physique Photographeque (Pa
ul Montel, 1987, 5th edition), Research Disclosu
re 307, 307105, edited by THJames, The Th
eory of the Photographic Process (published by Macmillan, 1
977, 4th edition), H. Frieser, Die Grundlagender Ph
otographischen Prozess mit Silver-halogeniden (Aka
demische 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- Ethyl rhodanine, 5-benzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine, diethyl rhodanine), phosphine sulfides (eg, trimethyl phosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2- Thiones, dipolysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates and elemental sulfur are included. 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-diethylphenylselenamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-) Tolyl selenophosphate, tri-n-butyl selenophosphate), selenoketones (eg, selenobenzophenone) isoselenocyanates, selenocarboxylic acids, selenoesters, and diacylselenides. 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;
295,462 and 1,396,696, JP-A-4-204640 and 4-271341.
And JP-A-4-330430 and JP-A-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 the 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 Nos. 49,484 and 5,049,485 can also be used.

In the reduction sensitization, a reducing compound is used as a sensitizer. For reducing compounds, see P. Grafkide
s, Chimie et Physique Photographique (Paul Monte
l Publishing, 1987, 5th edition), Research Disclosure 30
No. 7, 307105. 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,
Includes 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).

The chemical sensitization may be carried out by combining two or more kinds. As the combination, a combination of chalcogen sensitization and gold sensitization is particularly preferable. Further, reduction sensitization is preferably performed at the time of forming silver halide grains. The amount of sensitizer used is
It is determined by the type of silver halide grains generally used and the conditions of chemical sensitization. The amount of the chalcogen sensitizer used is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide,
It is preferably from ^{-7 to} 5 × 10 ^-3 mol. 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 6 to 11, preferably 7 to 10. Preferably, the pH is between 4 and 10. Temperature is 40 ~ 95 ℃
And more preferably 45 to 85 ° C.

The silver halide emulsion can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Examples of such compounds include azoles (eg, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted)), heterocyclic mercapto compounds Imidazoles (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, (especially, 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines), carboxyl group and sulfone group Such heterocyclic mercapto compounds having a water-soluble group such as thioketo compounds (eg, oxazolinethione), azaindenes (eg, tetraazaindenes (especially,
Hydroxy-substituted (1,3,3a, 7) tetraazaindenes)), benzenethiosulfonic acids and benzenesulfinic acid. Generally these compounds are known as antifoggants or stabilizers.

The timing of addition of the antifoggant or the stabilizer is as follows.
Usually, it is performed after chemical sensitization, but it can be selected during chemical sensitization or at a time before the start of chemical sensitization. That is, during the formation of silver halide emulsion grains, even during the addition of the silver salt solution or during the period from the addition to the start of chemical sensitization, during chemical sensitization (during the chemical sensitization time, preferably 50% from the start). More preferably within 20% of the time).

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 for recording 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 / R
L / 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 multilayer 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 similarly applied to X-ray photographic materials, black-and-white photographic materials, photographic materials for plate making, and photographic paper, in addition to color photographic materials.

Various additives of 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 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 page 24-28 Supersensitizer ~ page 649 right column 4 Brightening agent page 24 5 Anti-fogging agent, page 24-25 page 649 right column page 24, 31 Page Stabilizer 6 Light absorber, page 25-26 page 649 right column Filter dye, ~ 650 page left column UV absorber 7 Stain inhibitor 7 page 25 right column page 650 left column to right column 8 Dye image stabilizer page 25 Page 32 9 Hardener Page 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 Surfactant 13 Static inhibitor 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 gives stable photographic properties. N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) matansulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) also have fast and excellent curing rates.

Color photographic materials are available from Research Disclosure
Development can be carried out by a usual method described in 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. As a stabilizing treatment, a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 is exemplified instead of the washing step.

[0057]

EXAMPLES The present invention will be described below in more detail with reference to specific examples, but the present invention is not limited to these examples.

Example 1 Emulsion 1: silver chloride cubic emulsion A solution prepared by dissolving 25 g of deionized gelatin in 845 mL of an aqueous solution containing 4.5 g of sodium chloride was added to a 0.21 M silver nitrate aqueous solution (solution 1) while stirring at 50 ° C. ) 140 mL and 140 mL of a 0.21 M aqueous sodium chloride solution (solution 2) were quantitatively added for 10 minutes by a double jet method. 1
0 minutes later, 320 mL of a 2.2 M aqueous solution of silver nitrate (solution 3) and 320 mL of a 2.2 M aqueous solution of sodium chloride (solution 4) were further quantitatively added for 35 minutes by a double jet method. 5 minutes after the end of the addition,
After the temperature was lowered to 35 ° C., and the soluble salts were removed by a normal sedimentation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and sodium chloride and phenol were added.
Adjusted to 6.5. The obtained particles have a side length of 0.5 μm
Of silver chloride cubes.

"Emulsion 2: Cubic silver chloride emulsion doped with [Fe (CN) ₆ ] ^4- " (Comparative Example) In the preparation of Emulsion 1, Solution 4 was added at a concentration of 6.6 × 10 ^-7 M.
Emulsion 2 was prepared in the same manner as Emulsion 1 except that it contained [Fe (CN) ₆ ] ^4- .

"Emulsion 3-8: Cubic silver chloride emulsion doped with the titanium (IV) complex of the present invention" (the present invention) A solution obtained by adding 25 g of deionized gelatin to 845 mL of an aqueous solution containing 4.5 g of sodium chloride, While maintaining the temperature at 50 ° C. and stirring, 140 mL of a 0.21 M aqueous solution of silver nitrate (solution 5) and 140 mL of a 0.21 M aqueous sodium chloride solution (solution 6) were quantitatively added by a double jet method for 10 minutes. After 10 minutes, 320 mL of a 2.2 M silver nitrate aqueous solution (solution 7), 285 mL of a 2.2 M sodium chloride aqueous solution (solution 8), and 35 mL of an ethanol solution (solution 9) containing the complex of the present invention at a concentration of 3.9 mM were tripled. Further quantitative addition was performed for 35 minutes by the jet method. 5 minutes after the end of the addition,
After the temperature was lowered to 35 ° C., and the soluble salts were removed by a normal sedimentation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and sodium chloride and phenol were added.
Adjusted to 6.5. The obtained particles have a side length of 0.5 μm
Of silver chloride cubes.

To each of these emulsions, gelatin and sodium dodecylbenzenesulfonate were added, and gelatin, polymethyl methacrylate particles, 2,4-dichloro-
Coating was carried out together with a protective layer containing sodium 6-hydroxy-s-triazine at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 1 to 8, respectively.

The following sensitizing dye was added to the above emulsion at 3.8 × 1
^0-4 mol / mol Ag was added and spectral sensitization was performed.
And coated samples 9 to 16 and 17 to 24 were obtained.

[0063]

Embedded image

Emulsions 1 to 8 were added with 1.8 × 10 ^-2 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mol of silver, followed by addition of 2.5 × 10 ^-2 mol per mol of silver. ^-6 mol of sodium thiosulfate is added and optimally sensitized at 60 ° C.
Emulsions 9 to 16 were obtained. These emulsions were coated in the same manner as coating samples 1 to 8 to obtain coating samples 25 to 32. Emulsions 9 to 16 were subjected to spectral sensitization by adding the above sensitizing dye to 3.8 × 10 ⁻⁴ mol / mol Ag, and coating samples 33 to 48 were obtained in the same manner as coating samples 1 to 8.

[Emulsion 17: Silver chloride cubic emulsion] A silver chloride cubic emulsion was prepared in the same manner as in Emulsion 1 to obtain Emulsion 17.

"Emulsions 18 to 20: [Fe (CN) ₆ ] ^4- doped silver chloride cubic emulsion" (Comparative Example) In the preparation of Emulsion 1, 2.2 × 10 ^-7 ,
Emulsions 18, 19 and 20 were obtained by adding [Fe (CN) ₆ ] ^4- at a concentration of 2.2 × 10 ⁻⁶ and 2.2 × 10 ⁻⁵ M.

"Emulsions 21 to 25: Cubic silver chloride emulsion doped with the titanium complex of the present invention" (the present invention) In the preparation of the emulsion 8, the solution 9 (the [TiCl ₄ (2-MeBz
Im) The concentration of the titanium complex in ₂ ) ⁰
Emulsions 21 to 25 were obtained by preparing silver chloride cubic emulsions in the same manner as described above, using mM, 3.9 mM, 6.5 mM, 39 mM, and 390 mM.

To each of these emulsions, gelatin and sodium dodecylbenzenesulfonate were added, and gelatin, polymethyl methacrylate particles, 2,4-dichloro-
Coating was carried out together with a protective layer containing sodium 6-hydroxy-s-triazine at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 49 to 57, respectively.

The above sensitizing dye was added to the above emulsion at 3.8 × 1
Spectral sensitization was performed by adding ^0-4 mol / mol Ag, and coating samples 1-6
Was applied in the same manner as in Example 1 to obtain application samples 58 to 66 and 67 to 75.

After adding 1.8 × 10 ^-2 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mol of silver to emulsions 17 to 24, 2.5 × 10 4 mol per mol of silver was added. ^-6 mol of sodium thiosulfate is added and optimally sensitized at 60 ° C.
Emulsions 26-34 were obtained. These emulsions were coated in the same manner as for coating samples 1 to 8 to obtain coating samples 76 to 84. Also, emulsion
To 26 to 34, the above sensitizing dye was added to 3.8 × 10 ⁻⁴ mol / mol Ag to perform spectral sensitization, and coating samples 85 to 93 and 94 to 102 were obtained in the same manner as coating samples 1 to 8. .

These samples were subjected to sensitometric exposure.
(10 seconds or 10 ^-3 seconds) through an optical wedge, developed with a developer 1 having the following formulation at 20 ° C. for 5 minutes, stopped, fixed, washed with water, dried by a conventional method, The concentration was measured.
Fog was determined from the minimum optical density of the sample, and sensitivity was expressed as the logarithm of the amount of exposure required to obtain an optical density of fog +0.1, and was expressed as a relative value with the value for the type sample being 100. Table 1 shows that each of the coated samples 1 to 8 (spectral sensitizing dye blank sample) and the coated samples 9 to 16 (samples to which the spectral sensitizing dye was added) were exposed at a wavelength at which the intrinsic absorption of silver halide was observed. The relative sensitivities at the time of exposure and the relative sensitivities when each of the coated samples 17 to 24 (samples to which the spectral sensitizing dye was added) were exposed to a wavelength having an absorption of the spectral sensitizing dye were shown.
Table 2 shows coated samples 25 to 32 (spectral sensitizing dye blank samples)
And the coated samples 33 to 40 (samples to which the spectral sensitizing dye was added) were exposed to light at a wavelength at which the intrinsic absorption of silver halide was observed, and the coated samples 41 to 48 (spectral sensitizing dyes) ) Were exposed to light having a wavelength at which the spectral sensitizing dye had absorption. Tables 3 and 4 show the relative sensitivities of the emulsions in which the amount of the dopant was changed. Table 3 shows that each of the coated samples 49 to 57 (spectral sensitizing dye blank sample) and the coated samples 58 to 66 (samples to which the spectral sensitizing dye was added) were exposed at a wavelength at which the intrinsic absorption of silver halide was observed. The relative sensitivities at the time of exposure and the relative sensitivities when each of the coated samples 67 to 75 (samples to which the spectral sensitizing dye was added) were exposed at a wavelength at which the spectral sensitizing dye had absorption were shown. Table 4 shows that coated samples 76 to 84 (spectral sensitizing dye blank sample) and coated samples 85 to 93 (samples to which the spectral sensitizing dye was added) were exposed to light at a wavelength at which the intrinsic absorption of silver halide was observed. Relative sensitivity at the time, and coated samples 94-10
The relative sensitivity when each sample of Sample 2 (sample to which the spectral sensitizing dye was added) was exposed at a wavelength at which the spectral sensitizing dye had absorption was shown. Here, coating samples 9 to 16 and coating sample 1 in Table 1 were used.
7 to 24, coated samples 33 to 40 and coated samples 41 to 4 in Table 2
8. Coating samples 58 to 66 and coating samples 67 to 75 in Table 3 and coating samples 85 to 93 and coating samples 94 to 102 in Table 4 are the same samples for their corresponding emulsions, but were exposed at different wavelengths. , Two sample numbers were assigned to the same sample.

Developer 1 Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g NaCl 0.58 g Water is added to make 1 liter, and the pH is adjusted to 9.6.

[0073]

[Table 1]

[0074]

[Table 2]

Table 1 shows, as comparative examples, the relative sensitivities of an emulsion obtained by doping silver halide grains with [Fe (CN) ₆ ] ^4- and each unripened emulsion doped with each titanium complex of the present invention. . The doping concentration of each emulsion was 3 × 10 5 per mol of silver.
^-7 mol. In the emulsion prepared under these conditions, even in the emulsion doped with the well-known sensitizing dopant [Fe (CN) ₆ ] ^4- , no obvious sensitization was observed due to the small amount of complex doping. On the other hand, the titanium complex of the present invention shows a clear sensitization when any of the imidazole derivatives is used as a ligand, and the effect of the sensitization is particularly large in a sample to which a spectral sensitizing dye is added. all right. The effect of sensitization depends on the type of substituent in the imidazole derivative, but the greatest effect was obtained with a complex having 2-methylbenzimidazole as a ligand.

Table 2 shows the relative sensitivities of the S-sensitized emulsions. When the emulsion doped with each titanium complex of the present invention was subjected to S sensitization, the effect of sensitization became smaller than that of the unripened emulsion. However, when compared to the emulsion doped with [Fe (CN) ₆ ] ^4- , which had an effect of sensitization by performing S sensitization, most of the emulsions doped with the Ti complex had [Fe (CN) ⁴ ₆ ] Sensitivity higher than that of ^4- doped emulsion was observed.

[0077]

[Table 3]

[0078]

[Table 4]

From Tables 1 and 2, it is considered that the effect of sensitization is the greatest. Using [TiCl ₄ (2-MeBzIm) ₂ ] ⁰ , the dope concentration of the emulsion was changed and the relative sensitivity of the unripened emulsion was changed to [ Fe (C
N) ₆ ] ^4- doped emulsion (Table 3). [T] of the present invention
iCl ₄ (2-MeBzIm) ₂ ] ⁰ in the doped emulsion in each case [Fe (C
N) ₆ ] The sensitivity was significantly improved compared to the ^4- doped emulsion. In the case of this Ti complex, the sensitivity became maximum when the doping amount was 3 × 10 ⁻⁷ mol per mol of silver. The effect of sensitization was greater when the spectral sensitizing dye was added, and the greatest increase in sensitivity was exhibited particularly when exposure was performed at the absorption wavelength of the spectral sensitizing dye. In contrast, in the emulsion doped with [Fe (CN) ₆ ] ^4- , when exposed at the intrinsic absorption wavelength of silver halide, the internal sensitivity increases as the doping amount of the Fe complex increases, and the grain size increases. The sensitivity at the surface is reduced and the Ti
The emulsion was not so sensitive as to be doped with the complex. When exposure was performed at the absorption wavelength of the spectral sensitizing dye, the loss of surface sensitivity was smaller and the sensitivity increased as the doping concentration increased. It did not reach the emulsion. On the other hand, Table 4 shows the relative sensitivities when these emulsions were subjected to S sensitization. Again, in the case of the emulsions doped with Ti complex, a clear effect appeared when the spectral sensitizing dye was added. The effect of sensitization was large when exposed at an absorption wavelength of, and the greatest effect was obtained when doped at 5 × 10 ⁻⁷ mol per mol of silver. The sensitivity of these emulsions was greater than that of the emulsion doped with [Fe (CN) ₆ ] ^4- complex at any doping amount.

A silver chloride emulsion doped with a ruthenium complex and a manganese complex was also prepared in the same manner as the titanium complex shown above. However, the emulsion doped with the ruthenium complex became desensitized and became a hard emulsion. The resulting emulsion showed only desensitization.

Example 2 "Emulsion 35, 51, 57; Preparation of silver bromide cubic emulsion sample" 870
36 mL of deionized gelatin and 0.25 g of potassium bromide were added to and dissolved in mL of water. 36 mL of 0.088 M silver nitrate aqueous solution (solution 10) was stirred into this aqueous gelatin solution maintained at 75 ° C.
And 36 mL of 0.088 M aqueous potassium bromide solution (Solution 11) were added quantitatively by the double jet method for 10 minutes, followed by Solution 6 and Solution 7
Were added by the double jet method in 7 minutes.
Then, start with 898 mL of a 0.82 M silver nitrate aqueous solution (Solution 12).
Increase the flow rate from a flow rate of 53 mL / min and add for 95 minutes,
At the same time, a 0.90 M aqueous potassium bromide solution (solution 13) was added with pBr of 4.66.
Was added while controlling so as to maintain the pH of the mixture. Five minutes after the completion of the addition, the temperature was lowered to 35 ° C., the soluble salts were removed by a normal sedimentation method, the temperature was raised again to 40 ° C., 50 g of gelatin was added and dissolved, and potassium bromide and phenol were further added. And adjusted to pH 6.5. The resulting grains were monodispersed silver bromide cubes having a side length of 0.5 mm.

"Emulsions 36 to 42: Cubic silver bromide emulsion doped with the manganese (II) complex of the present invention" (Invention) In the method for preparing Emulsion 35, the Mn (II) complex of the present invention was added to the solution 13 in 8.2. × 10 ⁻⁸ M, (emulsions 36 and 39), 8.2 × 10 ⁻⁷ M (emulsions 37 and 40 and 42), 8.2 × 10 ⁻⁶ M (emulsions 38 and 4)
Emulsions 36 to 42 were obtained in the same manner as in Emulsion 35 except that each of the emulsions was contained at the concentration of 1). The complex added to each emulsion is shown in Table 5.

"Emulsions 52 to 53: Ruthenium (III) of the present invention"
Complex Doped Silver Bromide Cubic Emulsion "(Invention) In the method for preparing Emulsion 51, solution 13 of Ru (III)
Except for each containing the complex at a concentration of 8.2 × 10 ^-7 M
Emulsions 52-53 were obtained in the same manner as Emulsion 51.

"Emulsions 58 to 62: Cubic silver bromide emulsion doped with the titanium (IV) complex of the present invention" (the present invention) In the method for preparing the emulsion 57, the Ti (IV) complex of the present invention was added to the solution 13 in 8.2. Emulsions 58-62 were prepared in the same manner as Emulsion 57, except that they were each contained at a concentration of × 10 ^-7 M.

To each of the emulsions 35 to 42, 51 to 53, and 57 to 62, gelatin and sodium dodecylbenzenesulfonate were added, and gelatin, polymethyl methacrylate particles, Coating was carried out together with a protective layer containing sodium 2,4-dichloro-6-hydroxy-s-triazine at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 103 to 110 and 151 to 153, respectively. These emulsions were subjected to spectral sensitization by adding 4.9 × 10 ⁻⁴ mol / mol Ag of the sensitizing dye of Example 1 and coated in the same manner as coating samples 103 to 110.
1-126, 154-159, 169-174 were obtained, respectively.

The above silver bromide emulsions 35 to 42, 51 to 53, 57 to 62
Then, 1.2 × 10 ^-4 mol of sodium thiosulfate per mol of silver was added thereto, and the mixture was optimally chemically sensitized at 60 ° C. These chemically sensitized emulsions were coated in the same manner as for the above coated samples 103 to 110 to obtain coated samples 127 to 134 and 160 to 162, respectively. In addition, these emulsions subjected to chemical sensitization were prepared in Example 1
Sensitizing dye of 4.9 × 10 ^-4 mol / mol Ag was added and subjected to spectral sensitization, coated in the same manner as coating samples 103 to 110, and coated sample.
135-150, 163-168, 175-180 were obtained, respectively.

These samples were subjected to sensitometric exposure.
(1 sec., 10 ^-3 sec.) Through an optical wedge, developed with a developer 2 having the following formulation, developed at 20 ° C. for 10 minutes, stopped, fixed, washed with water, dried by a conventional method, Was measured. Fog is determined by the minimum optical density of the sample, and sensitivity is fog + 0.
It was expressed as a logarithm of the amount of exposure necessary to obtain an optical density of 1, and was expressed as a relative value with the value for the type sample being 100. Tables 5 and 6 show the coating samples 103 to 110 containing the manganese complex.
(Spectral sensitizing dye blank sample) and coated samples 111 to 118
Relative sensitivity when each sample (sample to which spectral sensitizing dye was added) was exposed at a wavelength at which the intrinsic absorption of silver halide was observed,
And the relative sensitivity when each of the coated samples 119 to 126 (samples to which the spectral sensitizing dye was added) was exposed to a wavelength having the absorption of the spectral sensitizing dye, and the coated samples 127 to 134 (chemical sensitized). Blank sample) and coated sample
135-142 (samples to which chemically sensitized spectral sensitizing dyes were added), and the relative sensitivity when each sample was exposed at a wavelength at which the intrinsic absorption of silver halide was observed, and the coated samples 143-150 (chemical samples) The relative sensitivities when each sample of the sensitized spectral sensitizing dye was exposed to a wavelength having an absorption of the spectral sensitizing dye were shown. Table 7 shows the intrinsic absorption of silver halide in each of the coated samples 151 to 153 containing the ruthenium complex (spectral sensitizing dye blank sample) and the coated samples 154 to 156 (samples to which the spectral sensitizing dye was added). The relative sensitivity when exposed at the wavelength, and the relative sensitivity when exposed to each of the coated samples 157 to 159 (samples to which the spectral sensitizing dye was added) at a wavelength at which the spectral sensitizing dye had absorption, and Sample 160-1
Wavelength at which intrinsic absorption of silver halide is observed in each of 62 (chemically sensitized spectral sensitizing dye blank sample) and coated samples 163 to 165 (chemically sensitized and spectral sensitizing dye added sample) And the relative sensitivity when exposed, and coating sample 166-1
The relative sensitivities when 68 samples (samples subjected to chemical sensitization and added with spectral sensitizing dye) were exposed to light having a wavelength at which the spectral sensitizing dye had absorption were shown. Table 8 shows the relative sensitivities of the coated samples 169 to 174 containing titanium complex (samples to which the spectral sensitizing dye was added) when the sample was exposed to light having a wavelength at which the spectral sensitizing dye had absorption. The relative sensitivities when each sample of 〜180 (a sample to which a chemical sensitization was applied and a spectral sensitizing dye was added) was exposed at a wavelength at which the spectral sensitizing dye had absorption were shown. In each table, there are samples having the same sample numbered with two sample numbers. However, since each sample was exposed at a different wavelength, two different sample numbers were assigned to the same sample. Numbered.

Developer 2 Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.0 g Water was added to make 1 liter, and the pH was adjusted to 9.6.

[0089]

[Table 5]

[0090]

[Table 6]

Tables 5 and 6 show the relative sensitivities of the silver bromide cubic emulsions doped with each manganese complex. Imidazole, 2-methylimidazole, and 2-propylimidazole were used as ligands of the manganese complex. In any of the emulsions doped with any of the complexes, almost no change in sensitivity was observed without the addition of the dye, whereas the addition of the spectral sensitizing dye increased the sensitivity. This tendency is particularly evident in the chemically sensitized samples. Although it is difficult to find a clear correlation between the amount of complex added and the sensitivity, the sensitivity tends to be higher when the doping amount is large for almost any complex.

[0092]

[Table 7]

The emulsion doped with the ruthenium complex has the same tendency as the emulsion doped with the manganese complex.
The emulsion to which the spectral sensitizing dye has been added shows clear sensitization. However, there was no difference in the magnitude of the effect of sensitization between the unripened emulsion and the chemically sensitized emulsion.

[0094]

[Table 8]

A silver bromide cubic emulsion doped with a titanium complex has a small internal sensitivity, and the sensitivity on the grain surface tends to be low in an unripened emulsion. Therefore, there was no tendency to increase the sensitivity, although there were some dopants that were desensitized when exposed at the intrinsic absorption wavelength of silver halide. Table 8 shows the relative sensitivity when a spectral sensitizing dye was added and exposure was performed at the absorption wavelength of the dye. Even when exposed at the absorption wavelength of the spectral sensitizing dye, the unripened emulsion tends to desensitize due to its internal sensitivity, but the chemically sensitized emulsion has a higher surface sensitivity than the emulsion without dopant. As a result, a highly sensitive emulsion was obtained in any of the emulsions doped with any of the titanium complexes.

Example 3 "Emulsion 69: Preparation of a sample of silver bromide octahedral emulsion" 36 g of deionized gelatin and 0.25 g of potassium bromide were added to and dissolved in 870 mL of water. While stirring this aqueous gelatin solution maintained at 75 ° C, 36 mL of 0.088 M aqueous silver nitrate solution (solution 14) and 0.08 M
36 mL of an 8 M aqueous potassium bromide solution (solution 15) was added quantitatively by the double jet method for 10 minutes, and then each of solution 6 and solution 7 was added.
176 mL was added by the double jet method for 7 minutes. Then, add 898 mL of 0.82 M silver nitrate aqueous solution (Solution 16) and 0.53 mL
The addition was carried out for 95 minutes at an accelerated flow rate from a flow rate of / min while simultaneously adding a 0.90 M aqueous potassium bromide solution (solution 17) while controlling the pBr at 2.93. Five minutes after the completion of the addition, the temperature was lowered to 35 ° C, the soluble salts were removed by a usual precipitation method, the temperature was raised again to 40 ° C, 50 g gelatin was added and dissolved, and potassium bromide and phenol were further added. Add,
The pH was adjusted to 6.5. The resulting particles have a sphere equivalent diameter.
It was a 0.5 mm monodispersed silver bromide octahedron.

"Emulsion 70-75: Mn (II) complex of the present invention, Ti (I
V) Complex-doped silver bromide octahedral emulsion "(Invention) In the method for preparing Emulsion 69, the Mn (II) complex or Ti (IV) complex of the present invention was added to the solution 17 at a concentration of 8.2 × 10 ^-7 M. Prepared in the same manner as Emulsion 69, except that
You got 75.

Gelatin and sodium dodecylbenzenesulfonate were added to these emulsions 69 to 75, respectively, and the mixture was coated on a triacetyl cellulose film support having an undercoat layer.
Coating was carried out together with a protective layer containing gelatin, polymethyl methacrylate particles and sodium 2,4-dichloro-6-hydroxy-s-triazine at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 181 to 187. These emulsions were subjected to spectral sensitization by adding the sensitizing dye of Example 1 to 4.9 × 10 ⁻⁴ mol / mol Ag, and coated in the same manner as coating samples 181 to 187. I got

The above silver bromide emulsions 69 to 75 were added per mole of silver.
8.0 × 10 ^-6 mol of sodium thiosulfate, 9.6 × 10 ^-6 mol of chloroauric acid and 3.4 × 10 ^-4 mol of potassium thiocyanate were added, and the mixture was optimally chemically sensitized at 60 ° C. These chemically sensitized emulsions were coated in the same manner as the above-mentioned coating samples 181 to 187 to obtain coating samples 202 to 208, respectively. The sensitizing dye of Example 1 was added to these chemically sensitized emulsions by 4.9.
× 10 ⁻⁴ mol / mol Ag was added and spectral sensitization was performed.
Coating samples 209 to 222 were obtained in the same manner as that of Nos. 187.

These samples were exposed to light for sensitometry.
(1 second, 10 ^-3 seconds) through an optical wedge,
After developing at 20 ° C. for 10 minutes with the developer 2, the film was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured. Fog is determined by the minimum optical density of the sample, and sensitivity is fog +0.1
The optical density was expressed as a logarithm of the amount of exposure necessary to obtain the optical density, and was expressed as a relative value with the value for the type sample being 100. Table 9 shows that each of the coated samples 181 to 187 (spectral sensitizing dye blank sample) and the coated samples 188 to 194 (sample to which the spectral sensitizing dye was added) were exposed at a wavelength at which the intrinsic absorption of silver halide was observed. Relative sensitivity at the time, and coating sample 195-201
The relative sensitivities when each sample of (Spectral sensitizing dye was added) was exposed to a wavelength having absorption of the spectral sensitizing dye are shown. Table 10 shows coated samples 202 to 208 (chemically sensitized). Relative sensitivity when each sample of spectral sensitizing dye blank sample and coated sample 209 to 215 (sample to which chemically sensitized spectral sensitizing dye was added) was exposed at a wavelength at which intrinsic absorption of silver halide was observed. , And the coated samples 216 to 222 (samples to which the chemically sensitized spectral sensitizing dye was added) show the relative sensitivities when each sample was exposed to light having a wavelength at which the spectral sensitizing dye had absorption. In each table, there are samples having the same sample numbered with two sample numbers. However, since each sample was exposed at a different wavelength, two different sample numbers were assigned to the same sample. Numbered.

[0101]

[Table 9]

[0102]

[Table 10]

In the case of the octahedral silver bromide emulsion, the effect of sensitization was not observed without adding a dye in each of the dope emulsions, i.e., unripened emulsions (Table 9) and chemically sensitized emulsions (Table 10). Was. [MnC
l ₄ (2-proIm) ₂ ] ^2- had the least effect of sensitization in the cubic emulsion, but the manganese complex showed the greatest effect in this silver bromide octahedral emulsion. Among the titanium complexes, the complex [TiCl ₄ (BzIm) ₂ ] ⁰ having benzimidazole as a ligand had the largest effect of sensitization.

Example 4 "Emulsions 76-82; octahedral silver bromide emulsion (2)" The emulsion obtained in Example 3 was optimally chemically sensitized and spectrally sensitized. The emulsion was used as an emulsion for the third layer of the light-sensitive material of Sample 201 of Example 2 of Example No. 146237, and was subjected to the same processing as in the example of JP-A-Hei-Hei.

Example 5 "Emulsion 83-89; silver bromide octahedral emulsion (3)" The emulsion obtained in Example 3 was optimally chemically sensitized and spectrally sensitized. The emulsion was used as an emulsion for the third layer of the light-sensitive material of Sample 110 of Example 1 of No. 20462, and was subjected to the same processing as in the example of the above-mentioned JP-A-Hei-Hei.

[0106]

The present invention is based on the finding that when a complex having an imidazole derivative as a ligand is contained in a silver halide emulsion, advantages in photographic properties are obtained.
In particular, when a tetrachloro complex having two molecules of an imidazole derivative as a ligand is doped into silver halide grains, an undoped emulsion or hexacyanoiron (II)
A silver halide light-sensitive material having high sensitivity and low intrinsic desensitization can be obtained as compared with an emulsion doped with a complex.

Claims (6)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, a metal complex having at least one compound represented by the following general formula I as a ligand (provided that the compound is a metal complex). Silver halide photographic light-sensitive material, characterized in that the emulsion contains a complex having iron and ruthenium as central metals). Formula I In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, a halogen, Cyano group, nitro group, mercapto group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group , Oxysulfonylamino group, ureido group, thioureido group, acyl group, oxycarbonyl group, carbamoyl group,
A substituent selected from a thiocarbonyl group, a thiocarbamoyl group, a sulfonyl group, a sulfinyl group, an oxysulfonyl group, a sulfamoyl group, a sulfino group, a sulfano group, a carboxylic acid and a salt thereof, a sulfonic acid and a salt thereof, and a phosphonic acid and a salt thereof. Represent. Here, R ₂ and R ₃ may be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein silver halide grains contained in the emulsion contain the metal complex. Item 6. The silver halide photographic material according to Item 1. 3. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide grains contained in the emulsion contain a compound represented by the following general formula II. A silver halide photographic light-sensitive material characterized by the following. Formula II In the formula, M represents any metal ion, L is a compound represented by the general formula I, X is a halogen ion, n is 3, 4 or 5, m is -5, -4, -3,- 2, -1, 0, +1 or +2. 4. The silver halide photographic material according to claim 3, wherein in the general formula II, M is a metal ion selected from ruthenium, titanium, manganese, platinum and tin. 5. A compound of the formula I wherein at least one of R ₁ , R ₂ and R ₃ is a methyl group, an ethyl group, n- or i-
2. The silver halide photographic material according to claim 1, which is a propyl group. 6. The silver halide light-sensitive material according to claim 3, wherein X = Cl ⁻ in the general formula II.