JP2000035626A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic sensitive material higher in sensitivity by incorporating a specified compound in an emulsion. SOLUTION: The silver halide photographic sensitive material provided on a support with at least one of emulsion layers containing the compound represented by formula I in which M is an optional metal atom or ion; L is a compound bonded to M and represented by formula II, wherein (x) is an integer of 1-4; (n) is an integer of -6 to +5; and L1 is an optional group bonded to M and L1 may be plural different chemical groups, when (x) is 1 or 2, and each of R1-R4 is a hydrogen atom or an alkenyl group or the like, and R2 and R3 may be bonded to each other to form a saturated carbon ring or aromatic ring or hetero ring. The silver halide in the emulsion layer to be used is not especially limited, and silver chloride and silver bromide and the like can be generally exemplified and it is preferred to use a grain size of >=0.1 μm.

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 four-coordinate complex having an imidazole derivative as a ligand.

[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, a substance other than silver ions and halide ions is used for the silver halide grains. Techniques for incorporating are well known. This technique is referred to as "doping technique", and a substance incorporated into silver halide grains is referred to as "dopant", and incorporating a dopant into a silver halide grain is referred to as "doping". 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 incorporated as a dopant into silver halide grains, even if the added amount is very small.

[0003] To increase the sensitivity of silver halide emulsions
Represents a group VIII metal complex having a cyanide ion as a ligand.
Techniques for doping silver halide grains have been known.
JP-B-48-35373 contains cyanide ions.
Yellow blood salt which is a hexacyano complex of iron as a dopant
Although disclosed for red blood salts, the effect of the present invention is coordination.
Regardless of the type of element, only if it contains iron ions
Can be In Japanese Patent Publication No. 49-14265, high illuminance
Silver halide emulsion with high sensitivity
In silver halide grains of 0.9 μm or less, silver ions
10 per mole ^-610 from mole^-3Group VIII metallization of moles
Compound during grain formation and spectral enhancement with merocyanine dye
Disclosed a sensitive emulsion, and according to this technique,
An emulsion is obtained. JP-A-5-66511, U.S. Pat.
No. 5,132,203 discloses hexacyanoiron (I
I) Doping the complex into the subsurface layer of silver halide grains
Indicates that a highly sensitive emulsion can be obtained. Also,
JP-A-2-20853 discloses that cyanide ions are provided.
Rhenium, ruthenium, osmium, iridium as ligands
Halo is highly sensitive when silver complex is doped into silver iodochloride
It is disclosed that a silver gemide emulsion can be obtained. on the other hand,
JP-A-1-121844 discloses that one particle is different.
Photosensitive halogen composed of two or more halogen compositions
Halo with the smallest bandgap energy of silver halide grains
1 mole of silver halide in that portion
R10^-7High sensitivity containing more than mole of divalent iron ions
An emulsion is disclosed.

In order to obtain a highly sensitive emulsion by the doping technique, a hexacyanoiron (II) complex or hexacyanoruthenium
Group VIII metal complexes such as (II) complexes are often used as dopants, but many other complexes using metal ions are also used as dopants. It covers a wide range of areas, including reciprocity failure improvement and high contrast. US Patent No. 2,4
No. 48,060 discloses that an emulsion doped with a platinum or palladium III-valent complex having a halogen ion as a ligand sensitizes. U.S. Pat. No. 3,790,39
No. 0 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 describes 3,
Rhodium with 4, 5 or 6 cyano ligands (II
I) Discloses silver halide grains formed in the presence of the complex. These patents show that dopants reduce high intensity failure. European Patent 0336425
No. 3,336,426 and JP-A No. 2-20.
Nos. 853 and 2-20854 disclose silver halide emulsions doped with rhenium, ruthenium, osmium or iridium having four or more cyano ligands. 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. As dopants other than transition metal ions, emulsions doped with bismuth and lead ions are described in U.S. Pat. No. 3,690,888. It is described in JP-A-7-128778.

As described above, metal complex doping of silver halide grains causes various changes in photographic characteristics, but most of metal complexes doped to silver halide grains until now have six-coordinate octahedral coordination. It was a complex with a structure. This is J.
Phys .: Condens. Matter 9 (1997) 3227-3240 and many other literatures and patents, for example, a metal complex having a six-coordinate octahedral structure such as a hexacyanoiron (II) complex Is doped into the silver halide grains, the (AgX ₆ ) ^5- (X ⁻ = halide ion) in the silver halide grains
Is a unit, and a part of the particles is replaced with a dopant. Therefore, a complex having a 6-coordinate octahedral structure having a similar structure to this unit has been considered to be suitable as a dopant. Examples in which a complex having a coordination structure other than a hexacoordinate octahedral structure is doped into silver halide grains are described in [PtCl ₄ ] ²⁻ and [PdCl ₄ ] ²⁻ in US Pat. No. 448,060, [Pt (CN) ₄ ] ^2- ,
Examples of doping with [Pd (CN) ₄ ] ²⁻ , [Ni (CN) ₄ ] ²⁻ are disclosed in JP-A-5-346633, [CoCl ₄ ] ²⁻ , [Co (CN)
₄ ] ^2- doped example is disclosed in JP-A-5-134344, and [Zn (CNO) ₄ ] ^2- doped is described in JP-A-4-30.
No. 5644, respectively. However, all of these four-coordinate complexes are compounds used as dopants as a series compound in a series of experiments using a complex having a six-coordinate octahedral structure as a dopant. No clear concept of doping the complex with the silver halide is shown, and it is presumed that the complex was used only from the viewpoint of the type of metal ion or ligand without considering the coordination structure. Other than those listed here, there is no known example in which a tetracoordinate complex is doped into silver halide grains.

For the ligand of the complex to be doped, not only cyanide ion but also many chemical species are used. Apart from cyanide ions, halogen ions are often used as ligands. For example, as an example in which M is an arbitrary metal and a complex having a structure of [MCl ₆ ] ^n- is doped, see JP-A-63-184740 and JP-A-Hei.
Nos. 285941 and 2-20852 and 2-2085
No. 5, each of hexachlororuthenium, hexachloroiridium, hexachlororhodium,
Hexachlororhenium is mentioned. European Patent 0336
No. 689 and JP-A-2-20855 disclose as a dopant a complex of a six-coordinate rhenium complex in which halogen, nitrosyl, thionitrosyl, cyan, water or thiocyan is used as the ligand. And
JP-A-3-118535 discloses a transition metal complex in which one ligand of a six-coordinate metal complex is carbonyl, and JP-A-3-118536 discloses two transition metal complexes of a six-coordinate metal complex. Emulsions containing therein a transition metal complex which is oxygen are disclosed as emulsions having useful photographic properties. Further, as disclosed in U.S. Pat. No. 5,360,712, an example is disclosed in which a complex having a heterocyclic compound as a ligand is used as a dopant.

However, any imidazole derivative
Examples of using a complex having (L ′) as a ligand as a dopant include [Fe (CN) ₅ (L ′)] ³⁻ and [Ru] described in the above-mentioned US Pat. No. 5,360,712. (CN) ₅ (L ')] ^3- only.
With a 6-cyano complex and a complex having a cyanide ion as a ligand, an emulsion having high sensitivity can be obtained, but as described in JP-A-8-62761,
Inhibits the formation of sensitizing nuclei by gold sensitizers. For this reason, in order to efficiently obtain a highly sensitive emulsion, it is desirable to use a complex having no cyanide ion, which is the same from the viewpoint of the toxicity of cyanide ion. As for complexes using imidazole derivatives as ligands without using cyanide ions as ligands, examples of not only 4-coordinate complexes but also 6-coordinate complexes used as dopants are not known.

[0008]

According to the present invention, the conventional 6
With the aim of removing the barrier of doping technology that only complexes having a coordinated octahedral structure have been used as dopants and providing more sensitive photographic photosensitive materials from a wider range of doping technologies, An object of the present invention is to obtain a silver halide photographic material having higher sensitivity by using a complex having a structure which has not been used as a dopant.

[0009]

The object of the present invention is to provide the following (1)
And (7) achieved by the silver halide photographic light-sensitive material.

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, characterized in that a compound represented by the following general formula I is contained in the emulsion: Photosensitive material. General formula I

[0011]

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In the formula, M represents any metal or metal ion, L is a compound represented by the following general formula II binding to M, x is 1, 2, 3, or 4, and n is -6 or more +5 Represents the following integers. Further, L ^I represents an optional chemical species that binds to M, when x is 1 or 2, L ^I may be a plurality of different species. General formula II

[0013]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, a halogen, a cyano group, a 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, thiocarbonyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group, sulfano group, carboxylic acid or a salt thereof,
It represents sulfonic acid or a salt thereof, phosphonic acid or a salt thereof. Here, R ₂ and R ₃ are closed to form a saturated carbocycle,
It may form an aromatic carbocyclic or heteroaromatic ring.

(2) In a silver halide photographic material having at least one silver halide emulsion layer on a support, silver halide grains contained in the emulsion contain a compound represented by the formula (I). (1) The silver halide photographic light-sensitive material as described in (1) above.

(3) In the general formula I, M is a metal selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, rhodium, palladium, silver, iridium, platinum, gold and tin. Or the silver halide photographic material as described in (1) or (2), which is a metal ion.

(4) In the compound represented by the general formula I, when x is 1, 2, or 3, at least one of L ^I is a halogen ion.
Or the silver halide photographic material according to (2).

(5) In the compound of the general formula I, M is Co, N
(4) The silver halide photographic material as described in (4) above, which is a metal ion selected from i and Cu.

(6) At least one of R ₁ , R ₂ and R ₃ in the compound of the general formula II is selected from a methyl group, an ethyl group, an n- and i-propyl group ( The silver halide photographic light-sensitive material according to 5).

(7) The silver halide photosensitive material as described in (6), wherein in the general formula I, L ^I = Cl ⁻ .

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Most of the complexes which have been used as dopants so far are complexes having a six-coordinate octahedral structure, and the complexes used as dopants in four-coordinate complexes also have a coordination structure. It is thought that it was used without being conscious. The fact that the tetracoordination complex can be used as a dopant for silver halide grains not only expands the range of choice of the dopant, but also expands the degree of freedom in designing an emulsion having desired photographic characteristics. .

Most of the complexes having a four-coordinate structure have a planar four-coordinate structure or a tetrahedral structure. Some complexes take other coordination structures, such as trigonal pyramids, but these are rare examples. So far, doping of silver halide grains has been disclosed,
Pt (II) complex, Pd (II) complex, Ni (II) complex, and (Co (CN)
₄ ] ^2- is a complex having a planar four-coordinate structure, and [CoCl ₄ ]
^2- and [Zn (CNO) ₄ ] ^2- are tetrahedral structure complexes. Plane 4
In a complex having a coordination structure, a metal ion is present at the center of a square, a rectangle, or a rhombus, and four ligands bonded to the metal ion are located at each vertex of each figure. Therefore, the metal ion and the four coordination atoms take a structure placed on the same plane (coordination plane). With this planar four-coordinate structure,
[AgX ₄ ] in the silver halide grains as if the [[AgX ₆ ] ^5- unit of the silver halide grains were replaced by the complex when the complex having a 6-coordinate octahedral structure was doped and incorporated into the grains. It is expected that by replacing ^3- as a unit with the complex, it will be incorporated into the particles.

On the other hand, in a tetracoordinate complex having a tetrahedral structure, no convenient unit can be found in the silver halide grains because it replaces the complex. For this reason, in order for a complex having this structure to be incorporated into silver halide grains, the complex itself needs to change to a coordination structure that matches the silver halide grain structure, but a complex having a tetrahedral structure In some, the coordination structure around the metal changes under certain conditions, and the original complex molecule changes to a planar tetracoordinate structure. If such a structural change can be caused during grain formation, it is expected that the [AgX ₄ ] ^3- unit and the complex can be replaced, and that the complex can be incorporated into silver halide grains. .

By appropriately changing the substituents in the molecule, the aromatic compound can be placed at the energy level at or near the intended position. on the other hand,
In a metal complex, the orbital of a metal interacts with the orbit of a compound or ion serving as a ligand to create a molecular orbital. Therefore, if a heterocyclic aromatic compound having a coordination site to a metal in the ring skeleton is used as a ligand of the complex, the energy level of the complex, particularly the energy level near the frontier orbital, is expected to be at the intended position. It is considered that the energy level can be set, and the energy level can be finely adjusted by selecting the type of the substituent in the heterocyclic compound as a ligand.

In the present invention, since the complex doped in the silver halide grains is substituted with [AgX ₄ ] ^3- , the ligand of the complex has a monovalent coordination having the same valence as the halogen ion. It is expected that the silver halide grains are more likely to be doped into silver halide grains. In imidazole and its derivatives, H ⁺ can be eliminated from NH in the molecule to become Im ⁻ , so that a complex using this as a ligand is more doped than a complex using another heterocyclic compound as a ligand. It is expected to be easy. In addition, imidazole, 2-
Comparing the electron-donating properties of methylimidazole, 2-ethylimidazole, and 2-propylimidazole to the metals, it can be seen that the electron-donating properties of the metals increase in the order described above. As described above, it is expected that imidazole and imidazole derivatives have a large effect on the molecular orbital of the complex molecule by changing the substituent.

Based on the above, specific examples of the complex of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[0027]

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[0028]

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In the present invention, a Cu (II) complex and a Ni (II) complex having a planar four-coordinate structure and a Co (I) complex having a tetrahedral structure are mainly used.
I) An experiment was performed using the complex. Among them, [CuCl ₂ (RI
m) ₂ ) ⁰ , (NiCl ₂ (R-Im) ₂ ) ⁰ , (CoCl ₂ (R-Im) ₂ ) ⁰ (RI
m = imidazole and an imidazole derivative represented by the general formula IV).

Each of the complexes of the present invention can be synthesized by several methods. For example, [CuCl ₂ (2-
MeIm) ₂ ) ⁰ , (NiCl ₂ (2-MeIm) ₂ ) ⁰ , (CoCl ₂ (2-MeIm)
m) ₂ ] ⁰ (2-MeIm = 2-methylimidazole)
J. Chem. Soc. (A) 1968,128, J. Chem. Soc. (A) 1967, 757
It is described in. In the present invention, the synthesis was carried out based on these methods with modification for each individual compound. [CoCl ₂ (thia) ₂ ] ⁰ (thia = thiazole) used as a comparative example is also described in J. Chem. Soc. (A) 1967,757.

[0031] Preferably the metal complex used in the present invention are both central metal II value, these metal ions Cl ^- but is a complex of two linked uncharged, the complex having a charge Can also be used. At this time, the complex molecule is completely dissociated from the counter ion in the aqueous solution, and exists in the form of an anion or a cation. Therefore, the counter ion is not important for photographic performance. When the complex molecule becomes an anion and forms a salt with the cation, the counter cation is 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. It is preferable to use an alkali metal ion such as an ion, an ammonium ion, or an alkyl ammonium ion represented by the following general formula V. General formula V

[0032]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ represent a substituent arbitrarily selected from a methyl group, an ethyl group, a propyl group, an isopropyl group and an n-butyl group. Of _{these, R 5, R 6, R} 7 and R ₈ are all equal substituent tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n- butyl) ammonium ion.

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

In the present invention, the complex was used as a ligand.
In the above general formula IV, R₁, R _Two, R_ThreeAnd R_Four
Is a hydrogen atom or a substituted or unsubstituted alkyl
(Methyl, ethyl, n-propyl, isopropyl
Group, n-butyl group, t-butyl group, hexyl group, octyl
Group, 2-ethylhexyl group, dodecyl group, hexadecyl
Group, t-octyl group, isodecyl group, isostearyl group,
Dodecyloxypropyl group, trifluoromethyl group,
Tansulfonylaminomethyl group), alkenyl group,
Rukinyl group, aralkyl group, cycloalkyl group (cyclo
Hexyl group, 4-t-butylcyclohexyl group, etc.)
Or an unsubstituted aryl group (phenyl group, p-tolyl group, p-
Anisyl group, p-chlorophenyl group, 4-t-butylphenyl
Group, 2,4-di-t-aminophenyl group, etc.), halogen (fluorine)
Element, chlorine, bromine, iodine), cyano group, nitro group, mel
Capto group, hydroxy group, alkoxy group (methoxy group,
Toxyl group, methoxyethoxy group, dodecyloxy group, 2-
Ethylhexyloxy group, etc.), aryloxy group (e.g.
Nonoxy group, p-tolyloxy group, p-chlorophenoxy group,
Alkylthio group, aryl, such as 4-t-butylphenoxy group
Thio group, acyloxy group, sulfonyloxy group, substitution
Or an unsubstituted amino group (amino group, methylamino group,
Methylamino group, anilino group, N-methylanilino group
Etc.), ammonium group, carbonamide group, sulfonamido
Group, oxycarbonylamino group, oxysulfonylua
Amino group, substituted ureido group (3-methylureido group,
Nylureido group, 3,3-dibutylureide group, etc.
Group, acyl group (formyl group, acetyl group, etc.)
Cicarbonyl group, substituted or unsubstituted carbamoyl group
(Ethyl carbamoyl group, dibutyl carbamoyl group,
Decyloxypropylcarbamoyl group, 3- (2,4-di-t-
Aminophenoxy) propylcarbamoyl group, piperidi
Carbonyl group, morpholinocarbonyl group, etc.), thioca
Rubonyl group, thiocarbamoyl group, sulfonyl group, sulf
Finyl group, oxysulfonyl group, sulfamoyl group,
Sulfino group, sulfano group, carboxylic acid or its
Salt, sulfonic acid or its salt, phosphonic acid or its salt
Can be used. And where R_TwoAnd R _ThreeIs ring closed
To form a saturated carbocyclic, aromatic carbocyclic or heteroaromatic ring
May be implemented. Among them, methyl group, ethyl group, n-
An alkyl group such as a propyl group is particularly preferred.

The four-coordination complex of the present invention is added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, or in other solutions. It is preferable to add the silver halide grains to the silver halide grains by adding them to the grain forming reaction solution. Further, these methods may be combined to dope silver halide grains.

When the four-coordination complex of the present invention is doped into silver halide grains, even if the silver halide grains are uniformly present inside the grains, JP-A-4-208936, JP-A-2-125245, and JP-A-3-188439. , A higher concentration of doping may be applied to the particle surface layer. See also U.S. Patent Nos. 5,252,451 and 5,256,530.
As disclosed in US Pat. No. 6,099,045, the surface phase of the particles 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 1 mole equivalent of silver halide.
1 × 10^-Ten1 x 10 or more ^-3Less than a mole is appropriate
Yes, preferably 1 × 10^-8More than 1 × 10^-FourLess than a mole
is there.

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 there are differences depending on the complex used as the dopant, the effect of sensitization can be obtained when grains having any of these halogen compositions are used as a host, and there is no general limitation on the halogen composition of the grains used in the emulsion. . The grain size of silver halide is
It is preferably at least 0.1 μm, more preferably 0.3 to 3 μm.

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 described in JP-A-63-151618. Circular monodisperse tabular grain emulsions are described in JP-A-1-131541. Also, JP-A-2-838 discloses that
An emulsion is disclosed in which 95% or more 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 monodisperse. EP 514 742 A discloses tabular grain emulsions prepared using a polyalkylene oxide block polymer and having a grain size variation coefficient of 10% or less.

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 US Pat. No. 4,063,951 and JP-A-5-28164 regarding silver bromide.
No. 0, EP 053 concerning silver chloride.
No. 4395A1 and US Pat. No. 5,264,337. The latter tabular grains are grains having various shapes having one or more twin planes. For silver chloride, US Pat. Nos. 4,399,215 and 4,983,508.
No. 5,183,732, JP-A-3-1376
Nos. 32 and 3-116113.

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 dislocations therein. The same publication produces silver chloride or silver chlorobromide epitaxy on the normal crystal grains, and the epitaxy is physically measured. It is disclosed that dislocations can be introduced by aging and / or conversion by 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. Sc.
i. Eng., 11, (1967) 57, T. Shinozawa, J. Soc. Pho
JAPAN, 35, (1972) 213, can be observed by a direct method using a transmission electron microscope at a 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 Monte
l Publisher, 1967), Photographic Emuls by GF Dufin
ion Chemistry (The Forcal Press, 1966), VL
Making and Coating Photographic E by Zelikman et al
mulsion (The Forcal Press, 1964) and the like. 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 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 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.

The silver halide emulsion is 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 (intrinsic desensitization due to the sensitizing dye) caused by the adsorption of the spectral sensitizing dye to the light having a wavelength longer than about 450 nm on the surface of the silver halide grain is reduced by doping the complex of the general formula I. I can do it. 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 (P
aul Montel, 1987, 5th edition), Research Disclos
ure 307, 307105, edited by THJames, The
Theory of the Photographic Process (Macmillan, 1977, 4th edition), H. Frieser, Die Grundlagen
der Photographischen Prozess mit Silver-halogenide
n (Akademische Verlags-geselbshaft, 1968). Examples of sulfur sensitizers 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 rhoda) Nin, 5-benzylidene-N-ethyl-rhodanine, diethylrhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2-thiones, dipolysulfides (examples) , Dimorpholine disulfide, cystine, hexathiocan-thione , Mercapto compounds (e.g., cysteine), include 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-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 800,958, British Patent 1,
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, telluropentathiol) Sodium 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 noble metal salts, see P. Grafkides, Chimie et.
Physique 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 reduction sensitization, a reducing compound is used as a sensitizer. For reducing compounds, see P. Grafkide
s, Chimie et Physique Photographique (Paul Mont
el company, 1987, 5th edition), Research Disclosure Magazine 3
07 volume 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 performed 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 to be used is generally 10 ^-8 to 10 ^-2 mol, preferably 10 ^{-7 to} 5 × 10 ^-3 mol, per mol of silver halide. The amount of the noble metal sensitizer used is 10 per mole of silver halide.
It is preferably from ^-7 to 10 ^-2 mol. There are no particular restrictions on the conditions for chemical sensitization. The pAg is from 6 to 11, preferably from 7 to 10. The pH is preferably from 4 to 10. The temperature is preferably 40-95 ° C,
More preferably, the temperature is 5 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 light-sensitive 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). Within the time, preferably within a time of up to 20%).

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, colorant For couplers, ultraviolet absorbers, anti-fading agents, dyes), photographic material supports and photographic material processing methods (eg, coating methods, exposure methods, development processing methods), Research Disclosure 176, 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 Page 24 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, pages 25 to 26, page 649, right column Filter dyes, page 650, left column, UV absorber 7 Stain inhibitor, page 25, right column, page 650, left column to right column 8 Dye image stabilizer 25, page 32 Page 9 Hardening agent Page 26 Page 651 Left column Page 32 10 Binder 26 Same as above Page 28 11 Plasticizer, lubricant 27 Page 650 Right column 12 Coating aid, Pages 26-27 Same as above Surfactant 13 Static inhibitor 27 Page Same as above 14 Color coupler page 25 Page 649 Page 31 ──── ────────────────────────────

As the gelatin hardener, for example, active halogen compounds (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.

The color photographic material is 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.

[0066]

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 adding 25 g of deionized gelatin to 845 ml of an aqueous solution containing 4.5 g of sodium chloride, and keeping the temperature at 50 ° C while stirring, 140 ml of a 0.21 M silver nitrate aqueous solution (solution 1) And 140 ml of a 0.21M aqueous sodium chloride solution (solution 2) were added quantitatively in 10 minutes by the double jet method. After 10 minutes, 320 ml of a 2.2 M silver nitrate aqueous solution (solution 3) and 2.2 ml
320 ml of an M sodium chloride aqueous solution (solution 4) was further added by a double jet method for 35 minutes. 5 minutes after the end of the addition,
After the temperature was lowered to 35 ° C and the soluble salts were removed by the ordinary sedimentation method, the temperature was raised again to 40 ° C, gelatin was added and dissolved, sodium chloride was further added, and the pH was adjusted to 6.5 with sodium hydroxide. It was adjusted to become. Obtained particles have side length
It was a 0.5 μm monodispersed silver chloride cube.

"Emulsions 2 to 5: Cubic silver chloride emulsion (1) doped with the four-coordinate complex of the present invention" (the present invention)
Except that it includes a concentration of 0 ^-6 M, to prepare an emulsion 2-5 obtained in the same manner as in 1. In this emulsion, the dopant is uniformly distributed throughout the silver halide grains, except for the fine grain portions which are nuclei.

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 by an extrusion method at a silver amount of 2 g / m ² to obtain coating samples 1 to 5, 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.
Coating was performed in the same manner as in Sample No. 5, and coating samples 6 to 10 and 11 to 15 were obtained.

[0070]

Embedded image

The samples were exposed to sensitometric exposure (1
(0 second) was given through an optical wedge, developed with a developer 1 having the following formulation at 20 ° C. for 5 minutes, stopped, fixed, washed with water and dried by a conventional method, and the optical density 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
Each of coated samples 1 to 5 (spectral sensitizing dye blank sample) and coated samples 6 to 10 (sample to which spectral sensitizing dye was added) was exposed to light at a wavelength at which the intrinsic absorption of silver halide was observed. The relative sensitivities and the relative sensitivities when the coated samples 11 to 15 (samples to which the spectral sensitizing dye was added) were exposed to light having a wavelength at which the spectral sensitizing dye had absorption were shown. The coated samples 6 to 10 and the coated samples 11 to 15 were the same samples for the corresponding emulsions, but were exposed to different wavelengths. Therefore, the same samples were assigned two sample numbers.

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]

From the results shown in Table 1, the solid content of silver halide
When exposed at the wavelength of absorption, the dye blank sample
Little change in sensitivity due to doping
However, any of the doped emulsions
Also showed an increase in sensitivity. On the other hand, spectral sensitizing dyes
If exposed at a wavelength where_Two(2-MeI
m)_Two]⁰With clear desensitization in emulsions doped with
Of [CuCl_Two(2-proIm)_Two] ⁰, [NiCl_Two(2-MeIm)_Two]⁰To
Significant increase in sensitivity in doped emulsion
I understood. For chemically sensitized emulsions, the exposure wavelength and exposure
Irrespective of light time, clear feeling compared to undoped emulsion
No increase was observed.

Example 2 "Emulsion 6-a: Cubic silver chloride emulsion" Emulsion 6-a was prepared in the same manner as in Emulsion 1.

"Emulsion 6-b: Cubic silver chloride emulsion doped with a planar tetracoordinate complex having thiazole as a ligand" (Comparative Example) 25 g of deionized gelatin was added to 845 ml of an aqueous solution containing 4.5 g of sodium chloride and dissolved. While keeping the solution at 50 ° C. and stirring, 140 ml of 0.21 M aqueous solution of silver nitrate (solution 1) and 140 ml of 0.21 M aqueous solution of sodium chloride (solution 2) were quantitatively added by a double jet method over 10 minutes. After 10 minutes, 2.2 M aqueous silver nitrate solution (solution 3) 320 ml, 2.5M aqueous sodium chloride solution (solution 4) 285 ml, and, at a concentration of 2.0 × 10 ^-5 M [CoCl ₂ (thi
a) 35 ml of a methanol solution (solution 5) containing ₂ ] ⁰ (thia = thiazole) was further quantitatively added for 35 minutes by a triple jet method. Five minutes after the completion of the addition, the temperature was lowered to 35 ° C, soluble salts were removed by a normal sedimentation method, the temperature was raised again to 40 ° C, gelatin was added and dissolved, sodium chloride was further added, and hydroxide was added. It was adjusted to pH 6.5 with sodium. The resulting grains were monodispersed silver chloride cubes having a side length of 0.5 μm.

"Emulsion 7-12: Silver chloride cubic emulsion (2) doped with the planar tetracoordination complex of the present invention (2)" (in the present invention) In the preparation of emulsion 6-b, [CoCl ₂ (thia) ₂ ] ⁰ Emulsions 7 to 12 were prepared in exactly the same manner as in the preparation of Emulsion 6-b except that each complex of the present invention was used.

"Emulsions 13 to 18: Cubic silver chloride emulsion (3) doped with the planar four-coordinate complex of the present invention" (the present invention) Emulsions 13 to 18 were prepared in the same manner as emulsions 7 to 12 described above.
However, in emulsions 13 to 18, solution 5 was a methanol solution containing a complex at a concentration of 2.0 × 10 ⁻⁴ M.

These emulsions were coated in the same manner as coating samples 1 to 5 shown in Example 1 and coated samples 16 to 22 and
37-42 were obtained respectively.

The sensitizing dye of Example 1 was added to the above emulsion for 3.
8 × 10 ⁻⁴ mol / mol Ag was added and subjected to spectral sensitization, coated in the same manner as for coated samples 6 to 10, and coated samples 23 to 36 and 43 to 54
I got

These samples were exposed to sensitometry (10 seconds) through an optical wedge in the same manner as in Example 1, then developed at 20 ° C. for 5 minutes, stopped, fixed, washed with a conventional method. After drying, the optical density was measured. Table 2 shows the results for emulsions 6 to 12, and Table 3 shows the results for emulsions 13 to 18. Table 2 shows that each of the coated samples 16 to 22 (spectral sensitizing dye blank sample) and the coated samples 23 to 29 (sample to which the spectral sensitizing dye was added) was exposed at a wavelength at which the intrinsic absorption of silver halide was observed. And the relative sensitivities when each of the coated samples 31 to 36 (samples to which the spectral sensitizing dye was added) were exposed to a wavelength at which the spectral sensitizing dye had absorption. Further, Table 3 shows coated samples 37 to 42 (spectral sensitizing dye blank samples)
And the relative sensitivity of each of the coated samples 43 to 48 (samples to which the spectral sensitizing dye was added) when exposed at a wavelength at which the intrinsic absorption of silver halide was observed, and the coated samples 49 to 54 (the spectral sensitizing dyes were The relative sensitivities when each sample of the sample (to which the sample was added) was exposed at a wavelength at which the spectral sensitizing dye had absorption were shown. At this time, the results of the coated samples 16, 23, and 30 as type samples are also shown in Table 3.

[0082]

[Table 2]

[0083]

[Table 3]

In Example 1, the four-coordinate complex of the present invention was added to a sodium chloride solution to obtain a dope emulsion. On the other hand, here, each complex was added as a solution separate from silver and halogen to form a dope emulsion. Obtained. This is because the emulsion is prepared in an environment in which the halogen ion interacts with each complex molecule before the addition to form a complex in which two halogens are coordinated.

Table 2 shows the results of emulsions containing the same doping amount (doping concentration) in the silver halide grains as the results shown in Table 1. In these samples, it was found that there was a dopant in which the sensitivity was increased even in the spectral sensitizing dye blank sample. In addition, in the samples to which the spectral sensitizing dye was added, when exposed at the intrinsic absorption wavelength of silver halide, the sensitivity of the Co ^II complex was higher than that of the emulsion without the dye, and these dopants decreased the intrinsic desensitization. I found out. In addition, when exposure was performed at the absorption wavelength of the spectral sensitizing dye, a large increase in sensitivity was observed in all samples, and the increase in sensitivity was the largest in the emulsion doped with [CoCl ₂ (2-MeIm) ₂ ] ^0. all right. On the other hand, a complex using thiazole as a ligand, which is described in U.S. Pat. No. 5,360,712 as being effective, was also compared and studied. A complex [CoCl ₂ (thia) ₂ ] ⁰ having exactly the same form as that of the present invention was used as a comparative example in order to avoid that the effect due to other than the ligand as a dopant affects the photographic properties. Comparing the respective doped emulsions, when exposed at the intrinsic absorption wavelength of silver halide,
The protective function that reduces the intrinsic desensitization observed with the Co ^II complex is not seen in the emulsion doped with [CoCl ₂ (thia) ₂ ] ^0, and the sensitivity when exposed at the absorption wavelength of the spectral sensitizing dye is also reduced. ,
The emulsion doped with [CoCl ₂ (thia) ₂ ] ⁰ is the Co ^{II of the} present invention.
It did not reach much of the complex. From these, it is considered that it is necessary to have imidazole or an imidazole derivative as a ligand in order to achieve the object of the present invention.

Table 3 shows the results when the addition amount of the dopant was increased 10 times. At this time, the same tendency as the result shown in Table 2 was observed, but the rate of increase in sensitivity was smaller when the doping amount was increased. However, in the case of the Ni complex, the effect of increasing the sensitivity was greater when the doping amount was large.

Example 3 "Emulsion 19: Cubic silver chloride emulsion" Emulsion 19 was prepared in the same manner as in Emulsion 1. "Emulsion 20-23: of the present invention [CoCl ₂ (2-MeIm) _2] ⁰ doped with silver chloride cubic emulsions (4)" (the present invention) Emulsion 20 was prepared in the same manner as Emulsion 2. Emulsions 20 to 23 were prepared in the same manner as Emulsions 7 to 12, except that the solvent of Solution 5 was water, methanol, and ethanol, respectively.

"Emulsions 24-26: [CoCl ₂ (2-proIm) of the present invention]
₂ ] ^0- doped silver chloride cubic emulsion (5) "(invention) Emulsions 24 to 26 were prepared in the same manner as emulsions 7 to 12, except that the solvent of solution 5 was water, methanol and ethanol, respectively.
I got

These emulsions were coated on a triacetyl cellulose film support in the same manner as in the coating samples 1 to 5 shown in Example 1 to obtain coating samples 55 to 59 and 70 to 72, respectively.

The emulsions 20 to 23 and 24 to 26 described in Example 1
Sensitizing dye of 3.8 × 10 ^-4 mol / mol Ag and spectral sensitization.
60-69 and 70-78 were obtained.

These samples were exposed to sensitometry (10 seconds) through an optical wedge in the same manner as in Example 1, then developed at 20 ° C. for 5 minutes, stopped, fixed, washed with water and dried by a conventional method. Then, the optical density was measured. Table 4 shows the results for the coated samples 55 to 69, and Table 5 shows the results for the coated samples 70 to 78. Table 4 shows that each of the coated samples 55 to 59 (spectral sensitizing dye blank sample) and the coated samples 60 to 64 (sample to which the spectral sensitizing dye was added) was exposed at a wavelength at which the intrinsic absorption of silver halide was observed. And the relative sensitivities when each of the coated samples 65 to 69 (samples to which the spectral sensitizing dye was added) were exposed to a wavelength at which the spectral sensitizing dye had absorption.
Table 5 shows coated samples 70 to 72 (spectral sensitizing dye blank samples)
And the coated samples 73 to 75 (samples to which the spectral sensitizing dye was added) were exposed at a wavelength at which the intrinsic absorption of silver halide was observed, and the coated samples 76 to 78 (the spectral sensitizing dyes were added). The relative sensitivities when each sample (the sample added) was exposed to a wavelength at which the spectral sensitizing dye had absorption. At this time, the results of the coated samples 55, 60, and 65 were also shown as type samples.

[0092]

[Table 4]

[0093]

[Table 5]

When an emulsion is prepared after the Cl ⁻ ion and the complex are allowed to coexist in a solution as in Example 1,
It is believed that two more Cl ^- ions interact with the complex to be doped, resulting in a hexacoordinate octahedral structure and addition into the reactor. On the other hand, when the emulsion is prepared by adding the complex as a solution different from the solution containing silver ions or halogen ions as in Example 2, the solvent molecules interact with the complex molecules with a weak force. It is considered that they are added to the reactor in this state. As described above, when the state of the complex at the time of addition was different, a clear difference occurred in the sensitivity of each of the obtained emulsions. Therefore, in order to examine the change in photographic characteristics based on the difference in the addition method, here, an emulsion prepared by coexisting the complex with Cl ^- ion by the double jet method and the solvent of the solution at the time of adding the complex by the triple jet method were used. Were replaced with water, methanol and ethanol to obtain emulsions, and their photographic sensitivity was examined. Table 4 shows emulsions doped with [CoCl ₂ (2-MeIm) ₂ ] ^0, which had the largest change in sensitivity. In the emulsions prepared by these methods, a clear sensitization was brought about when the spectral sensitizing dye was added to the emulsion prepared by the triple jet method. In particular, the sensitivity was remarkably increased when exposure was performed at the absorption wavelength of the spectral sensitizing dye, and the sensitivity was highest when methanol was used as a solvent. This tendency is [CoCl ₂ (2-proIm) ₂ ]
^{The same} was true for the emulsion doped with ⁰ . Therefore,
To prepare these doped emulsions, it can be said that it is preferable to dissolve the complex to be doped with methanol as a solvent and prepare the emulsion by a triple jet method. Since the sensitivity was lowered when particles were formed in the presence of a Co ^II complex with Cl ^- ions, a 6-coordinate octahedral structure such as [CoCl ₄ (2-MeIm) ₂ ] ⁰ or a structure similar thereto was adopted. When incorporated into silver halide grains, it is considered to be undesirable in terms of photographic sensitivity. In the emulsion prepared by the triple jet method,
It is possible that the complex is incorporated into the silver chloride particles with the solvent molecule, but considering the weak interaction between the complex molecule and the solvent molecule, the complex with them is directly incorporated into the particle. It is hard to imagine. (CoCl ₄ (2-MeI
m) ₂ ] ⁰ when incorporated into silver halide grains in a hexacoordinated octahedral structure, and when [CoCl ₂ (2-MeIm) ₂ ] ⁰ is incorporated into grains, Co ^II ions and It is conceivable that the distances from the third and fourth Cl ^- ions interacting with each other are different, and this is presumed to be affecting the photographic characteristics.

Example 4 "Emulsions 27-33: Cubic silver chloride emulsion in which the planar four-coordinate complex of the present invention is localized on the grain surface" (Inventive) A cubic silver chloride emulsion was prepared in the same manner as in Emulsion 1. . The silver chloride cubic emulsion is added in an amount of 1 × 10 ^-7 to 1 × 10
^-4 mol of [CoCl ₂ (2-MeIm) ₂ ] ⁰ was added, and the complex was adsorbed on the surface of the grains at 60 ° C. to form emulsions 27 to 33.

These emulsions were coated in the same manner as the coating samples 1 to 5 shown in Example 1 to obtain coating samples 79 to 85. The sensitizing dye of Example 1 was added to these emulsions.
3.8 × 10 ⁻⁴ mol / mol Ag was added to the resultant, and spectral sensitization was performed.

Emulsions 27 to 33 contained 1.8 × 10 ^-2 per mole of silver.
Moles of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and then 2.5 × 10 ^-6 moles of sodium thiosulfate per mole of silver, optimally at 60 ° C. After chemical sensitization, emulsions 34 to 40 were obtained. These chemical sensitized emulsions were subjected to spectral sensitization by adding the above sensitizing dye to 3.8 × 10 ⁻⁴ mol / mol Ag.

Gelatin and sodium dodecylbenzenesulfonate were added to each of the chemically sensitized emulsions, 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 coated samples 100 to 106.

The emulsions subjected to chemical sensitization and spectral sensitization were coated in the same manner as coating samples 100 to 106 to obtain coating samples 107 to 120.

These coated samples were exposed to sensitometry (10 seconds) through an optical wedge in the same manner as in Example 1 and then developed at 20 ° C. for 5 minutes.
After washing with water and drying, the optical density was measured. Table 6 shows the results. Table 6 shows the specific absorption of silver halide in each of the coated samples 79 to 85 (spectral sensitizing dye blank sample) and the coated samples 100 to 106 (chemically sensitized spectral sensitizing dye blank sample). Relative sensitivity when exposed at the wavelength, coated samples 86 to 92 (samples with spectral sensitizing dye added) and coated samples 107 to 113 (samples with chemical sensitizing and spectral spectral sensitizing dye added) The relative sensitivities at the time of exposure at a wavelength at which the intrinsic absorption of silver can be seen are shown. (Shown as Sample Nos. 93 to 99 and 114 to 120).

[0101]

[Table 6]

Considering the possibility that the complex of the present invention is not doped inside the grains but localized near the grain surface, which affects the photographic properties, it was intentionally determined that [CoCl
The photographic characteristics of the emulsion having ₂ (2-MeIm) ₂ ] ⁰ adsorbed on the surface were examined. In these samples, when chemical sensitization was performed, an increase in sensitivity was observed when exposure was performed at the absorption wavelength of the spectral sensitizing dye, but it was found that an emulsion without chemical sensitization clearly caused desensitization. Although the details of this cause are unknown, the photographic characteristics are clearly different from the photographic characteristics of the emulsions doped with the four-coordinate complex of the present invention in Examples 1 to 3.

Example 5 "Emulsion 41; Preparation of Sample of Silver Bromide Emulsion" 36 g in 870 ml of water
Was added and dissolved in 0.25 g of potassium bromide. 36 ml of 0.088 M silver nitrate aqueous solution (solution 6) and 36 ml of 0.088 M potassium bromide aqueous solution (solution 7) were added to this aqueous gelatin solution kept at 75 ° C. with stirring for 10 minutes by a double jet method. 176 ml of each of the solutions 7 were added by the double jet method for 7 minutes. Then 0.82 M
Starting with 898 ml of an aqueous solution of silver nitrate (solution 8) and increasing the flow rate from a flow rate of 0.53 ml / min for 95 minutes, simultaneously adding a 0.90 M aqueous solution of potassium bromide (solution 9) with a silver potential of +120 mV (vs. a saturated calomel electrode) Was added while controlling to keep at
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 42-45: Cubic silver bromide emulsion doped with the Co (II) complex of the present invention" (Invention) In the method for preparing the emulsion 41, the Co (II) complex of the present invention was added to the solution 9 in 8.2. × 10 ^-7 M
(Emulsion 42, 44) or 8.2 × 10 ^-6 M (Emulsion 43, 45)
42-45 were obtained.

Gelatin and sodium dodecylbenzenesulfonate were added to these emulsions 41 to 45, 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 2,4-dichloro-6-hydroxy-s-triazine sodium salt at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 121 to 125. These emulsions also contained the sensitizing dye of Example 1 in an amount of 4.9 × 10 ⁻⁴ mol / mol.
Ag was added for spectral sensitization, and coating was performed in the same manner as for coating samples 121 to 125 to obtain coating samples 126 to 135.

The above silver bromide emulsions 41 to 45 were added per mole of silver.
Add 1.2 × 10 ^-4 mol of sodium thiosulfate and add 60 ℃
Optimized chemical sensitization. These chemically sensitized emulsions were coated in the same manner as the above-mentioned coating samples 121 to 125 to obtain coating samples 136 to 140. To these chemically sensitized emulsions, the sensitizing dye of Example 1 was added in an amount of 4.9 × 10 ⁻⁴ mol / mol Ag, and subjected to spectral sensitization. Samples 141 to 150 were obtained.

The samples were exposed to sensitometry exposure (1 second) through an optical wedge, developed with a developer 2 having the following formulation, developed at 20 ° C. for 10 minutes, and stopped in a conventional manner.
After fixing, washing and drying, the optical density was measured. Fog,
The sensitivity was determined by the minimum optical density of the sample, and the sensitivity was expressed by the logarithm of the exposure required to obtain an optical density of fog + 0.1, and was expressed as a relative value with the value of the type sample being 100. Table 7 shows the coated samples 121 to 125 (spectral sensitizing dye blank samples)
And coated samples 126-130 (samples with spectral sensitizing dye added)
The relative sensitivity when each sample was exposed at a wavelength at which the intrinsic absorption of silver halide was observed, and the spectral sensitizing dye showed absorption in each of the coated samples 131 to 135 (samples to which the spectral sensitizing dye was added). The relative sensitivities when exposed at the given wavelengths are shown. Table 8 shows that each of coated samples 136 to 140 (spectral sensitizing dye blank sample subjected to chemical sensitization) and coated samples 141 to 145 (chemical sensitized and spectral sensitizing dye-added sample) were added to each sample. The relative sensitivity when exposed at a wavelength at which the intrinsic absorption of silver halide can be seen, and the absorption of the spectral sensitizing dye in each of the coated samples 146 to 150 (samples subjected to chemical sensitization and added with spectral sensitizing dye) The relative sensitivities when exposed at the given wavelengths are shown. In addition,
Coated samples 126 to 130, coated samples 131 to 135, and coated samples
141-145 and 146-150 are the same samples for the corresponding emulsions respectively, but were exposed at different wavelengths,
The same sample was given two different sample numbers.

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.

[0109]

[Table 7]

[0110]

[Table 8]

In the samples not subjected to chemical sensitization shown in Table 7, no change in photographic characteristics due to doping was observed when no spectral sensitizing dye was added, as in the case of silver chloride. On the other hand, when the spectral sensitizing dye was added, the sensitivity was increased regardless of the exposure wavelength. However, in this case without chemical sensitization, no apparent difference in photographic properties based on the doping amount of the complex was observed.
On the other hand, when chemical sensitization was performed, a similar increase in sensitivity was observed when the spectral sensitizing dye was added, and the increase in sensitivity was larger when the dope amount was small.

Example 6 "Emulsion 51; Preparation of Sample of Silver Bromide Emulsion" Emulsion 51 was prepared in the same manner as emulsion 41 shown in Example 5.

"Emulsions 52-57: Cube (II) complex-doped silver bromide cubic emulsion of the present invention" (Invention) Emulsions 52-45 were prepared in the same manner as emulsions 42-45 shown in Example 5. However, the solution 9 contains the Cu (II) complex of the present invention at 8.2 × 10 ⁻⁸ , 8.2 ×
10 ^-7 and 8.2 × 10 ^-6 M were added, and emulsions 52 to 5 were added, respectively.
4 and 55 to 57. The amount of the complex added at this time corresponds to 1 × 10 ⁻⁷ , 1 × 10 ⁻⁶ , and 1 × 10 ⁻⁵ mol per mol of silver.

These emulsions 51 to 57 were coated in the same manner as in Example 5 to obtain coated samples 151 to 157. Further, 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 151 to 157 to obtain coating samples 158 to 171. Was.

The above emulsions 51 to 57 were chemically sensitized in the same manner as in Example 5, and these sensitized emulsions were coated in the same manner as the above coated samples 151 to 157, and coated samples 172 to 178. I got In addition, these emulsions subjected to chemical sensitization were prepared in Example 1
The sensitizing dye was added in an amount of 4.9 × 10 ⁻⁴ mol / mol Ag and subjected to spectral sensitization, followed by coating in the same manner as above to obtain coated samples 180 to 192.

The samples were exposed to sensitometric exposure (1 second, 10 ^-3 seconds) through an optical wedge, developed in the same manner as in Example 5, then stopped, fixed, and washed in a conventional manner. , Dried and measured optical density. Table 9 shows coated sample 15
1-157 (spectral sensitizing dye blank sample) and coated sample 158
To 164 (samples to which the spectral sensitizing dye was added), and the relative sensitivities when each sample was exposed to a wavelength at which the intrinsic absorption of silver halide was observed, and coating samples 165 to 171 (samples to which the spectral sensitizing dye was added) 3) shows the relative sensitivity when each sample was exposed to a wavelength at which the spectral sensitizing dye had absorption. Table 10 shows that each of the coated samples 172 to 178 (spectral sensitizing dye blank sample subjected to chemical sensitization) and the coated samples 179 to 185 (chemical sensitized and spectral sensitizing dye-added sample) were added to each sample. The relative sensitivity when exposed at a wavelength at which the intrinsic absorption of silver halide can be seen, and the absorption of the spectral sensitizing dye to each of coated samples 186 to 192 (samples subjected to chemical sensitization and added with spectral sensitizing dye) The relative sensitivities when exposed at the given wavelengths are shown.

[0117]

[Table 9]

[0118]

[Table 10]

In the emulsion doped with [CuCl ₂ (2-MeIm) ₂ ] ⁰ , the case where no chemical sensitization was performed and the case where chemical sensitization was performed, the case where no spectral sensitizing dye was added, and the case where When the dye was added, it was found that in each case, the photographic characteristics were very similar to those of the emulsion doped with the Co (II) complex shown in Example 5. On the other hand, in the emulsion doped with [CuCl ₂ (2-proIm) ₂ ] ⁰ , the presence or absence of chemical sensitization, the presence or absence of spectral sensitizing dye,
Regardless of the exposure time or the like, a large increase in sensitivity was observed in each case, and it was found that a large increase in sensitivity was obtained particularly when the doping amount was small.

Example 7 "Emulsion 65; Preparation of Sample of Silver Bromide Emulsion" Emulsion 65 was prepared in the same manner as for emulsion 41 shown in Example 5.

"Emulsions 66 to 70: [NiCl ₂ (2-MeI
m) ₂ ] ⁰ complex doped silver bromide cubic emulsion "(Invention) Prepared in the same manner as emulsions 42 to 45 shown in Example 5. However, the solution 9 contained [NiCl ₂ (2-MeIm) ₂ ] ⁰ of 8.2 × 10
^-8 , 4.1 × 10 ^-7 , 8.2 × 10 ^-7 , 8.2 × 10 ^-6 , 8.2 × 10 ^-5 M. The amount of the complex added at this time was 1
1 × 10 ^-7 , 5 × 10 ^-7 , 1 × 10 ^-6 , 1 × 10 ^-5 , 1 × 1 per mole
It corresponds to ^0-4 mol.

These emulsions 65 to 70 were coated in the same manner as in Example 5 to obtain coated samples 193 to 198. Further, 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 193 to 198 to obtain coating samples 199 to 210. Was.

The above emulsions 65 to 70 were chemically sensitized in the same manner as in Example 5, and these sensitized emulsions were coated in the same manner as the above-mentioned coating samples 193 to 198, and coated samples 211 to 216. I got In addition, these emulsions subjected to chemical sensitization were prepared in Example 1
4.9 × 10 ⁻⁴ mol / mol Ag was added to the resulting mixture to perform spectral sensitization, and the mixture was coated in the same manner as above to obtain coating samples 217 to 228.

The samples were exposed to sensitometric exposure (1 second, 10 ⁻³ seconds) through an optical wedge, developed in the same manner as in Example 5, then stopped, fixed, and washed in a conventional manner. , Dried and measured for optical density. Table 11 shows the coating sample 19
3-198 (spectral sensitizing dye blank sample) and coated sample 199
To 204 (samples to which spectral sensitizing dye was added), and relative sensitivities when exposed to wavelengths at which the intrinsic absorption of silver halide was observed, and coated samples 205 to 210 (samples to which spectral sensitizing dye was added) 3) shows the relative sensitivity when each sample was exposed to a wavelength at which the spectral sensitizing dye had absorption. Table 12 shows that each of the coated samples 211 to 216 (the spectrally sensitized dye blank sample subjected to chemical sensitization) and the coated samples 217 to 222 (the chemically sensitized and spectrally sensitized dye-added sample) were used. The relative sensitivity when exposed at a wavelength at which the intrinsic absorption of silver halide is observed, and the absorption of the spectral sensitizing dye in each of the coated samples 223 to 228 (samples subjected to chemical sensitization and added with spectral sensitizing dye). The relative sensitivities when exposed at the given wavelengths are shown.

[0125]

[Table 11]

[0126]

[Table 12]

In the emulsion doped with [NiCl ₂ (2-MeIm) ₂ ] ⁰ , similarly to the emulsion doped with the Co (II) complex shown in Example 5, the spectral sensitizing dye was used regardless of the presence or absence of chemical sensitization. The increase in sensitivity was observed when was added. When the chemical sensitization is not performed, the increase in the sensitivity is as follows.
The ^{maximum value is} about 10 ⁻⁷ to 1 × 10 ⁻⁶ mol, whereas 1 × 10 ⁻⁷ per mol of silver when chemically sensitized.
It was largest when the amount of addition was about mole.

Example 8 "Emulsion 77: Preparation of Tabular Grain Emulsion of Silver Iodobromide with (111) Main Plane" 0.38 g of KBr, low molecular weight gelatin (molecular weight: 1)
5,000) 1 liter of dispersion medium solution containing 0.5 g (pH = 5)
To the reaction solution at 40 ° C.
By a double jet method, 0.29 M of silver nitrate and 0.29 M of KBr solution were added in 20 ml each for 40 seconds. After the addition, the dispersion medium solution was heated to 75 ° C. over 15 minutes, and 15 minutes after the temperature increase, a dispersion medium solution containing 35 g of alkali-treated gelatin and 250 ml of water was newly added. After adjusting the pH to 6.0, 734 ml of a 1.2 M silver nitrate solution was added while accelerating the flow rate. During this time, pBr
A mixed solution of KBr solution and KI solution (solution 10) was added at the same time so as to keep 2.93. At this time, I
^- is 3 mol% and comprising an amount of KI solution and KBr solution is added.

"Emulsion 78-80: Silver iodobromide tabular emulsion doped with the four-coordinate complex of the present invention" (the present invention)
Except that it includes a concentration of 0 ^-6 M, to prepare an emulsion 78-80 obtained in the same manner as Emulsion 77.

These emulsions were coated in the same manner as in Example 1 to obtain coating samples 229 to 232. The sensitizing dye of Example 1 was added to these emulsions at 4.9 × 10 ⁻⁴ mol / mol A
g, spectrally sensitized, and coated in the same manner.
33-240 were obtained.

The above emulsions 77 to 80 contained 8.0 × 1 per mol of silver.
0 ^-6 moles of added sodium thiosulfate and 3 × 10 ^-6 mol of chloroauric acid and potassium thiocyanate sulfate was optimally chemically sensitized at 60 ° C.. These chemically sensitized emulsions were coated in the same manner as the above coated samples 229 to 232 to obtain coated samples 241 to 244. The emulsions subjected to these chemical sensitizations were subjected to spectral sensitization by adding the sensitizing dyes of the examples to 4.9 × 10 ⁻⁴ mol / mol Ag, and then coated in the same manner as the coated samples 241 to 244. sample
245-252 were obtained.

The samples were exposed to sensitometric exposure (1 second, 10 ⁻³ seconds) through an optical wedge, developed in the same manner as in Example 5, then stopped, fixed, and washed in a conventional manner. , Dried and measured for optical density. Table 13 shows the coating sample 22
9 to 236 (blank sample of spectral sensitizing dye) and coated sample 233
To 236 (samples to which spectral sensitizing dye was added), and the relative sensitivities when each sample was exposed to a wavelength at which the intrinsic absorption of silver halide was observed, and coating samples 237 to 240 (samples to which spectral sensitizing dye was added) 2) shows the relative sensitivity when each sample was exposed to a wavelength at which the spectral sensitizing dye had absorption. Table 14 shows that each of the coated samples 241 to 244 (spectral sensitizing dye blank sample subjected to chemical sensitization) and the coated samples 245 to 248 (chemical sensitized and spectral sensitizing dye-added sample) were added to each sample. The relative sensitivity when exposed at a wavelength at which the intrinsic absorption of silver halide can be seen, and the absorption of the spectral sensitizing dye in each of coated samples 249 to 252 (samples subjected to chemical sensitization and added with spectral sensitizing dye) The relative sensitivities when exposed at the given wavelengths are shown.

[0133]

[Table 13]

[0134]

[Table 14]

The silver iodobromide tabular emulsion includes a silver bromide cubic emulsion.
The effect of sensitization was large with [CuCl _Two(2-proIm)_Two]⁰,
(NiCl_Two(2-MeIm)_Two]⁰, [CoCl_Two(2-proIm)_Two]⁰Each complexion
The body was used for dope. Highly sensitive milk in all samples
As in the case of cubes,
Sensitization with fees was significant. In these emulsions,
Sensitization was also observed with the school sensitized emulsion, but 10^-3Second exposure
The degree of increase was slightly smaller.

Example 9 "Emulsion 85-87; silver iodobromide tabular grain emulsion having a (111) major plane (3)" The emulsion obtained in Example 8 was optimally chemically sensitized and spectrally sensitized. After giving the feeling, the emulsion was used as an emulsion of the third layer of the photosensitive material of Sample 201 of Example 2 of JP-A-9-146237, and the same processing as in the example of JP-A-9-146237 was performed to obtain good results. Was.

Example 10 "Emulsion 88-90; Tabular grain emulsion of silver iodobromide having a (111) major plane (4)" The emulsion obtained in Example 8 was optimally chemically sensitized and spectrally sensitized. After giving the feeling, the emulsion was used as an emulsion of the third layer of the light-sensitive material of Sample 110 of Example 1 of JP-A-10-20462, and the same processing as in the example of JP-A-10-20462 was carried out to obtain good results. Was.

[0138]

The present invention is based on the finding that the inclusion of a complex having a four-coordinate coordination structure in a silver halide emulsion has advantages in photographic properties. That is, when each complex having a planar four-coordinate or tetrahedral coordination structure used in the present invention is doped into silver halide grains, as in the example, undoped without depending on the halogen composition of the silver halide. A silver halide light-sensitive material having a high sensitivity and a small intrinsic desensitization as compared with the emulsion can be obtained.

Claims (7)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that a compound represented by the following general formula I is contained in the emulsion. Formula I Wherein M represents any metal or metal ion, and L is M
A compound represented by the following general formula II, wherein x is 1,
2, 3, or 4, and n represent an integer of -6 or more and +5 or less. L ^I represents any chemical species that binds to M,
when x is 1 or 2, L ^I may be a plurality of different species. Formula II In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, a halogen, a cyano group, a nitro group, a mercapto group, A hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, a sulfonyloxy group, an amino group, an ammonio group, a carbonamide group, a sulfonamide group, an oxycarbonylamino group, an oxysulfonylamino group, a ureido group, Thioureido group, acyl group, oxycarbonyl group, carbamoyl group, thiocarbonyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group,
It represents a sulfano group, 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. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
2. The silver halide photographic material according to claim 1, wherein the silver halide grains contained in the emulsion contain a compound represented by the formula (I). 3. In the general formula I, M is titanium, vanadium, chromium, manganese, iron, cobalt, nickel,
The silver halide photographic material according to claim 1 or 2, wherein the material is a metal or a metal ion selected from copper, zirconium, rhodium, palladium, silver, iridium, platinum, gold, and tin. 4. A compound represented by the general formula I:
But two, or, when three silver halide photographic material as claimed in claim 1 or claim 2 wherein at least one of L ^I, characterized in that a halogen ion. 5. A compound of general formula I wherein M is Co, Ni,
5. The silver halide photographic material according to claim 4, wherein the material is a metal ion selected from Cu and Cu. 6. At least one of R ₁ , R ₂ and R ₃ in the compound of general formula II is a methyl group, an ethyl group, n
6. The silver halide photographic material according to claim 5, wherein the material is selected from-and i-propyl groups. 7. The silver halide photosensitive material according to claim 6, wherein in the general formula I, L ^I = Cl ⁻ .