JP2000112052A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material high in sensitivity by incorporating a complex having a function of extending the existence time of photoelectrons generated by exposure longer than the case containing specified complex alone, in an emulsion. SOLUTION: A cyano-complex 2 having a function of extending the existence time of photoelectrons generated by exposure longer than the case containing cyano-complex 1 alone is contained into an emulsion together with the cyano- complex 1 represented by formula. In the formula, M is an optional metal atom, L is an optional ligand, (x) is 3, 4, 5 or 6 and (n) is -4, -3, -2 or -1. When the emulsion is doped with the cyano-complex having CN ions as ligands (cyano-complex 1) and further, doped with the second complex (cyano-complex 2), the photoelectron existence time si extended longer than the emulsion doped with the complex 1 alone and the further increase in photographic sensitivity is brought.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material. In particular, the present invention relates to a high-sensitivity silver halide photographic material using a dopant technique.

[0002]

2. Description of the Related Art As one of the techniques for modifying silver halide grains to improve the performance of silver halide photographic light-sensitive materials as expected, a technique incorporating a substance (dopant) other than silver ions and halide ions. (Dope technology).
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] Among the transition metal ions, a silver halide emulsion doped with a lead ion or a cadmium ion can provide a highly sensitive emulsion, and at the same time, Phys. Stat. Sol. (B) 197
8,88,705, Photogr.Sci.Eng. 1982,26,20, Photogr.Sci.
As shown in Eng. 1984, 28, 92, these dopants are known to increase the lifetime of photoelectrons generated by exposure as compared to the case without any doping. Photoelectrons are excited electrons generated by the absorption of light by silver halide grains, and their existence time (electron lifetime) is measured by microwave photoconduction as shown in the above three documents. . Microwave photoconductivity is a method of observing a fast decay process of photoelectrons by measuring a temporal change in electric conductivity in a microwave region, usually using a coated film as a measurement sample. Irradiated microwaves often include Phys.Stat.Sol. (B) 1978,88,705,
9GHz used in Photogr.Sci.Eng.1982, 26, 20;
Or 35 used in Photogr.Sci.Eng.1984,28,92
GHz is used. In addition, a laser beam such as an Nd-YAG laser is used as a light source for exposure.

On the other hand, in order to enhance the sensitivity of silver halide emulsions, a technique has been known in which not only a transition metal ion but also a transition metal complex having a cyanide ion as a ligand is doped into silver halide grains. Was. In particular, there are many examples of disclosure of a high-sensitivity emulsion obtained by doping a group VIII metal complex having six cyanide ions as ligands. Tokiko 48-35
No. 373 discloses a yellow blood salt which is a hexacyanoiron (II) complex and a red blood salt which is a hexacyanoiron (III) complex as a dopant containing a cyanide ion. However, according to the present invention, the effect of sensitization is irrelevant to the type of ligand and is limited to the case where iron ions are contained. There are many other examples in which a highly sensitive emulsion was obtained by doping a hexacyanoiron (II) complex. For example, JP-A-5-66511, U.S. Pat.
No. 32,203 and the like. A highly sensitive emulsion obtained by doping a cyano complex in addition to an iron complex is known. Japanese Patent Application Laid-Open No. 2-20853 discloses that silver iodochloride is doped with a complex of rhenium, ruthenium, osmium and iridium. It is disclosed that a silver halide emulsion having high sensitivity can be obtained.

In the emulsion doped with the complex having a cyanide ion as a ligand as described above, it is known that the existence time of photoelectrons is prolonged similarly to the case of the emulsion doped with lead ion or cadmium ion. Have been. Procee
dings of IS & T / SPSTJ's oct.1997, p.137 and ICPS, 19
98, Final program and Proceedings, Vol. 1, p. 106, showed that the photoelectron abundance time of hexacyanoiridium (III) -doped emulsions was sufficiently longer than that of undoped emulsions. Ari, ICPS, 1998, Fin
al program and Proceedings, Vol. 1, p. 92, ICPS, 199 for hexacyanoruthenium (II) -doped emulsions and hexacyanoiron (II) -doped emulsions.
8, Final program and Proceedings, Vol. 1, p. 89, show the effect of extending the existence time of photoelectrons. As disclosed in Japanese Patent Application Laid-Open No. 8-286306, when the existence time of photoelectrons becomes longer, the probability that the electrons contribute to the formation of a latent image increases, and the photographic sensitivity improves. Therefore, in order to obtain a highly sensitive emulsion, it is important to lengthen the existence time of photoelectrons, but as a dopant giving the effect, there has been no known other than a hexacyano complex.

A technique is known in which one dopant is doped with another dopant together with a hexacyano complex in one particle. These are used to obtain an emulsion having high sensitivity and good reciprocity characteristics and preferable gradation. JP-A-3-18837, JP-A-2-125245, JP-A-4-51233, and JP-A-4-51232 disclose a hexacyanoiron (II) complex and a hexachloroiridium (I
V) An emulsion in which a complex is used in combination is described. JP-A-4-124463, JP-A-8-314043, and U.S. Pat. No. 5,576,172 disclose a hexacyanoruthenium (II) complex and a hexachloro Iridium (I
V) Describes an emulsion combined with a complex. In these patents, by using each dopant together, an emulsion with high sensitivity at high illuminance side is obtained, which is the effect of sensitizing hexacyano iron (II) complex and the effect of improving reciprocity failure of iridium complex Were added to each other, resulting in an emulsion having high sensitivity on the high illuminance side. Emulsions doped with iridium ions or hexachloroiridium (IV) include those described in J. Imaging Sci. 1988, 32, 187 and ICPS '94:
Phys. Chem. Imaging Syst., IS &T's 47 ^th Annu. Conf.
As described in (1994), Vol. 1, 67, the existence time of photoelectrons does not become long like the emulsion doped only with the hexacyano complex, and the existence time becomes short. The existence time of the photoelectrons in the emulsion using the hexacyano complex in combination with these iridium compounds should be shorter than the existence time of the photoelectrons in the emulsion doped only with the hexacyano complex due to the effect of shortening the existence time of the photoelectrons of the iridium compound. Is predicted. Also, US Pat.
4,888, U.S. Pat. No. 5,480,771, U.S. Pat. No. 5,500,335, EP 0610670,
European Patent 0606893, European Patent 0606894
Pentachloronitrosylosmium (II), hexacyanoruthenium
(II) and three complexes of hexachloroiridium (IV), or pentachloronitrosylosmium (II),
Hexacyanoiron (II) and hexachloroiridium
It has been shown that by doping the three complexes of (IV) simultaneously into one silver halide grain, a high-sensitivity and high-contrast emulsion can be obtained, but in the case of the osmium complex also J. Imagi
As shown in ng Sci., 1987, 31, 55, the existence time of photoelectrons is known to be short, and the existence time of photoelectrons in these emulsions is also longer than that observed in the hexacyano complex. It is thought that there is no.

[0007] As described above, the existence time of photoelectrons, which has been increased by doping the hexacyano complex, has been described as follows.
There is no known technique for further increasing the length by using another dopant in combination.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic material having a higher sensitivity by obtaining an emulsion in which the existence time of photoelectrons is longer than that of an emulsion doped with a hexacyano complex. And

[0009]

The object of the present invention is to provide the following (1)
To (24).

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, a cyano complex (complex-1) represented by the following general formula I in the emulsion; When used with the complex-1, the complex
A silver halide photographic light-sensitive material characterized in that the emulsion contains a complex (complex-2) having a function of prolonging the existence time of photoelectrons generated by exposure as compared with a case containing only -1. General formula I

[0011]

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In the formula, M represents any metal, L represents any ligand, x is 3, 4, 5, or 6, and n is -4, -3, -2 or -1.

(2) The silver halide photographic light-sensitive material as described in (1), which comprises complex-1 and complex-2 having no cyanide ion as a ligand.

(3) In a silver halide photographic material having at least one silver halide emulsion layer on a support, a complex-1 and a cyanide ion are coordinated to silver halide grains contained in the emulsion. (1) The silver halide photographic material as described in (1), which comprises a complex-2 having no child.

(4) The silver halide photographic material as described in (3), which comprises a complex 1 which is a 6-cyano complex and a complex 2 which does not have a cyanide ion as a ligand.

(5) Either complex-1 which is a 6-cyano complex and a chain or cyclic hydrocarbon are used as a base structure, or a part of carbon or hydrogen atoms in the base structure is replaced with another atom or atomic group. (3) The silver halide photographic light-sensitive material as described in (3) above, which comprises a complex-2 having the compound replaced by a ligand as a ligand.

(6) The silver halide photographic light-sensitive material according to (3), which comprises a complex 1 which is a 6-cyano complex and a complex 2 which has a heterocyclic compound as a ligand.

(7) A complex comprising complex-1 which is a 6-cyano complex and complex-2 represented by the following general formula II:
The silver halide photographic light-sensitive material described in 1. General formula II

[0019]

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In the formula, M ′ represents an arbitrary metal ion, L ′ is a compound represented by the general formula III, X is a halogen ion, y is 1, 2 or 3, m is −5, −4 , -3, -2, -1, 0, +
1 or +2. General formula III

[0021]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group and an aryl group. , Halogen, cyano group, nitro group,
Mercapto group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, ammonium group,
Carbonamido group, sulfonamido 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,
It represents a substituent selected from a sulfamoyl group, a sulfino group, a sulfano group, a carboxylic acid and a salt thereof, a sulfonic acid and a salt thereof, and a phosphonic acid and a salt thereof. Also, where
R ₂ and R ₃ may be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring.

(8) A complex comprising complex-1 which is a 6-cyano complex and complex-2 represented by the following general formula IV:
The silver halide photographic light-sensitive material described in 1. General formula IV

[0024]

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In the formula, M ″ represents an arbitrary metal ion, L ′ is a compound represented by the general formula III, X is a halogen ion, z is 1 or 2, k is −3, −2, −. 1, 0, +1 or +2.

(9) The silver halide photographic material as described in (7), wherein M 'in the general formula II is a metal ion selected from titanium, manganese, platinum and tin.

(10) The silver halide photographic material as described in (8), wherein M ″ in the general formula IV contains a complex which is a metal ion selected from cobalt, copper and nickel.

(11) R ₁ , R ₂ and R ₃ in the general formula III
At least one of which is a substituent selected from a methyl group, an ethyl group, an n- or i-propyl group, the silver halide photographic material as described in (9) or (10).

(12) The silver halide photographic material as described in (11), wherein the complex-1 is 6 cyanorthenium or yellow blood salt.

(13) The silver halide photographic material as described in (11), wherein the complex-1 is a yellow blood salt.

(14) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, silver halide grains contained in the emulsion are added to a 6-cyano complex (complex-3) and A complex which has a function of extending the existence time of photoelectrons by using together with Complex-3, but does not extend the existence time of photoelectrons generated at the time of exposure alone (complex-4). A silver halide photographic light-sensitive material comprising:

(15) The silver halide photographic light-sensitive material according to (14), which comprises complex-3 and complex-4 having no cyanide ion as a ligand.

(16) A compound in which complex-3 and a chain or cyclic hydrocarbon are used as a parent structure, or a compound in which a part of carbon or hydrogen atoms of the parent structure is replaced by another atom or atomic group. (14) The silver halide photographic material as described in (14) above, which contains a complex-4 as a ligand.

(17) The silver halide photographic light-sensitive material as described in (14), which contains a complex-3 and a complex-4 having a heterocyclic compound as a ligand.

(18) Complex-3 and complex-4 represented by the general formula II
(14) The silver halide photographic material as described in (14) above.

(19) Complex-3 and complex-4 represented by the general formula IV
(14) The silver halide photographic material as described in (14) above.

(20) The silver halide photographic material as described in (18), wherein M 'in the general formula II is a metal ion selected from titanium, manganese, platinum and tin.

(21) The silver halide photographic material as described in (19), wherein M ″ in the general formula IV is a metal ion selected from cobalt, copper and nickel.

(22) R ₁ , R ₂ and R ₃ in the general formula III
And at least one of them is a substituent selected from a methyl group, an ethyl group, an n- or i-propyl group.

(23) The silver halide photographic material as described in (22), wherein the complex-3 is 6 cyanorthenium or yellow blood salt.

(24) The silver halide photographic material as described in (22), wherein the complex-3 is a yellow blood salt.

The above silver halide photographic materials (1) to (24) are preferably carried out in the following modes (25) to (28).

(25) In a silver halide photographic material having at least one silver halide emulsion layer on a support, silver halide grains contained in the emulsion comprise at least 80% by volume of complex-3 of the complex-3. A silver halide photographic light-sensitive material, wherein the light-sensitive material is contained in the surface layer from the portion exceeding 100% to 100%, and the same particle contains Complex-4.

(26) The complex represented by the general formula II or the general formula IV, wherein the silver halide grains contain the complex-3 in a surface layer of at least a portion exceeding 80% to 100% in a grain volume, and The silver halide photographic material as described in (25), wherein -4 is uniformly contained in the grains.

(27) The silver halide grains contain at least a complex-3 in the surface layer of at least 80% to 100% in the grain volume, and the same grains are represented by the general formula II or IV Silver photographic light-sensitive material according to (25), wherein the complex-4 is contained in the same part of the grain as the complex-3 is contained.

(28) A complex -4 represented by the general formula II or IV is added to silver halide grains at least 9 times the grain volume.
(25) The silver halide photograph described in (25), wherein complex-3 is contained in the surface layer from 0% to 100%, and 5% to 20% of the whole grain volume immediately inside the surface layer contains complex-3. Photosensitive material.

[0047]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, photoelectrons are excited electrons generated by the absorption of light by silver halide grains, and their existence time is measured by measuring the time-dependent change in electrical conductivity after photoexcitation. It can be observed that the density of the generated photoelectrons decreases as a result of this, but here, this was measured by microwave photoconductivity, which measures the temporal change in electrical conductivity in the microwave region. The irradiated microwave is Photogr. Sci. Eng. 1984,
35GHz microwave as used in 28, 92,
According to this document, a measuring method including a measuring device can measure the existence time of photoelectrons. Here, a coated film was used as a measurement sample. The existence time of photoelectrons is determined by J. Ima
g. Sci. Tech., 1994, 38, 526 and J. Imag. Sci. Tech., 1
Although it is also known to define each component included in the photoelectron decay process as shown in 997, 41, 118, in the present invention, the intensity of the microwave photoconductivity obtained by exposure has the maximum intensity. The time required to decay to 1 / e is defined as the "existence time of photoelectrons". Further, a laser beam such as an Nd-YAG laser can be used as a light source for exposure, but in the present invention, the third harmonic (355 nm) of the Nd-YAG laser,
And Optical parametric Oscil using this as the excitation light source
lation (460 nm) was used as the exposure light source. In consideration of fluctuations in the intensity of irradiation light originating from the excitation light source, in the present invention, "a sample whose photoelectron existence time is longer than 10%" was used as a dopant for extending photoelectron existence time.

It is known that, in an emulsion doped with a complex having a cyanide ion as a ligand such as a hexacyano complex, the existence time of photoelectrons generated by exposure is extended and the photographic sensitivity is increased. When the second complex (complex-2) is further doped into the emulsion doped with the complex having cyanide ion as a ligand (complex-1), the photoelectron becomes smaller than the emulsion doped only with complex-1. Can be made longer, which leads to a further increase in photographic sensitivity. Specific examples of the complex used as complex-1 in the present invention are shown below.
However, the compound of the present invention is not limited to this.

[0049]

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These complexes may be used not only as complex-1 but also as complex-2. In addition, it is preferable to use the complex described below as the complex-2.

When M is an arbitrary metal and L ′ is an imidazole derivative, [MCl ₂ L ′ ₂ ] ⁰ or [MCl ₄ L ′ ₂ ] ⁿ (
(n = integer) can be preferably used as the complex-2 of the present invention. In an emulsion doped with these complexes, an imidazole derivative may be used as a ligand.
It is not clear how this affects the prolongation of the photoelectron existence time, but at least when the imidazole derivative has H at the 1-position, it can be deprotonated to become an anion, and halogen When replacing the (AgCl ₄ ) ^3- unit or the (AgCl ₆ ) ^{5 -} unit in the silver halide grains with the doping complex, the charge is more reasonable than in the case where another uncharged ligand is used. It is thought that it can be replaced. In addition, even in such an anionized state, the imidazole derivative does not have a high ability as a bridging ligand as compared with pyrazole, so that there is little possibility of forming a complex of two or more nuclei before being doped into silver halide grains. Are also considered advantageous in doping.

As the imidazole derivative in the present invention
Is a group represented by the general formula III ₁, R_Two, R_Threeand
R_FourIs a hydrogen atom, a substituted or unsubstituted alkyl group (methyl
Group, ethyl group, n-propyl group, isopropyl group, n-butyl group
Tyl, t-butyl, hexyl, octyl, 2-ethyl
Lehexyl group, dodecyl group, hexadecyl group, t-octyl
, Isodecyl, isostearyl, dodecyloxy
Cypropyl group, trifluoromethyl group, methanesulfonate
An alkenyl group, an alkynyl group,
Aralkyl groups, cycloalkyl groups (cyclohexyl groups,
4-t-butylcyclohexyl group, etc.), substituted or 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, chlorine, odor
Iodine), cyano group, nitro group, mercapto group,
Doxy group, alkoxy group (methoxy group, butoxy group,
Toxiethoxy group, dodecyloxy group, 2-ethylhexyl
An aryloxy group (phenoxy group, p-
Tolyloxy group, p-chlorophenoxy group, 4-t-butylphenyl
Phenoxy, alkylthio, arylthio, acyl
Ruoxy group, sulfonyloxy group, substituted or unsubstituted
Amino group (amino group, methylamino group, dimethylamino
Group, anilino group, N-methylanilino group, etc.), ammonium
Group, carbonamido group, sulfonamido group, oxycal
Bonylamino group, oxysulfonylamino group, substituted urethane
Id group (3-methylureido group, 3-phenylureido group,
3,3-dibutylureido group, thioureido group, acyl group
(Formyl group, acetyl group, etc.), oxycarbonyl group,
A substituted or unsubstituted carbamoyl group (ethyl carbamoy
Group, dibutylcarbamoyl group, dodecyloxypropyl
Rucarbamoyl group, 3- (2,4-di-t-aminophenoxy) p
Ropylcarbamoyl group, piperidinocarbonyl group, mole
Holinocarbonyl group, etc.), thiocarbonyl group, thiocal
Bamoyl, sulfonyl, sulfinyl, oxys
Ruphonyl group, sulfamoyl group, sulfino group, sulf
Ano group, carboxylic acid or its salt, sulfonic acid or its
Is preferably a phosphonic acid or a salt thereof,
R_TwoAnd R_ThreeIs closed to form a saturated carbocycle, aromatic carbocycle or
A terrorist aromatic ring may be formed. Of these, methyl
Group, ethyl group, alkyl group such as n-propyl group is a substituent
More preferably.

Specific examples of the complex of the present invention among the above-mentioned complexes using the imidazole derivative as a ligand are shown below, but the compounds of the present invention are not limited thereto.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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The central metal of the metal complex preferably used in the present invention is a ruthenium (III), titanium (IV), manganese (II), platinum (IV), and tin (IV) in a hexacoordination complex. And the four-coordinate complexes were Cu (II), Ni (II) and Co (II). In each complex the central metal Cl ^- has two or four combined with a titanium (IV) complexes, platinum (IV) complex,
Tin (IV), Cu (II), Ni (II) and Co (II) complexes are uncharged. In the four-coordinate complex, the [AgX ₄ ] ^3- unit in the silver halide grain is replaced with the complex molecule to be incorporated into the grain. These uncharged complexes are uncharged but soluble in water. However, since the titanium (IV) complex has a high deliquescence, it is desirable to handle it in a non-aqueous solution such as alcohol. To increase the solubility of the uncharged complex in water, the charge of the central metal
For example, the complex molecule may have a charge other than the IV value, and the complex molecule may have a charge. The ruthenium (III) complex and the manganese (II) complex are monovalent and divalent complexes, respectively. These charged complex molecules are completely dissociated from the counter ion in the aqueous solution to form an anion. Alternatively, the counterion is not important for photographic performance because it exists in the form of a cation. When the complex molecule becomes an anion and forms a salt with the cation, the counter cation is a sodium ion, potassium ion, rubidium ion, cesium which is easily dissolved in water and is suitable for the precipitation operation of the silver halide emulsion. 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

[0060]

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Where R_Five, R₆, R₇And R₈Is methyl
Group, ethyl group, propyl group, iso-propyl group, n-butyl
Represents a substituent arbitrarily selected from the groups. Above all, R_Five,
R₆, R ₇And R₈Are all the same substituents
Methyl ammonium ion, tetraethyl ammonium
Ion, tetrapropylammonium ion and tet
La (n-butyl) ammonium ion is preferred. Also,
From the convenience in synthesizing the complex, the compound represented by the above general formula I
H in the imine part of the compound⁺Imidazo with ions
It is also preferred that the lithium cation be a counter cation.

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

The complex used in combination with the hexacyano complex in the present invention can be synthesized by several methods. For example, a titanium complex and a tin complex can be obtained by reacting titanium tetrachloride or tin tetrachloride with an imidazole derivative under dry nitrogen while cooling. As a specific synthesis example, a method for synthesizing (bisimidazole) titanium tetrachloride and a tin complex thereof is described in J. Gen.
Chem. USSR 1967, 36, 1078, and other titanium complexes and tin complexes can be synthesized in a similar manner. Further, tetrachloromanganese complex, platinum complex, and ruthenium complex each having imidazole as a ligand are described in J.
Inst. Chem. (India) 1989, 61, 129; Russ. J. Inorg.
Chem. 1981, 26, 1179 and Inorg. Chem. 1987, 26, 844, and each derivative can be obtained in a similar manner. Also, (CuCl ₂ (2-MeIm) ₂ ) ⁰ , (NiCl
₂ (2-MeIm) ₂ ] ⁰ , [CoCl ₂ (2-MeIm) ₂ ] ⁰ (2-MeIm = 2-methylimidazole) can be synthesized by the method described in J. Chem. Soc. (A) 19
68, 128, and J. Chem. Soc. (A) 1967, 757. In the present invention, the synthesis was carried out based on these methods with modification for each individual compound.

The complex containing a hexacyano complex and an imidazole derivative in the present invention as a ligand may be added directly to a reaction solution at the time of forming silver halide grains, or may be added to an aqueous halide solution for forming silver halide grains. It is preferable to add it to the other solution and then to the silver halide grains by adding it to the grain forming reaction solution. Further, these methods may be combined to dope silver halide grains. In the case of titanium (IV) complex and cobalt (II) complex, the complex is dissolved in a small amount of methanol solution or ethanol solution separately from the silver nitrate aqueous solution and the halide aqueous solution, and added to the reaction solution simultaneously with the silver nitrate aqueous solution and the halide aqueous solution. Is most preferred. 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, or a complex having a hexacyano complex and an imidazole derivative as ligands may be doped by different methods.

In the present invention, when each of the complexes is doped into silver halide grains, both the hexacyano complex and the complex having an imidazole derivative as a ligand may be uniformly present inside the grains, or may be present only inside the grains. May be present. Further, they may be present in the particle surface layer, and as disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188373,
In both cases, high concentration doping may be performed by the particle surface layer.
These complexes do not need to be doped at the same position in the silver halide grains, and the complex-1 can be present in the grain surface layer and the complex-2 can be uniformly distributed in the grains, or only in the inside of the grains. Complex-2 may be present. Further, complex-2 may be present in the particle surface layer and complex-1 may be distributed in the layer immediately inside. In these, the complex-1 and the complex-2 may be present in the silver halide grains such that they are interchanged.
Nos. 5,252,451 and 5,25.
As disclosed in US Pat. No. 6,530, the particle surface phase may be modified by physical ripening with fine particles doped with these complexes.

The doping amount of each complex is suitably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻³ mol per mol of silver halide per mol of hexacyano complex, preferably from 1 × 10 ⁻³ mol to 1 × 10 ⁻³ mol per mol of silver halide. × 10 ^-6 or more 1 × 10 ^-4 mol, with respect to the complexes used in combination with hexacyano complex is suitably halide 1 1 × 10 ^-9 mol or more per mol 1 × 10 ^-3 mol or less, preferably 1 It is not less than × 10 ^{−8 and not} more than 1 × 10 ⁻⁴ mol.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochloride and silver iodobromide are used. be able to. Although the size of the silver halide grains is not limited, grains having a sphere equivalent diameter of 0.1 to 3 mm are preferred. The shape of the silver halide grains may be a regular crystal system (normal crystal grains), an irregular crystal system, or various shapes having one or more twin planes. Regular crystal systems include cubic, octahedral, dodecahedral, tetradecahedral, icosahedral and forty-octahedral. Irregular crystal forms include spherical and potato-like. Grains having one or more twin planes include hexagonal tabular grains and triangular tabular grains having two or three parallel twin planes. In the tabular grains, the grain size distribution is preferably monodispersed. The preparation of monodisperse tabular grains is described in JP-A-63-11928. Monodisperse hexagonal tabular grains are disclosed in
No. 151618. Circular monodisperse tabular grain emulsions are described in JP-A-1-131541. JP-A-2-838 discloses that at least 95% of the total projected area is occupied by tabular grains having two twin planes parallel to the main plane, and the size distribution of the tabular grains is small. Emulsions that are monodisperse are disclosed. European Patent 51
No. 4,742, A discloses a tabular grain emulsion having a grain size variation coefficient of 10% or less, prepared using a polyalkylene oxide block polymer.

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

The silver halide grains may have dislocation lines in the grains. With respect to the technique of introducing dislocations into silver halide grains while controlling the dislocations, see JP-A-63-22023.
No. 8, there is a description. According to this publication, a specific high iodine phase is provided inside a tabular silver halide grain having an average grain diameter / grain thickness ratio of 2 or more, and the outside thereof is covered with a phase having a lower iodine content than the high iodine phase. Thereby, dislocations can be introduced. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in stability of a latent image, and a reduction in pressure fog can be obtained. According to the invention described in this publication,
Dislocations are mainly introduced at the edge of tabular grains. Also,
Tabular grains having dislocations introduced at the center are described in US Pat. No. 5,238,796. further,
Japanese Patent Application Laid-Open No. 4-348337 discloses a normal crystal grain having a dislocation therein, wherein the normal crystal grain is formed with silver chloride or silver chlorobromide epitaxy, and the epitaxy is subjected to physical ripening and It is disclosed that dislocations can be introduced by conversion by halogen and / or halogen. The introduction of such dislocations has the effect of increasing sensitivity and reducing pressure fog. Dislocation lines in silver halide grains are described, for example, in JF Hamilton, Photo.
Sci. Eng. 1967, 11, 57, T. Shinozawa, J. Soc. Pho
JAPAN, 1972, 35, 213, can be observed by a direct method using a transmission electron microscope at low temperature. That is, silver halide grains taken out with care not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for electron microscope observation, and the sample is cooled so as to prevent damage (printout) by electron beams. Observation is performed by a transmission method in a state where the state has been set. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate.
Using an electron microscope (200 kV or more with respect to a thickness of m) enables more clear observation. From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from a plane perpendicular to the main plane can be obtained. The present invention is effective when 50% or more of the silver halide grains contain 10 or more dislocation lines per grain.

In the preparation of the silver halide emulsion, there is no particular limitation on the additives that can be added from the time of grain formation to the time of coating. A silver halide solvent can be used to promote growth during the crystal formation process, and to effectively enhance chemical sensitization during grain formation and / or chemical sensitization. As the silver halide solvent, water-soluble thiocyanates, ammonia, thioethers and thioureas can be used. Examples of the silver halide solvent include thiocyanates (U.S. Pat.
No. 448534 and No. 3320069).
Ammonia, thioether compound (US Pat.
Nos. 57, 3574628, 3704130, 4297439 and 4276347),
Thione compounds (JP-A Nos. 53-144319 and 53-143)
Nos. 82408 and 55-77737), amine compounds (described in JP-A-54-100717),
Thiourea derivatives (described in JP-A-55-2982), imidazoles (described in JP-A-54-100717) and substituted mercaptotetrazole (described in JP-A-57-2025)
No. 31).

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

Instead of adding a silver salt solution and a halogen solution to a reaction vessel, a method in which 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 amount of the sensitizing dye to be added is preferably 0.001 to 100 mmol per mol of silver halide, and is 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 each complex of the present invention. Can be done. 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 T
heory of the Photographic Process (published by Macmillan,
1977, 4th edition), by H. Frieser, Die Grundlagender P
hotographischen Prozess mit Silver-halogeniden (Ak
ademische Verlags-geselbshaft, 1968). Examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate), thioureas (eg, diphenylthiourea, triethylthiourea,
N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide, N-phenylthioacetamide), rhodanines (eg, rhodanine, N- Ethyl rhodanine, 5-benzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine, diethyl rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2- Thiones, dipolysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates and elemental sulfur are included. Activated gelatin can also be used as a sulfur sensitizer.

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

In the tellurium sensitizer, an unstable tellurium compound is used as a sensitizer. Unstable tellurium compounds are described in Canadian Patent No. 800,958;
295,462 and 1,396,696, JP-A-4-204640 and 4-271341.
And JP-A-4-330430 and JP-A-5-303157. Examples of tellurium sensitization include telluroureas (eg, tetramethyltellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylenetellurourea), phosphine tellurides (eg, butyl- Diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride,
Ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride , Bis (ethoxycarbonyl) telluride), isotellurocyanates (eg, allyl isotellurocyanate), telluroketones (eg, telluroacetone, telluroacetophenone), telluramides (eg, telluroacetamide, N, N-dimethyltellurobenzamide) , Tellurohydrazides (eg, N, N ',
N′-trimethyltellurobenzhydrazide), telluroesters (eg, t-butyl-t-hexyltelluroester), colloidal tellurium, (di) tellurides, and other tellurium compounds (eg, potassium telluride, telluropentathiol) Sodium salt).

In noble metal sensitization, a salt of a noble metal such as gold, platinum, palladium or iridium is used as a sensitizer. For precious metal salts, see P. Grafkides, Chimie et P
hysique Photographique (Paul Montel, 1987,
5th edition), Research Disclosure, Vol. 307, 307105
There is a description in the issue. Gold sensitization is particularly preferred. Examples of gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. In addition, U.S. Pat.
The gold compounds described in the specifications of JP-A Nos. 49,484 and 5,049,485 can also be used.

In the reduction sensitization, a reducing compound is used as a sensitizer. For reducing compounds, see P. Grafkide
s, Chimie et Physique Photographique (Paul Monte
l Publishing, 1987, 5th edition), Research Disclosure 30
No. 7, 307105. Examples of reduction sensitizers include aminoiminomethanesulfinic acid (thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine), polyamine compounds (eg, diethylenetriamine,
Triethylenetetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites,
Includes aldehyde compounds and hydrogen. Further, reduction sensitization can be carried out in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).

The chemical sensitization may be 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 used is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide,
It is preferably from ^{-7 to} 5 × 10 ^-3 mol. The use amount of the noble metal sensitizer is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. There are no particular restrictions on the conditions for chemical sensitization. The pAg is from 6 to 11, preferably from 7 to 10. Preferably, the pH is between 4 and 10. Temperature is 40 ~ 95 ℃
And more preferably 45 to 85 ° C.

The silver halide emulsion can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the 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 adding the antifoggant or the stabilizer is as follows.
Usually, it is performed after chemical sensitization, but it can be selected during chemical sensitization or at a time before the start of chemical sensitization. That is, during the formation of silver halide emulsion grains, even during the addition of the silver salt solution or during the period from the addition to the start of chemical sensitization, during chemical sensitization (during the chemical sensitization time, preferably 50% from the start). More preferably within 20% of the time).

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

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

B is a blue-sensitive layer, G is a green-sensitive layer, R is a red-sensitive layer, H is the highest-speed layer, M is an intermediate-speed layer, L is a low-speed layer, S is a support, and CL is a multilayer effect. Layer. Non-photosensitive layers such as a protective layer, a filter layer, an intermediate layer, an antihalation layer and an undercoat layer are omitted. The high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse.
(3) is described in US Pat. No. 4,184,876. For (4), Research Disclos
ure, Vol. 225, No. 22534, JP-A-59-177551
And JP-A-59-177552.
Further, (5) and (6) are described in JP-A-61-345.
No. 41 discloses this. Preferred layer constitutions are (1)
(2) and (4). The silver halide photographic material of the present invention can be similarly applied to X-ray photographic materials, black-and-white photographic materials, photographic materials for plate making, and photographic paper, in addition to color photographic materials.

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

種類 Additive type RD-17643 RD-18716 RD-22534 ── １ 1 Chemical sensitizer page 23 648 right column page 24 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648 right column page 24-28 Supersensitizer ~ page 649 right column 4 Brightening agent page 24 5 Anti-fogging agent, page 24-25 page 649 right column page 24, 31 Page Stabilizer 6 Light absorber, pages 25 to 26, page 649, right column Filter dye, 650 page 650, left column UV absorber 7 Stain inhibitor, page 25, right column, page 650, left column to right column 8 Dye image stabilizer page 25 Page 32 9 Hardener Page 26 Page 651 Left column Page 32 10 Binder 26 Same as above Page 28 11 Plasticizers and lubricants 27 Page 650 Right column 12 Coating aids, Pages 26 to 27 Same as above Surfactant 13 Static inhibitor Page 27 Same as above 14 Color coupler page 25 Page 649 Page 31 ───── ───────────────────────────

Examples of the gelatin hardener include 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.

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

[0093]

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 "Measurement of the existence time of photoelectrons" The measurement of the existence time of photoelectrons was carried out using a 35 GHz microwave in accordance with the method described in Photogr. Sci. Eng. 1984, 28, 92. Was measured. The measurement was performed at room temperature using a coating sample described later. For exposure, use the third harmonic of Nd-YAG laser.
5 nm light was applied. The existence time of photoelectrons was determined as the time until the intensity of microwave photoconductivity was reduced to 1 / e of the maximum intensity.

"Emulsion 1: Cubic silver chloride emulsion" 30 g of deionized gelatin was added to 1125 ml of an aqueous solution containing 4.8 g of sodium chloride.
The solution containing 24 ml of 1N nitric acid was added and dissolved, and while stirring at 45 ° C., 18 ml of a 0.35 M silver nitrate aqueous solution (solution 1) and 0.35 M
18 ml of an aqueous M sodium chloride solution (solution 2) was added quantitatively by the double jet method over 3 minutes. 10 minutes later, solution 1 (270ml)
And solution 2 (270 ml) were added by the double jet method for 18 minutes while accelerating the initial flow rate to 6 ml / min. 3 minutes later, 1.2
680 ml of M silver nitrate aqueous solution (solution 3) and 680 ml of 1.2 M sodium chloride aqueous solution (solution 4) were further added by a double jet method at an initial flow rate of 7 ml / min for 40 minutes while accelerating. From 28 minutes after the start of this addition to the end of the addition,
The solution was warmed to 60 ° C. over 12 minutes. Two minutes later, solution 3 (85
ml) and solution 4 (85 ml) were quantitatively added in 10 minutes by the double jet method. Four minutes after the completion of the addition, the temperature was lowered to 40 ° C., the soluble salts were removed by a normal sedimentation method, and then the temperature was raised to 40 ° C. again.
Gelatin was added and dissolved, and adjusted to pH 6.5. The resulting grains were monodispersed silver chloride cubes having a side length of 0.5 μm.

"Emulsion 2: Silver chloride cubic emulsion doped with [Fe (CN) ₆ ] ^4- " In the preparation of emulsion 1, 90% to 100% by volume of silver chloride particles were included in the surface layer. Emulsion 2 was prepared in the same manner as Emulsion 1, except that 1.5 × 10 ^-4 mol of [Fe (CN) ₆ ] ^4- was added per mol of silver.

"Emulsion 3: [CoCl ₂ (2-MeIm) ₂ ] ^0- doped silver chloride cubic emulsion] In the preparation of Emulsion 1, 90% to 100% of the silver chloride grains are contained in this portion in the surface layer. Emulsion 3 was prepared in the same manner as Emulsion 1, except that 1 × 10 ⁻⁷ mol of [CoCl ₂ (2-MeIm) ₂ ] ⁰ was added per mol of silver. [CoCl ₂ (2-MeIm) ₂ ] ⁰ was added as a methanol solution.

"Emulsion 4: [TiCl ₄ (2-proIm) ₂ ] ^0- doped silver chloride cubic emulsion"
Emulsion 4 was prepared in the same manner as Emulsion 1, except that 1 × 10 ⁻⁷ mol of [TiCl ₄ (2-proIm) ₂ ] ⁰ was uniformly added per mol of silver chloride grains. (TiCl ₄ (2-proI
m) ₂ ] ⁰ was added as a methanol solution.

"Emulsion 5: [Fe (CN) ₆ ] ^4- and [CoCl ₂ (2-Me
Im) ₂ ] ^0- doped silver chloride cubic emulsion ”(invention) In the preparation of Emulsion 2, in addition to containing [Fe (CN) ₆ ] ^4- in the surface layer of 90% to 100% of silver chloride particles, 1x per mole of silver
An emulsion containing 10 ^-7 moles of [CoCl ₂ (2-MeIm) ₂ ] ⁰ uniformly in the grains was prepared to obtain emulsion 5-1. In addition to the portion containing [[Fe (CN) ₆ ] ⁴⁻ of silver chloride particles, 1 × 10 ⁻⁷ mol of [CoCl ₂ (2-MeIm) ₂ ] ⁰ per mol of silver in this portion. Is prepared as emulsion 5-2, and silver 1 contained in this part is added to the same grain surface layer as the part containing [Fe (CN) ₆ ] ^4-.
An emulsion containing 1 × 10 ⁻⁷ mol of [CoCl ₂ (2-MeIm) ₂ ] ⁰ per mol was prepared to prepare Emulsion 5-3. In the preparation of Emulsion 1, a surface layer of 97% to 100% by volume of silver chloride particles was formed.
This part contains 3.3 × 10 ⁻⁷ mol of [CoCl ₂ (2-MeIm) ₂ ] ⁰ per mol of silver contained in this part, and the sub-surface layer of 87% to 97% by volume of silver chloride particles has this part. It was ⁴ moles of [Fe (CN) _6] ^4- emulsion 5-4 were prepared emulsion containing ^- per mole of silver 1.5 × 10 contained. Further, in the emulsion 5-3, the emulsion in which the added amount of [CoCl ₂ (2-MeIm) ₂ ] ⁰ was 1 × 10 ⁻⁶ mol per mol of silver contained in this portion was 5-3a,
The emulsion prepared at 5 × 10 ^-6 mol was 5-3b, the emulsion prepared at 1 × 10 ^-5 mol was 5-3c, and the emulsion prepared at 5 × 10 ^-5 mol was 5-3d. 5-4a was used for the emulsion in which the addition amount of CoCl ₂ (2-MeIm) ₂ ] ⁰ was 3.3 × 10 ^-6 mol per mol of silver contained in this portion, and 5-5a was used for the emulsion in which 1.7 × 10 ^-5 mol was used per mol of silver contained in this part.
Emulsions having 4b and 3.3 × 10 ^-5 moles were prepared as 5-4c, and those having 1.7 × 10 ^-4 moles as 5-4d were prepared. [CoCl ₂ (2-MeIm) ₂ ] ⁰ was added to the reaction solution as a methanol solution.

"Emulsion 6: [Fe (CN)₆]^Four-And [TiCl_Four(2-pr
oIm)_Two]⁰Doped silver chloride cubic emulsion "(Invention) In the preparation of Emulsion 2, 90% to 100% of silver chloride
(Fe (CN)₆]^Four-And 1 × per mole of silver
Ten^-7Mol of TiCl_Four(2-proIm)_Two]⁰Is uniformly contained in the particles.
The resulting emulsion was prepared as Emulsion 6-1. In addition, silver chloride particles
(Fe (CN)₆] ^Four-Other than the part containing
1 × 10^-7Mol of TiCl_Four(2-proIm)_Two]⁰Including
Emulsion 6-2, [Fe (CN)₆]^Four-Same as the part containing
One mole of silver contained in this part was applied to the part of the particle surface layer.
1 × 10^-7Mol of TiCl_Four(2-proIm)_Two]⁰Emulsion containing
This was prepared as Emulsion 6-3. Also, in preparing Emulsion 1,
To a surface layer of 97% to 100% by volume of silver chloride particles.
3.3 × 10 per mole of silver contained in the part^-7Mole of TiC
l_Four(2-proIm)_Two]⁰And the volume of silver chloride particles
87% to 97% of the subsurface layer
1.5 × 10 per le^-FourMoles of Fe (CN)₆]^Four-Emulsion containing
This was prepared as Emulsion 6-4. [TiCl_Four(2-proIm)_Two]⁰Hame
It was added to the reaction solution as a ethanol solution.

Emulsions 1 to 6 contained 8.2 × 10 ^-5 per mol of silver.
Mole compound, 6.8 × 10 ^-4 mole compound, 1.6 × 10 ^-4
Moles of the compound, 1.7 × 10 ⁻⁵ per mole of silver
Moles of sodium thiosulfate, 3.2 × 10 ^-5 per mole of silver
Molar potassium chloroaurate was added, and 7.4 × 10 ⁻⁴ moles of the compound were further added to optimally sensitize at 60 ° C. These emulsions were subjected to spectral sensitization by adding 3.8 × 10 ^-4 mol / mol Ag of the following sensitizing dyes.

[0102]

Embedded image

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 . A dye blank sample was also applied in the same manner as described above. Dye blank samples corresponding to emulsions 1 to 6 were coated samples 1 to 6, respectively, and dye-added samples were coated samples 7 to 12, respectively.

After applying sensitometric exposure (10 seconds or 10 ^-3 seconds) to these coated samples via an optical wedge,
After developing at 20 ° C. for 5 minutes with Developer 1 obtained by the following formulation, the solution was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured. Fog is determined by the minimum optical density of the sample. Sensitivity is expressed as the logarithm of the amount of exposure required to obtain an optical density of fog + 1.0. Doping with [Fe (CN) ₆ ] ^4- under each exposure condition The sensitivity of the sample coated with Emulsion 2 was expressed as a relative value with 100 as the sensitivity. The gradation is represented by the slope of the linear portion of the characteristic curve (the slope from fog + 0.2 to fog + 1.0). Table 2 shows the relative sensitivities when each of the coated samples 1 to 6 (spectral sensitizing dye blank sample) was exposed at a wavelength at which the intrinsic absorption of silver halide was observed, and Table 3 shows the coated samples 7 to 6.
The relative sensitivity when 12 samples (samples to which the spectral sensitizing dye was added) were exposed at a wavelength at which the spectral sensitizing dye had absorption was shown. Table 4 shows the relative sensitivities of the samples in which the addition amount of the dopant was changed (samples exposed to a wavelength at which the spectral sensitizing dye absorbed the dye-added sample).

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

[0106]

[Table 1]

Table 1 shows the existence time of photoelectrons. The photoelectron existence time is shown as the time until the intensity of the microwave photoconduction decreases to 1 / e. Since the emulsion used for the measurement was subjected to gold-sulfur sensitization, etc., and the inefficiency in the silver chloride grains was eliminated as much as possible, even if the emulsion was not doped with any complex, the photoelectrons remained for a relatively long time. Can exist. In the emulsion doped with only [Fe (CN) ₆ ] ^4- , the existence time of photoelectrons was about 1.4 times that of the undoped emulsion when no dye was added. On the other hand, (CoCl ₂ (2-MeIm) ₂ ) ⁰ (2-MeIm = 2-methylimidazole) or (TiCl ₄ (2-proIm) ₂ ) ⁰ (2-proIm = 2
In the emulsion doped with (-propylimidazole), the existence time of photoelectrons tends to increase slightly compared to the emulsion not doped with any complex, but this increase does not exceed the error range. Think. In an emulsion in which (Fe (CN) ₆ ) ^4- and (CoCl ₂ (2-MeIm) ₂ ) ⁰ were used together in the same grain, an emulsion in which both were mixed in a surface layer of 10% by grain volume,
And, [CoCl ₂ (2-MeIm) ₂ ] ⁰ complex was added to the surface layer of 3% by particle volume, and [Fe (CN) ₆ ] ^4- complex was added to the inner 10% subsurface layer. The existence time of photoelectrons was greatly extended in the emulsion, and especially in the latter, the existence time was 1.44 times that of the emulsion doped only with [Fe (CN) ₆ ] ^4- and almost double that of the undoped emulsion. In the case of Ti ^IV complex, the existence time of photoelectrons was prolonged when used together with [Fe (CN) ₆ ] ^4- in the same particle, but not only the emulsion where Co ^II complex was doped with Ti ^IV complex at the same doping position, but also , [Fe (CN) ₆ ] ^{4- in terms} of particle volume
It was found that even in an emulsion in which Ti ^IV complex was added uniformly in the grains and added to the surface layer of 10%, the existence time of photoelectrons was prolonged, and the existence time of photoelectrons was the longest at this time. The above is the case of the sample without the addition of the dye. However, the change of the existence time of the photoelectrons in the sample to which the dye was added was almost the same as that in the case where the dye was not added.

[0108]

[Table 2]

[0109]

[Table 3]

Table 2 shows the relative sensitivities of the dye blank samples of each emulsion when subjected to blue exposure. As is well known, the sample (Sample 2) doped only with [Fe (CN) ₆ ] ^4- becomes a large and highly sensitive emulsion as compared with the sample (Sample 1) not doped with any complex. ing. (TiCl ₄
The sample doped with (2-proIm) ₂ ] ⁰ (sample 4) is [Fe (C
N) ₆ ] A clear increase in sensitivity was observed, albeit inferior to the ^4- doped emulsion. The samples (6-1 to 6-4) in which these dopants are used together in one grain have higher sensitivity than the sample doped only with [Fe (CN) ₆ ] ^4- regardless of the dopant topography. Was. In particular, doping [Fe (CN) ₆ ] ^4- on the particle surface (90% to 100% of the particle volume)
_The emulsion having ₄ (2-proIm) ₂ ] ⁰ uniformly distributed in the grains was the emulsion having the highest sensitivity. Table 3 shows the relative sensitivity and gradation of the emulsion obtained by subjecting the dye-added sample to negative blue exposure.
For the Ti ^IV complex, as in the case of the sample without the dye added,
When used in combination with [Fe (CN) ₆ ] ^4- , a more sensitive emulsion was obtained, and the sensitivity was highest especially when the Ti ^IV complex was uniformly doped in the grains. Further, in the emulsion doped with the Co ^II complex, as in the case of the Ti ^IV complex, the emulsion doped alone had a higher sensitivity than the emulsion without the dope. When this Co ^II complex was used in combination with [Fe (CN) ₆ ] ^4- , all emulsions were more sensitive than the emulsions doped with [Fe (CN) ₆ ] ^4- alone, but the effect was large. As in the case of the Ti ^IV complex, it is greatly influenced by its topography,
Both (Fe (CN) ₆ ] ^4- and [CoCl ₂ (2-MeIm) ₂ ] ⁰ are localized on the particle surface (90% to 100% outside the particle volume), and when [CoCl ₂ (2- MeIm) ₂ ] ⁰ is the particle surface (outside the particle volume
97% to 100%) and [Fe (CN) ₆ ] ^4- were localized on the subsurfaces of the grains (87% to 97% of the grain volume), respectively, to obtain emulsions with high sensitivity. As can be seen from the correspondence between these results and the results in Table 1, in the emulsion containing [Fe (CN) ₆ ] ^4- , the emulsion in which the existence time of photoelectrons is longer has higher sensitivity, and the existence time of photoelectrons is increased. It has been shown that longer lengths have an effect on the sensitivity of the emulsion. In the emulsion containing only Co ^II complex or Ti ^IV complex, the relationship between the existence time of photoelectrons and the sensitivity is not clear, and it is predicted that sensitization is brought about by processes other than electronic processes, but the details are clear. Is not made. In addition, the emulsion doped with [Fe (CN) ₆ ] ^4- and Co ^II complex not only increased the sensitivity, but also exhibited the effect of hardening.However, the relationship between this effect and the existence time of photoelectrons is also presently unknown. Is not clear.

[0111]

[Table 4]

Table 4 shows that [Fe (CN) ₆ ] ^4- , [CoCl ₂ (2-MeI
m) ₂ ] ^{0 for} both particle surface (90% to 100% outside particle volume)
[CoCl ₂ (2-MeIm) ₂ ] ⁰ on the grain surface (97% to 100% outside the grain volume) and [Fe (CN) ₆ ] ^4- on the grain sub-surface (grain volume) (87% to 97%), the sensitivity and gradation of the emulsion with the local doping concentration of the Co ^II complex varied. In these emulsions, the sensitivity is high when the doping concentration of the Co ^II complex is low, and the sensitivity increases once the doping concentration increases, regardless of the position where the dopant is added. However, it was found that the sensitivity tends to increase again as the doping concentration is further increased. Although the details of this behavior are unknown, it is considered that these emulsions are preferably in the region where the concentration of the Co ^II complex is either lower or higher than in the intermediate region.

Example 2 "Measurement of the existence time of photoelectrons" The measurement of the existence time of photoelectrons was performed in the same manner as in Example 1 except for the exposure wavelength. For the exposure, Optical parametric Oscillation (460 nm) using the third harmonic (355 nm) of an Nd-YAG laser as an excitation light source was used. The existence time of photoelectrons was determined as the time until the intensity of microwave photoconduction decreased to 1 / e of the maximum intensity.

"Emulsion 7; Preparation of Sample of Silver Bromide Octahedral Emulsion" 36 g of deionized gelatin and 0.25 g of potassium bromide were dissolved in 895 ml of water. This gelatin aqueous solution is stirred while being kept at 75 ° C., and a 0.083 M silver nitrate aqueous solution (solution 5) 36 ml
And 0.083 M potassium bromide aqueous solution (solution 6) (36 ml) were added quantitatively by the double jet method over 10 minutes, followed by solution 5 (176.4
ml) and solution 6 (176.4 ml) were added in 7 minutes by the double jet method. One minute later, 14 ml of a 0.84 M aqueous potassium bromide solution was added, and one minute later, 675 ml of a 0.82 M silver nitrate aqueous solution (solution 7) was accelerated from a flow rate of 1.8 ml / min.
The addition was performed for 0 minutes, and at the same time, an aqueous 0.83 M potassium bromide solution (solution 8) was added while controlling the pBr at 2.93. 3 minutes after completion of addition, 1N sodium hydroxide
8.8 ml was added, and after one minute, solution 7 (222.5 ml) was added for 25 minutes, and at the same time, solution 8 was added while controlling to keep pBr 2.93. 1N 1 minute after the addition is completed
8.8 ml of sulfuric acid were added. After another minute, the temperature was lowered to 35 ° C., and the soluble salts were removed by the ordinary sedimentation method.
The temperature was raised to 40 ° C., 50 g of gelatin was added, and potassium bromide and zinc nitrate were added and dissolved to adjust the pH to 6.5. The resulting particles were monodisperse silver octahedrons having a sphere equivalent diameter of 0.68 mm.

"Emulsion 8: [Fe (CN) ₆ ] ^4- Doped Silver Bromide Octahedral Emulsion" In the preparation of Emulsion 7, this portion was added to a surface layer of 90% to 100% by volume of silver bromide particles. Silver contained in 1
Emulsion 8 was prepared in the same manner as Emulsion 7, except that 2.5 × 10 ^-4 mol of [Fe (CN) ₆ ] ^4- was added per mol.

"Emulsion 9: [CoCl ₂ (2-MeIm) ₂ ] ^0- Doped Silver Bromide Octahedral Emulsion"" Silver contained in 1
Emulsion 9 was prepared in the same manner as Emulsion 7, except that 1 × 10 ^-6 mol of [CoCl ₂ (2-MeIm) ₂ ] ⁰ was added per mol.

“Emulsion 10: [CoCl ₂ (2-proIm) ₂ ] ^0- doped silver bromide octahedral emulsion”
Emulsion 10 was prepared in exactly the same manner except that Cl ₂ (2-MeIm) ₂ ] ⁰ was changed to [CoCl ₂ (2-proIm) ₂ ] ⁰ .

"Emulsion 11: [TiCl ₄ (2-proIm) ₂ ] ^0- Doped Silver Bromide Octahedral Emulsion"
Emulsion 11 was prepared in the same manner as Emulsion 7, except that 1 × 10 ^-6 mol of [TiCl ₄ (2-proIm) ₂ ] ⁰ was uniformly added to the silver bromide grains per mol.

"Emulsion 12: [Fe (CN)₆]^Four-And [CoCl_Two(2-Me
Im)_Two]⁰-Doped silver bromide octahedral emulsion "(Invention) In the preparation of Emulsion 8, 90% to 100% of
(Fe (CN)₆]^Four-And 1 × per mole of silver
Ten^-6Mole of CoCl_Two(2-MeIm)_Two]⁰Is uniformly contained in the particles
The emulsion was prepared to obtain Emulsion 12-1. In addition, silver bromide particles
(Fe (CN)₆]^Four-In addition to the portion containing
1 × 10^-6Mole of CoCl_Two(2-MeIm)_Two]⁰Milk containing
Emulsion 12-2, (Fe (CN)₆]^Four-Same particles as the part containing
1 mol / mol of silver contained in this portion of the surface layer
× 10^-6Mole of CoCl_Two(2-MeIm)_Two]⁰Preparing an emulsion containing
Emulsion 12-3 was obtained. In the preparation of Emulsion 7,
97% to 100% surface layer by volume of silver particles contained in this part
3.3 × 10 per mole of silver^-6Mole of CoCl_Two(2-MeI
m)_Two]⁰From 87% to 9% by volume of silver bromide particles
2.5% per mole of silver contained in this part
× 10^-FourMoles of Fe (CN)₆ ]^Four-Prepare an emulsion containing
-4.

"Emulsion 13: [Fe (CN) ₆ ] ^4- and [CoCl ₂ (2-pr
OIM) _2] ⁰ silver bromide octahedral emulsion "doped (the invention) in the preparation of the emulsion 12, the [CoCl ₂ (2-MeIm) _2] ⁰ [CoCl
Emulsion 13-1 to Emulsion 13-4 were prepared in exactly the same manner as Emulsion 12, except that ₂ (2-proIm) ₂ ] ⁰ was substituted.

"Emulsion 14: [Fe (CN) ₆ ] ^4- and [TiCl ₄ (2-pr
oIm) ₂ ] ^0- doped silver bromide octahedral emulsion ”(this invention) In the preparation of Emulsion 12, [[CoCl ₂ (2-MeIm) ₂ ] ⁰
Emulsion 14-1 to Emulsion 14-4 were prepared in exactly the same manner as Emulsion 12, except that Cl ₄ (2-proIm) ₂ ] ⁰ was replaced.

The silver bromide emulsions 7 to 14 were added in an amount of 1.3 × 10 ^-5 mol of sodium thiosulfate, 6.5 × 10 ^-6 mol of chloroauric acid, and 3.5 × 10 ^-4 mol of thiocyanate per mol of silver. Potassium acid was added and optimally sensitized at 60 ° C.

Gelatin and sodium dodecylbenzenesulfonate were added to the chemically sensitized emulsions 7 to 14, respectively, and gelatin, polymethyl methacrylate particles, 2, and 3 were added to a triacetyl cellulose film support having an undercoat layer. Coating was carried out together with a protective layer containing sodium 4-dichloro-6-hydroxy-s-triazine at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 12 to 19. 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 for coated samples 12 to 19, and coated samples 20 to 27 I got

These samples were exposed to sensitometric exposure (1 second, 10 ⁻³ seconds) through an optical wedge, and then developed with a developer 2 having the following formulation at 20 ° C. for 10 minutes. Stopping, fixing, washing with water, and drying were performed by a conventional method, and the optical density was measured.
Fog is determined by the minimum optical density of the sample. Sensitivity is expressed as the logarithm of the amount of exposure required to obtain an optical density of fog + 1.0. Doping with [Fe (CN) ₆ ] ^4- under each exposure condition The value for the sample coated with Emulsion 8 was 100 and the relative value was expressed as 100. The gradation is represented by the slope of the linear portion of the characteristic curve (the slope from fog + 0.2 to fog + 1.0). Table 6 shows the coated samples 12 to 19 (spectral sensitizing dye blank samples), and Table 7 shows the coated samples 20 to 27 (samples to which the spectral sensitizing dye was added). The relative sensitivities when exposed at the given wavelengths are shown.

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.

[0126]

[Table 5]

Table 5 shows the existence time of photoelectrons. In the experiment here, Optical parametric Oscillation was used as the exposure light source when measuring the existence time of photoelectrons,
As a whole, the existence time of photoelectrons was observed to be short. In these silver bromide emulsions, the change in the existence time of photoelectrons was smaller than that in the silver chloride emulsion shown in Example 1. However, [Fe (CN) ₆ ] ^4- is contained in the particle surface layer of 90% to 100% by particle volume, and [CoCl ₂ (2-MeIm) ₂ ] ⁰ is uniform in the particles,
Or, [Fe (CN) _6] As seen in emulsion is in the same position as the ^4, [Fe (CN) _6] ^4- and [CoCl _{2 (2-MeI}
It was found that the emulsion containing m) ₂ ] ⁰ was clearly longer than the emulsion doped only with [Fe (CN) ₆ ] ^4- . On the other hand, in the emulsion using [Fe (CN) ₆ ] ^4- and [TiCl ₄ (2-proIm) ₂ ] ⁰ together, it was not possible to see a clear extension of the photoelectron existence time as in the case of silver chloride. .

[0128]

[Table 6]

[0129]

[Table 7]

Table 6 shows the photographic sensitivity and gradation of the dye blank sample. In the silver bromide octahedral emulsion, the emulsion doped with each Co ^II complex gives a highly sensitive emulsion without the addition of a dye.
[Fe (CN) ₆ ] ^{4- with} higher sensitivity than emulsion doped with ^IV complex
A sensitivity close to that of the emulsion doped with was obtained. The Co ^II complex than emulsions doped with [CoCl _{2 (2-proIm) 2]} ^0, [CoCl
_The emulsion doped with ₂ (2-MeIm) ₂ ] ⁰ was more sensitive. Emulsions doped with these Co ^II complexes together with [Fe (CN) ₆ ] ^4- in the surface layer of particles (90% to 100% of the particle volume) are better than emulsions doped only with [Fe (CN) ₆ ] ^4- The resulting emulsion was large and highly sensitive. Emulsions in which [Fe (CN) ₆ ] ^4- was placed on the surface layer of particles (90% to 100% of the particle volume) and the Co ^II complex was uniformly doped in the particles were equivalent to or slightly higher than this. It became a nice emulsion. On the other hand, an emulsion in which the Co ^II complex is doped on the particle surface (97% -100% of the particle volume) and [Fe (CN) ₆ ] ^4- is doped on the subsurface of the particle (87% -97% of the particle volume) The silver bromide octahedral emulsion did not give a highly sensitive emulsion, but was desensitized to a hard contrast emulsion. Although this increase in sensitivity and the increase in the existence time of photoelectrons are not as clear as in the case of silver chloride emulsions, a correspondence is also observed in the emulsions to which the dyes shown in Table 6 are not added, and the increase in sensitivity is large. Fe (CN) ₆ ) ^4- and (CoCl ₂ (2-
MeIm) ₂ ] ⁰ is added to the surface layer of the grains,
(CN) ₆ ] ^4- is present on the particle surface [CoCl ₂ (2-MeIm) ₂ ] ⁰
Was uniformly present in the grains, and the existence time of photoelectrons was longer than that of the sample doped only with [Fe (CN) ₆ ] ^4- .

A spectral sensitizing dye was added to each of the dope emulsions.
Table 7 shows the results of the samples subjected to the inus blue exposure.
did. In these samples, each Co^IIMilk with complex only
In the agent, (Fe (CN)₆]^Four-From the emulsion containing
The emulsion was highly sensitive, but these dopants and (Fe
(CN)₆]^Four-Emulsions combined with are more sensitive
Was. (CoCl_Two(2-MeIm)_Two]⁰− (Fe (CN)₆]^Four-Combination emulsion,
(CoCl_Two(2-proIm)_Two] ⁰− (Fe (CN)₆]^Four-Combination emulsion and
Also, (Fe (CN)₆]^Four-Emulsions and Co ^IIComplex
Is more sensitive than the emulsions used alone, especially
(Fe (CN)₆]^Four-The particle surface layer (90% to 100% of the particle volume)
%) (CoCl_Two(2-proIm)_Two]⁰Uniformly in the particles
The emulsion obtained was found to have high photographic sensitivity. [Ti
Cl_Four(2-proIm) _Two]⁰And [Fe (CN)₆]^Four-With emulsion
Also improved the sensitivity, but [CoCl_Two(2-proIm)_Two]⁰−
(Fe (CN)₆]^Four-It did not reach the sensitivity of the combined emulsion.

Example 3 "Emulsions 15 to 17; silver bromide octahedral emulsion (2)" Each of the emulsions obtained in Example 2 was optimally chemically sensitized and subjected to spectral sensitization.
A good result was obtained by using it as the emulsion of the third layer of the photosensitive material of Sample 201 of Example 2 of JP-A-9-146237 and performing the same processing as in the example of JP-A-9-146237.

Example 4 "Emulsions 18-20; silver bromide octahedral emulsion (3)" Each emulsion obtained in Example 2 was optimally chemically sensitized and subjected to spectral sensitization.
It was used as an emulsion for 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 gave good results.

[0134]

According to the present invention, an emulsion containing both a complex having an imidazole derivative as a ligand and a [Fe (CN) ₆ ] ⁴ -complex in one silver halide grain has a long photoelectron existence time. This is based on the finding that, as a result, there is an advantage in photographic characteristics. In particular, [CoCl ₂ (2-MeI
m) ₂ ) ⁰ , (CoCl ₂ (2-proIm) ₂ ) ⁰ , (TiCl ₄ (2-proIm)
m) ₂ ] ⁰ and [Fe (CN) ₆ ] ^4- were simultaneously doped into one silver halide grain, as compared with the emulsion doped only with [Fe (CN) ₆ ] ^4- as in the example. Thus, the existence time of photoelectrons becomes longer, and a silver halide photosensitive material having higher sensitivity and higher contrast can be obtained.

Claims (28)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
In the emulsion, a cyano complex represented by the following general formula I (complex-
1) and the use of the complex-1 together with the complex-1
A silver halide photographic light-sensitive material characterized in that the emulsion contains a complex (complex-2) having a function of prolonging the existence time of photoelectrons generated by exposure as compared with a case containing only the above. Formula I In the formula, M represents any metal, L represents any ligand, x is 3,
4, 5 or 6, n is -4, -3, -2 or -1. 2. The silver halide photographic light-sensitive material according to claim 1, comprising a complex-1 and a complex-2 having no cyanide ion as a ligand. 3. 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 complex-1 and complex-2 having no cyanide ion as a ligand. 4. The silver halide photographic light-sensitive material according to claim 3, comprising a complex 1 which is a hexacyano complex and a complex 2 which does not have a cyanide ion as a ligand. 5. A complex comprising a complex 6 which is a hexacyano complex and a chain or cyclic hydrocarbon as a parent structure, or wherein a part of carbon or hydrogen atoms of the parent structure is replaced by another atom or atomic group. Complex-2 with the substituted compound as ligand
4. The silver halide photographic light-sensitive material according to claim 3, comprising: 6. The silver halide photographic material according to claim 3, comprising a complex 1 which is a hexacyano complex and a complex 2 which has a heterocyclic compound as a ligand. 7. A complex 1 which is a 6-cyano complex and a compound represented by the following general formula:
4. The silver halide photographic material according to claim 3, comprising a complex-2 represented by II. Formula II In the formula, M ′ represents an arbitrary metal ion, L ′ is a compound represented by the general formula III, X is a halogen ion, and y is 1, 2
Or 3, m is -5, -4, -3, -2, -1, 0, +1 or +2. Formula III R ₁ , R ₂ , R ₃ and R ₄ in the formula may be the same or different, and include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group,
Aryl group, halogen, cyano group, nitro group, mercapto group, hydroxy group, alkoxy group, aryloxy group,
Alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, thioureido group, acyl group, oxycarbonyl group, Selected from carbamoyl, thiocarbonyl, thiocarbamoyl, sulfonyl, sulfinyl, oxysulfonyl, sulfamoyl, sulfino, sulfano, carboxylic acids and salts thereof, sulfonic acids and salts thereof, phosphonic acids and salts thereof Represents a substituent. Also, here, R ₂ and R ₃
May be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring. 8. A complex 1 which is a 6-cyano complex and a compound represented by the following general formula:
4. The silver halide photographic light-sensitive material according to claim 3, comprising a complex-2 represented by IV. General formula IV In the formula, M ″ represents an arbitrary metal ion, L ′ is a compound represented by the general formula III, X is a halogen ion, z is 1 or 2, k is −3, −2, −1, 0 , +1 or +2. 9. The silver halide photographic material according to claim 7, wherein M ′ in the general formula II is a metal ion selected from titanium, manganese, platinum and tin. 10. The silver halide photographic material according to claim 8, wherein M ″ in the general formula IV contains a complex that is a metal ion selected from cobalt, copper and nickel. 11. At least one of R ₁ , R ₂ and R _{3 in} the general formula III is a methyl group, an ethyl group, an n- or
The silver halide photographic material according to claim 9 or 10, wherein the substituent is a substituent selected from i-propyl groups. 12. The silver halide photographic material according to claim 11, wherein the complex-1 is hexacyanoruthenium or yellow blood salt. 13. The silver halide photographic material according to claim 11, wherein the complex-1 is a yellow blood salt. 14. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein a silver halide grain contained in the emulsion contains a 6-cyano complex (complex-3) and Alone does not extend the existence time of photoelectrons generated at the time of exposure, but when used together with complex-3, a complex (complex-4) having a function of extending the existence time of photoelectrons longer than that containing only complex-3 is obtained. A silver halide photographic light-sensitive material characterized by comprising: 15. A complex comprising Complex-3 and Complex-4 having no cyanide ion as a ligand.
The silver halide photographic light-sensitive material described in 1. 16. A complex in which a complex of Complex-3 and a chain or cyclic hydrocarbon is used as a parent structure, or a compound in which some carbon or hydrogen atoms of the parent structure are replaced by another atom or atomic group. 15. The silver halide photographic material according to claim 14, comprising a complex-4 as a ligand. 17. The silver halide photographic material according to claim 14, comprising a complex-3 having a complex-3 and a heterocyclic compound as a ligand. 18. The silver halide photographic material according to claim 14, comprising a complex-3 and a complex-4 represented by the general formula II. 19. The silver halide photographic material according to claim 14, comprising a complex-3 and a complex-4 represented by the general formula IV. 20. M 'in the general formula II is titanium, manganese,
19. The silver halide photographic material according to claim 18, wherein the material is a metal ion selected from platinum and tin. 21. The silver halide photographic material according to claim 19, wherein M ″ in the general formula IV is a metal ion selected from cobalt, copper and nickel. 22. At least one of R ₁ , R ₂ and R _{3 in} the general formula III is a methyl group, an ethyl group, an n- or
22. The silver halide photographic light-sensitive material according to claim 20, which is a substituent selected from i-propyl groups. 23. The silver halide photographic material according to claim 22, wherein the complex-3 is 6 cyanorthenium or yellow blood salt. 24. The silver halide photographic material according to claim 22, wherein the complex-3 is a yellow blood salt. 25. In a silver halide photographic material having at least one silver halide emulsion layer on a support, silver halide grains contained in the emulsion exceed complex-3 by at least 80% by grain volume. A silver halide photographic light-sensitive material, wherein the light-sensitive material is contained in the surface layer from part to 100%, and the same particle contains complex-4. 26. A silver halide grain comprising a complex-3 in a surface layer from at least 80% to 100% of the surface layer by grain volume, wherein the complex represented by the general formula II or IV is added to the same grain. 26. The silver halide photographic material according to claim 25, wherein 4 is uniformly contained in the grains. 27. A silver halide grain containing complex-3 in a surface layer from at least a portion of more than 80% to 100% in a grain volume, and the same grain is represented by the general formula II or the general formula IV. 26. The silver halide photographic light-sensitive material according to claim 25, wherein the complex-4 is contained in the same part of the grain where the complex-3 is contained. 28. A silver halide grain containing at least 90% of the grain volume of a complex-4 represented by the general formula II or IV.
26. The silver halide photographic light-sensitive material according to claim 25, wherein the complex-3 is contained in the surface layer in an amount of more than 100% to 100%, and 5% to 20% of the entire grain volume immediately inside the surface layer contains complex-3. material.