JPH10293377A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material having the capability of restraining a sensitivity drop due to the rise of contrasty, and having high contrasty as well as a sharp form at the foot of a characteristic curve by applying the constitution that a specific a ruthenium complex is contained in the silver halide grains of an emulsion. SOLUTION: Regarding a silver halide photosensitive material having at least one silver halide emulsion layer on a base material, silver halide grains contained in the emulsion are made to contain the ruthenium complex expressed by the formula I, where L stands for the compound expressed by the formula II, X for a halogen, (n) for a numeral of 4 or 5, (m) for a numeral of 1 or 2, and (1) for numerals of 0, -1 and -2. In the formula II, R1 to R4 stand for hydrogen atoms, or an alkyl group, an alkenyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, a halogen, a ciano group, a nitro group, a mercapto group, an aryl cio group, carboxylic acid or the slat thereof, a surfonic acid or the salt thereof, and the like. R2 and R3 may be cyclized to form a saturated carbocycle, an aromatic carbocycle or hetero- aromatic cycle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-doped silver halide photographic material. In particular, the present invention relates to a silver halide photographic material having a high sensitivity, a high contrast, and a sharp foot.

[0002]

2. Description of the Related Art Silver halide emulsions for photography are required to be practically harder. For example, it is desired that a photosensitive material for graphic arts has a high contrast even if the sensitivity is lowered. Here, the high contrast means the exposure amount on the horizontal axis,
This means that the gradient of the gradation portion (linear portion) of the characteristic curve when the optical density is represented on the vertical axis is large. Regarding the gradation, it is also important that the toe of the characteristic curve is cut off (the characteristic curve has a sharp rise in an exposure amount region where the optical density starts to increase). As in the case of graphic arts photosensitive materials, even in silver halide photographic materials such as color photographic paper, the fact that the portion corresponding to the low-density portion of the characteristic curve has a high contrast, that is, that the legs are cut, indicates that there is no omission. It is desirable to obtain good crisp images.

As described above, high contrast silver halide photographic light
One way to obtain materials is to use metal doping technology
is there. Metal doping technology means metal ion alone or coordination
Incorporation of Metal Complexes Containing Metal into Silver Halide Grains
(Doping) technology, which allows
The properties of the grains have been modified so that the overall performance of the emulsion is expected.
Can be improved. By metal doping technology, hard
Group VIII metal ion
It is known to dope compounds containing
Rhodium trichloride (UK Patent No. 77
No. 5197), ruthenium, palladium, osmium, platinum
Of each salt (Photog. Sci. And Eng. 27 (2) p81, 1983 and
And Research Disclosure 13452 June 1975)
I have been. Emulsions doped with these compounds have high contrast
It becomes a photographic material, but with a large loss in sensitivity
Was. In JP-A-63-184740 (publication), K_TwoRuCl_Five(OH_Two)
The first ruthenium compound was applied per mole of silver halide.
10^-9~Ten^-FourIncluding moles and K_ThreeIrCl₆And others
The iridium compound is added in an amount of 10 per mole of silver halide.^-7~Ten ^-Five
By obtaining emulsion containing moles, high gradation photographic materials
Have gained. With this technology, ruthenium compounds can be used alone
In some cases, sensitivity is attributed to reciprocity failure
Or there is a significant loss in gradation,
Iridium compounds as additional compounds
Was essential. Japanese Patent Laid-Open No. 2-3032 discloses
Halogenating ruthenium salts such as lolorthenium
1 × 10 per mole of silver^-9~ 1 × 10^-FiveContains moles and hides
An emulsion containing a azine compound is used to obtain a high contrast image.
Although it is disclosed as a loop technology, in this technology,
To obtain the desired photographic performance, in addition to the dopant,
It was necessary to use a drazine compound. Also,
In Kaihei 2-20852, nitrosyl or thionitros
By doping a transition metal complex with
Indicates that a high gradation photographic material can be obtained.
However, this was again accompanied by a significant decrease in sensitivity.

As described above, in a high-contrast silver halide photographic light-sensitive material achieved by the doping technique, as the gradation becomes higher only with a single dopant, the sensitivity is greatly reduced, and the high sensitivity is maintained while maintaining the gradation. In order to obtain high gradation while maintaining sensitivity, it was necessary to use other techniques in addition to a single dopant. Furthermore, when some complexes are used as dopant species, such as a rhodium complex having a chloride ion as a ligand, the composition of the complex changes sensitively depending on the halogen concentration in the aqueous solution, and a single complex in the aqueous solution is formed. It is difficult to handle as a substance, and as a result, it is difficult to keep the performance of the photographic light-sensitive material constant due to a plurality of doped species (K. Endo and M.
Saikawa, J. Photogr. Sci., 38, 210 (1990)).

[0005]

SUMMARY OF THE INVENTION In the present invention, a silver halide is provided which minimizes the decrease in sensitivity due to the increase in contrast observed in the conventional doping techniques, and which has a sharper characteristic curve with a sharper curve. It is an object of the present invention to provide a photographic material and to provide a silver halide light-sensitive material which always provides constant photographic performance irrespective of the halogen concentration in an aqueous solution.

[0006]

According to the present invention, in a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the emulsion are represented by the general formula I It has been found that the above object can be achieved by a silver halide photographic material characterized by containing a ruthenium complex represented by the formula: General formula I

[0007]

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In the formula, L is a compound represented by the general formula II, X
Is halogen, n is 4 or 5, m is 1 or 2,
l is 0, -1, -2. General formula II

[0009]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, aryl, halogen, cyano, nitro, Mercapto group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, Ureido group, thioureido group, acyl group, oxycarbonyl group, carbamoyl group, thiocarbonyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group, sulfano group, carboxylic acid or a salt thereof,
It represents sulfonic acid or a salt thereof, phosphonic acid or a salt thereof. Here, R ₂ and R ₃ are closed to form a saturated carbocycle,
It may form an aromatic carbocyclic or heteroaromatic ring.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The complex used for doping in the present invention will be described in detail below.

In the above general formula I, the Ru complex is represented by n =
It is preferable that the composition has a composition of 5, m = 1 and l = -2, and X = Cl ⁻ .

The metal complex used in the present invention is completely dissociated from the counter cation in the aqueous solution and exists in the form of an anion. Therefore, the counter cation is not important for photographic performance. As counter cations, alkali metal ions such as sodium ion, potassium ion, rubidium ion, and cesium ion, which are easily dissolved in water when forming a salt with a complex anion and are suitable for the precipitation operation of a silver halide emulsion. , An ammonium ion, or an alkyl ammonium ion represented by the following general formula III is preferably used. General formula III

[0014]

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Wherein R ₅ , R ₆ , R ₇ and R ₈ are methyl, ethyl, propyl, iso-propyl, n-
Represents a substituent arbitrarily selected from a butyl group. Above all, R
_5, R _6, R ₇ and R ₈ are all equal substituent tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n- butyl) ammonium ion. Further, from the viewpoint of convenience in synthesizing the complex, it is also preferable to use, as a counter cation, an imidazolium cation in which an H ⁺ ion is added to the imine portion of the compound represented by the general formula II.

In the above general formula II used as a ligand of the ruthenium complex in the present invention, R ₁ , R ₂ , R ₃
And R ₄ are a hydrogen atom or a substituted or unsubstituted alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group,
Octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, t-octyl group, isodecyl group, isostearyl group, dodecyloxypropyl group, trifluoromethyl group, methanesulfonylaminomethyl group, etc.), alkenyl group, alkynyl group, Aralkyl groups, cycloalkyl groups (cyclohexyl group, 4-t-butylcyclohexyl group, etc.), substituted or unsubstituted aryl groups (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, bromine, iodine), cyano group Nitro group, mercapto group, hydroxy group, alkoxy group (methoxy group, butoxy group, methoxyethoxy group, dodecyloxy group, 2-ethylhexyloxy group, etc.), aryloxy group (phenoxy group, p-
Alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, substituted or unsubstituted amino group (amino group, methylamino group, dimethylamino group, anilino group) such as tolyloxy group, p-chlorophenoxy group, 4-t-butylphenoxy group, etc. Group, N-methylanilino group, etc.),
Ammonio group, carbonamide group, sulfonamide group,
An oxycarbonylamino group, an oxysulfonylamino group, a substituted ureido group (3-methylureido group, 3-phenylureido group, 3,3-dibutylureido group, etc., a thioureido group, an acyl group (formyl group, acetyl group, etc.),
Oxycarbonyl group, substituted or unsubstituted carbamoyl group (ethyl carbamoyl group, dibutyl carbamoyl group,
Dodecyloxypropylcarbamoyl group, 3- (2,4
-Di-t-aminophenoxy) propylcarbamoyl group, piperidinocarbonyl group, morpholinocarbonyl group, etc.), thiocarbonyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group, sulfano group , A carboxylic group or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof. Here, R ₂ and R ₃ may be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring. Among them, methyl group, ethyl group, n-
A propyl group and a formyl group are preferred.

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

[0018]

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[0019]

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The complex of the present invention can be synthesized by several methods. For example, it can be obtained by reacting ruthenium trichloride with an imidazole derivative in hydrochloric acid. As a specific synthesis example, a method for synthesizing bis (imidazolium) (imidazole) pentachlororuthenate is described in the literature (Inorg.Chem., 26,844 (1987)), and other complexes are synthesized by a similar method. You can do it.

The ruthenium complex of the present invention 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, or to another solution. It is preferable that the silver halide grains are contained in the silver halide grains by being added to the formation reaction solution. Further, these methods may be combined to dope silver halide grains.

When the ruthenium metal complex of the present invention is doped into silver halide grains, the silver halide grains may be uniformly present in the grains, or may be used as described in JP-A-4-208936 and JP-A-2-12-12.
As described in JP-A No. 5245 and JP-A-3-18837, a high concentration doping may be performed on the particle surface layer. No. 5,252,451 and US Pat.
As disclosed in U.S. Patent No. 256,530, the grain surface phase may be modified by physical ripening with doped fine particles.
Further, a method in which fine particles doped with a complex are prepared, and the fine particles are added and physically ripened to dope the silver halide particles with the complex is also preferable. Further, the above doping methods may be used in combination.

The doping amount of the ruthenium complex is suitably from 1 × 10 ⁻⁸ mol to 1 × 10 ⁻³ mol, and preferably from 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol, per mol of silver halide. It is.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochloride, and silver iodobromide are used. However, it is desirable that the silver chloride is silver chloride or silver chlorobromide in which 50 mol% or more is silver chloride. It is preferably silver chloride or silver chlorobromide in which 90% or more is silver chloride, and more preferably pure silver chloride grains. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but a cubic is preferred. The average grain size of the silver halide is preferably from 0.1 μm to 0.7 μm, more preferably from 0.1 μm to 0.5 μm,
It is preferable that the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10% or less, with a narrow particle size distribution.

In the silver halide grains, the inside and the surface layer may have a uniform phase or may be different. Further, a localized layer having a different halogen composition may be provided inside or on the surface of the grain.

The photographic emulsion used in the present invention is P. Glafki
by des Chimie et Physique Photograhique (Paul Monte
l Publisher, 1967), GFDufin, Photographic Emuls
ionChemistry (The Forcal Press, 1966), VLZel
Making and Coating Photographic Emuls by ikman et al
ion (The Forcal Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt and a soluble halide salt may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. Is also good.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. 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, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds, described in JP-A-53-82408 and JP-A-55-77737.
No. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent to be added varies depending on the type of the compound used, the intended grain size, and the halogen composition, but it is 10 ^-5 to 1 per mol of silver halide.
0 ^-2 mol is preferred.

In the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions.

In order to make the particle size uniform,
British Patent No. 1,535,016, JP-B-48-368
Nos. 90 and 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide in accordance with the grain growth rate, and British Patent No. 4,242,
No. 445 and Japanese Patent Application Laid-Open No. 55-158124, it is preferable to use a method of changing the concentration of the aqueous solution and to grow the solution quickly within a range not exceeding the critical saturation.

The emulsion of the present invention is preferably a monodisperse emulsion.
The coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 20% or less, more preferably 15% or less.

The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm
０．５0.5 μm.

The silver halide emulsion used in the present invention is:
It may contain a metal ion belonging to Group VIII or a metal complex having them as a central metal. In order to achieve high contrast and low fog, it is preferable to contain, for example, a ruthenium compound having OH ₂ , a halogen ion or the like as a ligand other than the rhodium compound, the iridium compound, and the heterocyclic derivative. In addition, K ₄ (Fe (C
Doping with a hexacyano metal complex such as N) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageously performed.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex as a ligand such as halogen, amines, oxalato,
Those having water and the like, for example, hexachlororhodium (III) complex, pentachloroaquarhodium complex, tetrachlorodiaquarhodium complex, hexabromorhodium (III) complex, hexaaminerhodium (III) complex, trizalatrodium (III) ) Complexes and the like. These rhodium compounds are used after being dissolved in water or a suitable solvent.
Commonly used methods for stabilizing solutions of rhodium compounds include aqueous hydrogen halide solutions (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or alkali halides (eg, KCl, NaCl, KBr, NaBr) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

Rhenium, ruthenium and osmium used in the present invention are described in JP-A-63-2042 and
Nos. 285941 and 2-20852 and 2-2085
It is added in the form of a water-soluble complex described in No. 5, etc. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ^n- where M represents Ru, Re or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counter ion is not important, and an ammonium ion or an alkali metal ion is used. Preferred ligands L include OH ₂ , halogen ions, cyanide, cyanic acid,
Ligands such as nitrosyl and thionitrosyl;
Need not all be the same ligand. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [ReBr ₅ (NS)] ^2- [Re (CN) ₅ (NO)] ^2- [ReO ₂ (CN ) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₅ (OH ₂ )] ^2- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CO) Br ₅ ] ^2- [ OsCl ₆ ] ^3- [OsCl ₅ (NO)] ^2- [Os (CN) ₅ (NO)] ^2- [OsBr ₅ (NS)] ^2- [Os (CN) ₆ ] ^4- [OsO ₂ (CN) ₄ ] ^4-

The addition amount of these compounds is 1
It is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol per mol, particularly preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol.

Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, hexaammineiridium, and pentachloronitrosyliridium. Examples of the ruthenium compound used in the present invention include hexachlororuthenium and pentachloronitrosylruthenium. Examples of the iron compound used in the present invention include potassium hexacyanoferrate (II) and ferrous thiocyanate.

The doping amount and the doping ratio of the metal complex of the present study in the silver halide grains were determined by the atomic absorption method and the inductively coupled method (ICP method).
Plasma Spectrometry; ICPMS (Inductively Coupled Plas)
ma Mass Spectrometry)
Can be quantified by using the above method.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, a noble metal sensitization method, and the like can be used, and these are used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

The sulfur sensitization method used in the present invention is usually
This is performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The addition amount of the sulfur sensitizer varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 1
0 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is,
Usually, an unstable type and / or a non-unstable type selenium compound is added, and the emulsion is stirred at a high temperature of 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748, JP-B-43-13489, JP-A-3-217061, JP-A-4-109240, and JP-A-4-109240.
Compounds described in 324855 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in No. 31284.

Specifically, US Pat. No. 1,623,49
No. 9, No. 3,320,069, No. 3,772,0
No. 31, British Patent Nos. 235,211 and 1,12
No. 1,496, No. 1.295,462, No. 1,3
96,696, Canadian Patent No. 800,958, JP-A-4-204640, JP-A-4-271341, and JP-A-4-271341.
No. 333043, No. 5-303157, Journal
Of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibi
d, 1102 (1979), ibid, 645 (1979), Journal of
Chemical Society Perkin Transaction (J. Chem., Soc. Perkin. Trans.) 1,2191 (1980), S. Pata
i ed., The Chemistry of Organic Selenium and Tellurium Campounds
stry of Organic Serenium and Tellunium Compounds),
The compounds described in Vol. 1 (1986) and Vol. 2 (1987) can be used. Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

The noble metal sensitization method used in the present invention includes gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 per mol of silver halide. About moles can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may be coexistent during the formation or physical ripening of silver halide grains.

In the present invention, reduction sensitization can be used. As reduction sensitizers, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in European Patent Application No. 293,917.

The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example,
Particles having different average particle sizes and different sensitivity). Above all, to obtain high contrast,
As described in JP-A-6-324426, it is preferable to coat an emulsion having a higher sensitivity as it is closer to the support.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used.

Useful sensitizing dyes for use in the present invention include, for example, Research Disclosu
re) Item 17643 Item IV-A (p.23, December 1978), Item
18341 References cited or cited in Section X (August 1979, p. 437).

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected.

For example, A) for an argon laser light source, compounds of (I) -1 to (I) -8 described in JP-A-60-162247 and I-I- described in JP-A-2-48653.
Compounds 1 to I-28, compounds I-1 to 1-13 described in JP-A-4-330434, U.S. Pat. No. 2,16
The compounds of Examples 1 to 14 described in U.S. Pat. No. 1,331, the compounds of 1 to 7 described in German Patent No. 936,071 and B) A helium-neon laser light source are described in JP-A-54-18726. Compounds described in I-1 to I-38 described in JP-A-6-75322;
35 compounds and I described in JP-A-7-287338.
Compounds -1 to I-34; C) For LED light sources, compounds 1 to 20 described in JP-B-55-39818, and compounds of I-1 to I-37 described in JP-A-62-284343. And compounds of I-1 to I-34 described in JP-A-7-287338, and D) For a semiconductor laser light source, I-1 to I-12 described in JP-A-59-191332.
The compound of I-1 to I-22 described in JP-A-60-80841, the compound of I-1 to I-29 described in JP-A-4-335342, and the compound of JP-A-59-1922
Compounds I-1 to I-18 described in JP-A-42-42, E) Tungsten and xenon light sources for plate making cameras are represented by the general formula [1] described in JP-A-55-45015.
Compounds (1) to (19), compounds I-1 to I-97 described in Japanese Patent Application No. 7-346193, and JP-A-6-242.
Compounds of 4-A to 4-S, compounds of 5-A to 5-Q, compounds of 6-A to 6-T described in No. 547 are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect, or a substance which does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, 17643 (1978).
Issued on December 23), page 23, IV, J, or JP-B-49-2
Nos. 5500 and 43-4933, and JP-A-59-190.
32 and 59-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvents such as -tetrafluoropropanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like may be dissolved in a mixed solvent or added to the emulsion.

Further, as disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding a dispersion to an emulsion,
No. 23389, No. 44-27555, No. 57-220
As disclosed in No. 91 or the like, a dye is dissolved in an acid,
A method in which the solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or a base, U.S. Pat.
Nos. 822, 135 and 4,006,025, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion, No. 102733, No. 58-10514
A method of directly dispersing a dye in a hydrophilic colloid as disclosed in No. 1 and adding the dispersion to an emulsion. As disclosed in JP-A-51-74624, a method of dissolving a dye using a compound for red shifting and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the silver halide grain forming step and / or before the desalting, during the desilvering step and / or after the desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after the chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step, during the chemical ripening step, or when the chemical ripening is completed. May be divided and added before or after completion of chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be divided and added. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. ^Per mol of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is preferable.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as needed. Preferred layer arrangement is red-sensitive from the support side,
The order is green-sensitive and blue-sensitive, the order of blue-sensitive layer, green-sensitive layer and red-sensitive layer or the order of blue-sensitive, red-sensitive and green-sensitive. Any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or may be composed of three layers to further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer such as fine grain silver halide may be provided under the high-sensitivity layer, particularly under the high-sensitivity blue-sensitive layer to improve the sensitivity. It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations may be used depending on the case. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Various color couplers can be used in the photographic material of the present invention, and specific examples thereof are described in Research Disclosure, Vol. 176, No. 17643 (1978), VII-C.
-G are described in the patents. As the yellow coupler, for example, US Pat. No. 3,933,501
No. 4,022,620, No. 4,326,02
No. 4, No. 4,401,752, JP-B-58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760 are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. For example, US Pat. Nos. 4,310,619 and 4,351,
897; EP 73,636; US Pat.
Nos. 061,432 and 3,725,067, Research Disclosure 24,220 (1984), and
-335552, Research Disclosure 24,
No. 230 (1984), JP-A-60-43659 and U.S. Pat. Nos. 4,500,630 and 4,540,654 are preferred. Examples of the cyan coupler include phenol-based and naphthol-based couplers. For example, U.S. Pat. Nos. 4,052,212 and 4,146,39.
No. 6, No. 4,228,233, No. 4,296,2
No. 00, No. 2,369,929, No. 2,801,
No. 171, No. 2,772,162, No. 2,89
No. 5,826, No. 3,772,002, No. 3,7
No. 58,309, No. 4,334,011, No. 4,
No. 327,173, West German Patent Publication No. 3,329,729.
Patent No. EP 121,365A, US Patent No. 3,4
No. 46,622, No. 4,333,999, No. 4,
Preferred are those described in 451,559, 4,427,767 and EP 161626A.

Colored couplers for correcting unnecessary absorption of coloring dyes are described, for example, in the aforementioned Research Disclosure, Vol. 176, No. 17643 (1978), section VII-G, US Pat. No. 4,163,670, and JP-B-57. -39413, U.S. Pat. Nos. 4,004,926 and 4,138,25.
No. 8 and British Patent No. 1,146,368 are preferred.

Examples of couplers in which a coloring dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,57.
No. 0 and West German Patent (Publication) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,084,820.
Nos. 0,211 and 4,367,282, and British Patent No. 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler that releases the development inhibitor is described in Research Disclosure, Vol. 176, No. 17643 (1978).
Patents described in section IF, JP-A-57-151944
No., No. 57-154234, No. 60-184248
And those described in U.S. Pat. No. 4,248,962 are preferred. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No.
Nos. 097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, US Pat.
No. 4,427, the competing couplers described in U.S. Pat.
No. 283,472, No. 4,338,393, No. 4,310,618, etc., and multi-equivalent couplers described in JP-A-60-185950, JP-A-50-24252, etc. Redox compounds or DIR coupler-releasing couplers, couplers which release dyes that recolor after release as described in EP 173,302A;
Disclosure No. 11449, No. 24241, JP-A-61
And bleach accelerator releasing couplers described in U.S. Pat. No. 4,553,477 and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound described in EP 277,589 A2 together with a coupler. In particular, a combination with a pyrazoloazole coupler or a pyrrolotriazole coupler is preferable. That is, a compound that chemically bonds to an aromatic amine-based developing agent remaining after the color developing process to form a chemically inert and substantially colorless compound, and / or an aromatic amine-based compound remaining after the color developing process. It is possible to simultaneously or solely use a compound that chemically reacts with the oxidized form of the color developing agent to form a chemically inert and substantially colorless compound, for example, a color developing agent remaining in a film upon storage after processing. Further, it is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the oxidized product and the coupler.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Is preferably added.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure 17123
No. (1978), or by using a black color coupler described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136. Thus, the present invention can be applied to black-and-white photosensitive materials for X-rays and the like. Plate making films such as squirrel film or scanner film,
The present invention is also applicable to indirect medical or industrial X-ray films, negative black-and-white films for photography, black-and-white photographic paper, COM or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, a peeling (peel apartment) type or JP-B-46-16356, JP-B-48-33697,
JP-A-50-13040 and British Patent 1,33
No. 5,524, the rigidity of a peeling-free film unit can be obtained. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above types of formats is advantageous in widening the processing temperature latitude. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used by being sealed in a processing solution container as a developing solution component.

[0074]

The present invention will be described below in more detail with reference to specific examples, but the present invention is not limited thereto. Example 1 "Emulsion 1: Silver chloride cubic emulsion" 4.5 g of sodium chloride
A solution prepared by adding 25 g of deionized gelatin to 845 ml of an aqueous solution containing
140 ml of an aqueous silver nitrate solution (solution 1) and 140 ml of a 0.21 M aqueous sodium chloride solution (solution 2) were quantitatively added for 10 minutes by a double jet method. After 10 minutes, 320 ml of a 2.2M aqueous solution of silver nitrate (solution 3) and 320 ml of a 2.2M aqueous solution of sodium chloride (solution 4) were further quantitatively added for 35 minutes by a double jet method. Five minutes after the completion of the addition, the temperature was lowered to 35 ° C., the soluble salts were removed by a normal sedimentation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and sodium chloride and phenol were further added. The pH was adjusted to 6.5. The obtained grains were monodispersed silver chloride cubes having a side length of 0.5 μm.

"Emulsion 2;" A silver chloride cubic emulsion doped with (NH ₄ ) ₂ [RhCl ₅ (OH) ₂ ] "(comparative example) (NH ₄ ) ₂ [RhCl ₅ (OH) ₂ ] is 2.8 × 10
Emulsion 2 was prepared in the same manner as Emulsion 1 except that the emulsion was contained at a concentration of ^-6 moldm ^-3 .

"Emulsion 3:" A silver chloride cubic emulsion doped with K ₂ [RuCl ₅ (NO)] "(Comparative Example) K ₂ [RuCl ₅ (NO)] was added to Solution 4 of Emulsion 1 at 2.8 × 10 4 ^-6 m
Emulsion 3 was prepared in the same manner as Emulsion 1, except that it contained at a concentration of oldm- ³ .

"Emulsion 4;" Cu3 Cubic Emulsion Doped with K ₃ [RuCl ₆ ] "(Comparative Example) K ₃ [RuCl ₆ ] was added to solution 4 of Emulsion 1 at 2.8 × 10 ^-6 moldm
Emulsion 4 was prepared in the same manner as Emulsion 1, except that it was contained at a concentration of ^-3 .

"Emulsion 5;" A silver chloride cubic emulsion doped with K ₂ [RuCl ₅ (OH ₂ )] "(Comparative Example) 2.8 of K ₂ [RuCl ₅ (OH ₂ )] was added to Solution 4 of Emulsion 1. × 10 ^-6 m
Emulsion 5 was prepared in the same manner as Emulsion 1, except that it contained at a concentration of oldm- ³ .

"Emulsion 6;" A silver chloride cubic emulsion doped with K ₃ [Cr (CN) ₆ ] "(Comparative Example) K ₃ [Cr (CN) ₆ ] was added to Solution 4 of Emulsion 1 at 2.8 × 10 4 ^-6 mol
Emulsion 6 was prepared in the same manner as Emulsion 1, except that it contained dm- ³ .

"Emulsions 7 to 18; Cubic silver chloride emulsion doped with the ruthenium complex of the present invention" (Invention) The ruthenium complex of the present invention was added to Solution 4 of Emulsion 1 at 2.8 × 1.
Except at a concentration of 0 ^-6 moldm ^-3 were prepared emulsion 7 to 18 obtained in the same manner as Emulsion 1.

Among the above emulsions 7 to 18, the doping ratio in the silver halide grains of the pentachlororuthenium complex having 5-imidazolecarboxaldehyde, 2-propylimidazole and 2-methylimidazole as ligands was determined. The doping ratio was 52%, 63%, and 68%, respectively, as determined by atomic absorption spectrometry of ruthenium, which is the central metal of the metal complex thus obtained.

From the ESR spectra of the three complexes whose doping rates were measured, all of these complexes were found in the emulsion in the same manner as in the case of the conventionally known hexachlororuthenium complex or pentachloroaquaruthenium complex. The ruthenium ion of the central metal was found to be trivalent. Further, from the ESR spectrum, it was found that the ruthenium ion was changed to divalent by exposing these doped emulsions.

In each of the complexes used in the present invention, a halogen ion (Cl ^- ion, Br
^- even under the condition where ions) are present in large excess, at room temperature for 3 hours the visible - change in the ultraviolet absorption spectrum was observed.

Emulsions 1 to 18 contained 1.8 × 1 per mole of silver.
0 ^-2 mol of 4-hydroxy-6-methyl-1,3,3
After addition of a, 7-tetrazaindene, 2.5 × 10 ⁻⁶ mole of sodium thiosulfate per mole of silver was added,
Optimal chemical sensitization at 0 ° C.

Gelatin and sodium dodecylbenzenesulfonate were added to these chemically sensitized emulsions, and gelatin, polymethyl methacrylate particles,
Coating was carried out together with a protective layer containing 2,4-dichloro-6-hydroxy-s-triazine sodium salt at a silver amount of 2 g / m ² by an extrusion method to obtain coating samples 1 to 18, respectively.

After sensitometric exposure (10 seconds) was applied to these samples through an optical wedge, the samples were developed at 20 ° C. for 5 minutes with a developing solution 1 obtained according to the following formulation.
After fixing, washing and drying, the optical density was measured. Fog was determined from the minimum optical density of the sample, and sensitivity was expressed as the reciprocal of the exposure required to obtain an optical density of fog + 0.1, and expressed as a relative value with the value for sample 1 being 100. Further, the gradation is expressed by the slope of the linear portion of the characteristic curve (from fog + 0.2 to fog +
(Slope between 1.0). Table 1 shows the relative sensitivity and gradation of each 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.

[0088]

[Table 1]

As shown in Table 1, each ruthenium complex doped with each ruthenium complex of the present invention, except for the complex having imidazole as a ligand, should be hardened in any case as compared with the case without undoping. I understood. In some complexes, rhodium complexes mentioned as comparative examples, [RuCl ₆ ] ³⁻ , [RuCl 2
₅ (OH ₂ )] ^2-A more intense emulsion. Comparison between the emulsion of the present invention and the emulsion doped with [RuCl ₅ (NO)] ^2-
The emulsion doped with [RuCl ₅ (NO)] ^2- is almost equivalent in gradation to the emulsion of the present invention, but the sensitivity is not as high as the 2-propylimidazole, 2- or 5
It was found that the emulsion doped with the complex having -imidazole carboxaldehyde as a ligand was clearly superior.

When the ruthenium complex of the present invention is doped, a high-contrast emulsion is obtained by using a hexachlorobenzene derivative having an imidazole derivative having an aromatic ring skeleton such as imidazole or benzimidazole as a ligand. This was the case where a ruthenium complex was doped. Therefore, although the detailed mechanism is not clear, in the present invention, in order for the doped emulsion to be a high contrast emulsion, it is considered that the imidazole group of the ruthenium complex to be doped must have any substituent. Can be

Example 2 “Emulsion 19; Preparation of Cubic Silver Chloroiodobromide Emulsion Doped with (NH ₄ ) ₂ [RhCl ₅ (OH ₂ )]” (Comparative Example) Solution I Water 1 liter Gelatin 20 g Sodium chloride 3 1.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg II liquid water 400 ml silver nitrate 100 g III liquid water 400 ml sodium chloride 27.1 g potassium bromide 21.0 g ammonium pentachloroaquairidium (III) (0.001% aqueous solution) 20 ml Potassium hexachlororhodate (III) (0.001% aqueous solution) 6 ml

The solution II and the solution III were simultaneously added to the solution I kept at 42 ° C. and pH 4.5 for 15 minutes while stirring to form core particles. Subsequently, the following solutions IV and V were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the grain formation. IV liquid water 400 ml Silver nitrate 100 g V liquid water 400 ml sodium chloride 27.1 g potassium bromide 21.0 g potassium hexacyanoferrate (II) (0.1% aqueous solution) 10 ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH5.
7. The pAg was adjusted to 7.5, and sodium thiosulfate was added.
0 mg, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, 8 mg of sodium benzenethiosulfonate, and 2 mg of sodium benzenethiosulfinate were chemically sensitized at 55 ° C. so as to obtain an optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene and phenoxyethanol as a preservative were added, and finally a silver chloroiodobromide cubic emulsion 19 containing 70 mol% of silver chloride and having an average particle diameter of 0.25 μm was obtained.

[0094] "Emulsion 20;" K ₂ [RuCl ₅ (NO)] to hexachlororhodate (III) potassium added to III solution doped cubic silver chloroiodobromide emulsion "(Comparative Example) The emulsion 19 Instead, an equimolar amount of K ₂ [RuCl
_[ Emulsion 20] was prepared in the same manner as in Emulsion 19 except that the composition contained [ ₅ (NO)].

"Emulsions 21 to 22: Cubic silver chloroiodobromide emulsion doped with the ruthenium complex of the present invention" (the present invention) In place of potassium hexachlororhodate (III) added to solution III of Emulsion 19, The ruthenium complex (complex having 5-imidazolecarboxaldehyde as a ligand or complex having 2-propylimidazole as a ligand) synthesized in the present invention is hexachlororhodium
Emulsions 21 and 22 were prepared in the same manner as in Emulsion 19 except that equimolar amounts of (III) potassium were added.

Sensitizing dye (1) was added to emulsions 19 to 22 by 3.8 ×
Spectral sensitization was performed by adding 10 ^-4 mol / mol Ag. Furthermore, KBr 3.4 × 10 ⁻⁴ mol / mol Ag, compound (1) 3.
2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.0 × 10 ⁻⁴
Mol / mol Ag, hydroquinone 1.2 × 10 ^-2 mol /
Mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3) 1.0 × 10 ⁻⁴ mol / mol Ag, compound (4)
6.0 × 10 ^-4 mol / mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 μm colloidal silica having a particle size of 20 wt% based on gelatin, 4 wt% compound based on gelatin (5 wt%) ) was added, Ag3.7g / m ² on a polyester support was coated to a gelatin 1.6 g / m ^2. An upper layer of a protective layer and a lower layer of a protective layer having the following composition, and an UL layer having the following composition, were applied thereon. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (6) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ² Lower protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2-benzald Kissim 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (5) 40 mg / m ² Compound (10) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ²

[0098]

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[0099]

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[0100]

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[0101]

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Coating was performed by the above method, and coated samples 19 to 22
Was obtained respectively. After exposure to sensitometry (10 seconds) was applied to these coated samples 19 to 22 through an optical wedge, development was carried out with a developer 2 or 3 having the following formulation at 20 ° C. for 5 minutes. After stopping, fixing, washing with water and drying, the optical density was measured. Fog was determined from the minimum optical density of the sample. Sensitivity was expressed as the reciprocal of the exposure required to obtain an optical density of fog + 0.1, and expressed as a relative value with the value for the coated sample 19 being 100. Further, the gradation was represented by the slope of the linear portion of the characteristic curve (the slope between fog + 0.2 and fog + 1.0). Tables 2 and 3 show the relative sensitivity and gradation of each sample.
It was shown to. Developer 2 Diethylenetriamine / 5-acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methylbenzo-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1-phenyl- 5-mercaptotetrazole 0.02 g Sodium sulfite 2 g Add water to make 1 liter, and adjust the pH to 9.7. Developer 3 Potassium hydroxide 60.0 g Diethylenetriamine / 5-acetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60.0 g 5-methylbenzotriazole 0.53 g 4-Hydroxymethyl-4-methyl-1- Phenyl-3-pyrazolidone 2.3 g 2-Mercaptobenzimidazole-5-sulfonate 0.45 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.15 g Sodium erythorbate 9.0 g Diethylene glycol 7.5 g Add water Make up to 1 liter and bring the pH to 10.79. When using the developer 3, the developer is diluted with 1 part of water with respect to 2 parts of the developer to adjust the pH to 10.65 before use.

[0103]

[Table 2]

[0104]

[Table 3]

As shown in Tables 2 and 3, the emulsions doped with a pentachlororuthenium complex having 2-propylimidazole or 5-imidazolecarboxaldehyde as a ligand in the present invention were considered in terms of sensitivity-gradation ratio. At this time, it can be seen that the emulsion is more excellent than an emulsion doped with a rhodium complex, [RuCl ₅ (NO) ² ] ² .

[0106]

The present invention is based on the finding that when a pentachlororuthenium complex having an imidazole derivative as a ligand is contained in a silver halide emulsion, advantages in photographic properties are obtained. That is, when the ruthenium complex synthesized in the present invention is doped into silver halide grains, a silver halide photosensitive material having high contrast and a small range of desensitization can be produced as in the examples.

Claims (3)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide grains contained in the emulsion have the following general formula I
A silver halide photographic material comprising a ruthenium complex represented by the formula: Formula I In the formula, L is a compound represented by the following general formula II, X is a halogen, n is 4 or 5, m is 1 or 2, l is 0,
-1, -2. Formula II In the formula, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, or an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, a halogen, a cyano group, a nitro group, a mercapto group, Hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, amino group, ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, ureido group, Thioureido group, acyl group, oxycarbonyl group, carbamoyl group, thiocarbonyl group,
Thiocarbamoyl group, sulfonyl group, sulfinyl group,
It represents an oxysulfonyl group, a sulfamoyl group, a sulfino group, a sulfano group, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof. Here, R ₂ and R ₃ may be closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring. 2. At least one of R ₁ , R ₂ and R ₃ in the compound of the general formula II is a methyl group, an ethyl group, n
2. The silver halide photographic material according to claim 1, wherein the photographic material is a-or i-propyl group or an aldehyde group. 3. The silver halide light-sensitive material according to claim 1, wherein in formula I, X = Cl ⁻ .