JPH0772576A - Silver halide photographic emulsion and its production and photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain excellent latent image stability and reciprocity characteristic by incorporating different kind iridium compd. in silver halide emulsion particles. CONSTITUTION:In the silver halide photographic emulsion in which the halogen composition of the silver halide emulsion particles is >=50mol.% silver halide content, at least two different kind iridium compd. or its some part is incorporated in the particles. In this case, it is preferable that the two different kind iridium compd. are the compd. having different ligand respectively. And also, it is preferable that at least one kind iridium compd. is the compd. containing >=1 bromine atom. And moreover, it is preferable that at least one kind iridium compd. is the compd. containing >=1 bromine atom, and as other kind iridium compd., the iridium compd. containing >=1 chlorine atom is used jointly.

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 light-sensitive material, and more particularly to a silver halide photographic light-sensitive material excellent in latent image stability and reciprocity law failure characteristics.

[0002]

BACKGROUND OF THE INVENTION In recent years, in order to finish a large amount of prints in a short delivery time, a photosensitive material for color photographic paper is required to have rapid processability. As one of the methods, it is known to accelerate color development by using a silver chloride emulsion or a silver chlorobromide emulsion having a high silver chloride content as a silver halide emulsion. For example, U.S. Pat.
4,225,666, JP-A-55-26589, 58-91444, 5
8-95339, 58-94340, 58-95736, 58-106538
No. 58, No. 58-107531, No. 58-107532, No. 58-107533,
No. 58-108533, No. 58-125612 and the like have the description of the above technology.

However, a silver chloride emulsion or a silver chlorobromide emulsion having a high silver chloride content has a drawback that reciprocity law failure characteristics are poor (that is, sensitivity and gradation change greatly depending on exposure illuminance). Therefore, it has been desired to improve the reciprocity law failure characteristic of a silver chloride emulsion or a silver chlorobromide emulsion having a high silver chloride content. Therefore, JP-A-51-139323 and JP-A-59-171947 disclose that reciprocity failure characteristics are improved by incorporating a metal compound of Group VIII of the Periodic Table. However, the above disclosed technique is not sufficient to solve the problems in silver chloride or silver halide having a high silver chloride content.

It is generally known that doping an iridium compound is effective for improving the reciprocity law failure of a silver halide emulsion. For example, Japanese Examined Patent Publication (Kokoku) No. 43-4935 discloses that gradation fluctuation is small over a wide exposure time range by adding an iridium compound during the preparation of silver halide grains. Also, U.S. Pat.
No. 7,751 describes that reciprocity law failure characteristics are improved by adding iridium from the surface of silver halide grains.

However, although the above problems have been almost solved, there is a problem in that the latent image stability is poor, that is, the density changes greatly depending on the time interval between exposure and processing. In particular, when the emulsion is doped with an iridium compound, which is well known as a compound that improves reciprocity law failure, the reciprocity failure is certainly improved, but the latent image stability in the initial stage after exposure is significantly deteriorated. By the Journal of Photographic Science
Photographic Science) 33, 201, which is not preferable in practice.

Japanese Unexamined Patent Publication (Kokai) No. 3-188437 discloses a technique for reducing reciprocity law failure and development density change with time from exposure to processing by incorporating an iridium compound and an iron compound in the surface layer side. ing. However, as a result of studies by the present inventor, although the reciprocity law failure is improved according to these techniques, there is still the problem that the gradation changes due to the change in the elapsed time until post-exposure processing, that is, latent image stability. It was found that there is a problem in that the property is poor, and that there is a practical defect due to softening in an inert treatment.

Japanese Unexamined Patent Publication (Kokai) No. 1-105940 discloses a technique for improving the initial latent image stability by doping iridium into a specific region, but further improvement is required.

In JP-A-4-9034, in a comparative example, K ₃ was added to a pure silver chloride emulsion containing no bromide ion.
Although IrBr ₆ is used, it is described that the latent image stability is poor and the tone is soft, which is not preferable.

As described above, there has been no technique for solving the deterioration of latent image stability caused by adding an iridium compound to silver halide having a high silver chloride content. In addition, although it is described that the iridium compound is added to the following known examples, it does not solve this problem, that is,
Research Disclosure Magazine Volume 176 (December 1978) RD-
17643 is known to adjust in the presence of iridium when making direct print emulsions. The internal latent image type emulsion of U.S. Pat. No. 3,923,513 describes that iridium ions are useful. Japanese Unexamined Patent Publication No. 2-20853 describes that sensitivity is increased by using an iridium complex having a cyano ligand.

[0010]

The object of the present invention is to provide excellent latent image stability (that is, a stable image can be obtained without depending on the elapsed time from exposure to development processing) and excellent reciprocity law failure characteristics. Another object is to provide a silver halide light-sensitive material.

[0011]

[Means for Solving the Problems] As a result of earnest research, although it is an iridium compound having poor latent image stability by itself, surprisingly, by combining at least two different kinds of iridium compounds, reciprocity law failure can be suppressed. It was found that the latent image stability (density fluctuation from exposure to development) can be improved without deterioration, and the problems of the present invention have been solved. That is, the above object of the present invention is such that the halogen composition of the silver halide emulsion grains has a silver chloride content of 50%.
A silver halide photographic emulsion having a mol% or more, which can be achieved by a silver halide photographic emulsion characterized in that the grains contain at least two different kinds of iridium compounds or a part thereof. Further, at least one of the iridium compounds has a bromine atom of 1 or less.
It is preferable that one or more chlorine atoms are contained and at least one of the iridium compounds contains one or more chlorine atoms. Further, the halogen composition of the silver halide emulsion grains is preferably such that the silver chloride content is 95 mol% or more. The above objects of the present invention can be achieved by a silver halide photographic light-sensitive material containing these emulsions. Further, the above object of the present invention is to provide a silver halide photographic emulsion wherein the halogen composition of the silver halide emulsion grains is 50 mol% or more, and the grains are at least two different types of iridium. It could be achieved by forming in the presence of the compound. Further, it is preferable that at least one of the iridium compounds contains one or more bromine atoms, and at least another of the iridium compounds contains one or more chlorine atoms. Further, the halogen composition of the silver halide emulsion grains is preferably such that the silver chloride content is 95 mol% or more.

The details of the present invention will be described below.

In the present invention, forming grains in the presence of an iridium compound means that the iridium compound is present at the time relevant to the formation of emulsion grains, and the iridium compound is present in advance in the kettle before grain formation. Alternatively, the iridium compound may be added continuously or temporarily during grain formation. Moreover, the addition timing of different iridium compounds may be the same or different. Preferably, the iridium compound of the present invention or a part thereof is contained in the emulsion grains. In addition, a part of the iridium compound of the present invention represents a complex ion formed by Ir.

In the silver halide photographic light-sensitive material of the present invention, from the effect of the present invention, it is preferable that the silver halide grains are silver chloride or silver chlorobromide grains containing substantially no iodine. Similarly, the silver chloride content is preferably 90 mol% or more. More preferably, it is 95 mol% or more.

The silver halide grain according to the present invention may be a grain having only a uniform composition, or may be a grain having a silver bromide localized phase on the surface or inside thereof. Further, it may be mixed with other silver halide grains having different compositions.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more, the silver chloride content in all silver halide grains contained in the emulsion layer. The proportion of silver halide grains of 90 mol% or more is preferably 60 mol% or more, more preferably 80 mol% or more.

The amount of the iridium compound used in the present invention can be used in the range of 1 × 10 ^-12 to 1 × 10 ^-5 mol / silver mol, preferably 1 × 10 ^-10 to 1 × 10 5. ^-7 mol /
It is a silver mole, and more preferably 1 × 10 ⁻⁹ to 1 × 10 ^−7.
Mol / silver mol.

The at least two different types of iridium compounds used in the present invention are preferably compounds each having a different ligand, and further, at least two different types of iridium compounds used in the present invention are It is preferable that at least one type of the compound is a compound containing at least one bromine atom. And, more preferably, at least one kind of iridium compound is a compound containing one or more bromine atoms, and another at least one kind of iridium compound is a compound containing one or more chlorine atoms. Is the combination of at least two different types of iridium compounds. Most preferred of at least two different types of iridium compounds of the present invention are:
At least one kind of iridium compound is a compound containing at least four bromine atoms, and another at least one kind of iridium compound is a compound containing at least four chlorine atoms. .

An example of the iridium compound of the present invention is shown below, but the present invention is not limited to this.

(I-1) K ₂ IrCl ₆ , (I-2) K [IrCl ₅ (N
O)], (I-3) K [IrBr ₅ (NO)], (I-4) K ₃ IrCl ₆ ,
(I-5) K ₂ IrBr ₆ , (I-6) K ₃ [Ir (NO ₃ ) ₆ ], (I-
7) IrCl ₄ , (I-8) K ₂ [IrBr ₅ (OH ₂ )], (I-9) K
₂ [IrCl ₅ (OH ₂ )], (I-10) IrBr ₃ , (I-11) (NH ₄ ) ₂ [I
_{rCl 6], (I-12} ) Na 3 [IrBr 6], (I-13) Na 2 [IrB
_{r 6], (I-14} ) Na 3 [IrCl 6], (I-15) [IrCl (NH 3) 5] C
_{l 2, (I-16)} cis- [IrCl 2 (C 2 H 8 N 2) 2] Cl, (I-17) H 2
_{IrCl 6, (I-18)} (NH 4) 2 [IrBr 6], (I-19) [Ir 4 (CO)
₁₂ ], (I-20) H ₂ [Ir ₄ Cl ₈ (CO) ₈ ], and the grain size of the silver halide grains are not particularly limited, but when considering various photographic performances such as rapid processability and sensitivity. , Preferably 0.2-1.6μ
m, more preferably 0.25 to 1.2 μm. In addition,
The particle size of silver halide grains can be measured by various methods generally used in the technical field.
As a typical method, Loveland's "particle size analysis method"
(ASTM Symposium on Right Microscopy, 1955, pp. 94-122) or "The Theory of Photographic Process" (Mies and James, 3rd edition, published by Macmillan, Inc. (1966)) ) In Chapter 2.
That is, the particle size can be obtained by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle distribution can be fairly accurately represented using diameter or projected area. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably in the grain distribution of the silver halide grains,
A monodisperse silver halide having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) The grain size as used herein means a cubic silver halide grain. The length of one side, the diameter in the case of a spherical silver halide grain, and the diameter of a cube or a grain other than a spherical shape when the projected image is converted into a circular image of the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any one of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Furthermore, pAg described in Japanese Patent Application Laid-Open No. 54-48521 is one type of simultaneous mixing method.
The controlled double jet method can also be used.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor as described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Patent 2,921,164, etc., and taking out the reaction mother liquor from the reactor described in JP-B-56-501776 and the like, You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-2
No. 6589, Japanese Patent Publication No. 55-4273, and The Journal of
Photographic Science (J. Photogr. Sci.)
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared by the method described in the literature such as 21, 39 (1973) and the like, and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape or a mixture of grains having various shapes.

In the present invention, a compound such as a cadmium salt, a zinc salt, a lead salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof is used in the process of forming and / or growing the silver halide grains. Can be used to add a metal ion to be incorporated inside and / or on the surface of the particle. The metals used include, in the periodic rule, Group VIA, Group VIIA, Group VIII, Group IIB, Group IIIB.
Group IVB group, preferably Mn, Fe, Co, N
i, Zn, Ga, Ge, Mo, Ru, Pd, Cd, In, Sn, W, Re, O
It is a salt or complex salt of s, Ir, Pt, Tl, Au. These can be used alone or in combination. Preferred metal salts or complex salts are Japanese Patent Application Nos. 2-162332, 2-253667 and 3-253.
109173, 4-251468, 4-82250, JP-A-4-12562
No.9, No.4-251469, No.4-253081, etc. Further, by placing in a suitable reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface. Particularly, examples of desirable compounds include K ₂ Fe (CN) ₆ which is an iron compound and Ga (NO ₃ ) _{3 which} is a gallium compound.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may remain contained. Research Disclosure when removing the salts
It can be performed based on the method described in RD17643.

In the present invention, the silver halide grain used in the emulsion may be a grain in which a latent image is mainly formed on the surface. Further, particles formed mainly inside the particles may be used. However, more preferred are surface latent image-forming silver halide grains in which a latent image is mainly formed on the surface.

The emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxanol dye can be used.

The silver halide emulsion used in the present invention can be sensitized by a sensitizing method using a reducing substance, a sensitizing method using a chalcogen sensitizer, a sensitizing method using a noble metal compound, and the like. A combination of sensitizing methods can be used. Sulfur sensitization, gold sensitization, and a combination thereof, gold sulfur sensitization, are particularly preferred in the present invention.

As the chalcogen sensitizer applied to the silver halide emulsion used in the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfates such as sodium thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine.

The noble metal sensitizer applied to the silver halide emulsion used in the present invention is preferably a gold sensitizer. The gold sensitizer may have a monovalent or trivalent gold oxidation number, and chloroauric acid, sodium chloroaurate, potassium chloroaurate, and the like can be used.

The amount of the gold sensitizer used varies depending on the type of silver halide emulsion, the type of gold compound, the ripening conditions, etc., but is usually 1 × 10 ^-9 to 1 × per mol of silver halide.
10 ⁻⁴ mol is preferable, and more preferably 1 × 10 ⁻⁸ to 1 × 10 5.
^-5 mol.

The dye-forming coupler used in the silver halide photographic light-sensitive material of the present invention is usually selected so that a dye which absorbs the light in the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A yellow dye-forming coupler is used in the blue-sensitive emulsion layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, the silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

The light-sensitive material of the present invention contains a color antifoggant,
Image stabilizer, hardener, plasticizer, anti-irradiation dye, polymer latex, ultraviolet absorber, formalin scavenger, development accelerator, development retarder, optical brightener, matting agent, lubricant, antistatic agent, interface An activator or the like can be optionally used. These compounds are described, for example, in JP-A Nos. 62-215272 and 63-46436. The light-sensitive material of the present invention can form an image by performing color development processing known in the art.

[0039]

EXAMPLES Examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 30 minutes while controlling the following (solution A) and solution (B) to pAg6.5 and pH3.0 by pAg controlled double jet method in 1000 ml of 2% gelatin aqueous solution kept at 40 ° C. And added simultaneously, and then the following (solution C) and (solution D) were added to pAg7.
3. Simultaneously added over 120 minutes while controlling the pH to 5.5.

At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make the total volume 200 ml.

(Solution B) Silver nitrate 10 g Water was added to make the total amount 200 ml.

(Solution C) Sodium chloride 78.7 g Potassium bromide 0.157 g Water was added to bring the total volume to 446 ml.

(D liquid) 190 g of silver nitrate Water was added to make the total amount to 380 ml.

After the addition is completed, Kao Atlas Co., Ltd. Demol N
Desalination was carried out using a 10% aqueous solution of magnesium sulfate and a 30% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.
40 μm, coefficient of variation (standard deviation of particle size / average particle size) 0.07,
A monodisperse cubic emulsion EMP-1 having a silver chloride content of 99.9 mol% was obtained.

To EMP-1, the following compounds were used at 65 ° C.
The optimum sensitization was carried out to obtain a green-sensitive silver halide emulsion Em-1.

Sodium thiosulfate 1.5 mg / mol AgX stabilizer SB-1 * 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 * 3 × 10 ⁻⁴ mol / mol AgX * SB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole

[0049]

[Chemical 1]

Next, an emulsion different from Em-1 was prepared by adding 1 × 10 ⁻⁸ mol of iridium compound I-1 to the solution (C liquid) per mol of silver, and this was designated as Em-2. .

Further, an iridium compound added to Em-2
Instead of I-1, the same amount of iridium compound shown in Table 2 was added to prepare an emulsion as shown in the table.
It was set to Em-3 to Em-19. The two iridium compounds used in each of the emulsions Em-10 to Em-16 were used in equal amounts, and the total amount was the same as that of Em-2.

Furthermore, in Em-18 and Em-19, the following compounds
IR-1 and IR-2 were added to the solution (solution C) at 1 × 10 ^-5 per mol of silver.
Mol added.

IR-1: K ₂ Fe (CN) ₆ IR-2: Ga (NO ₃ ) ₃ Polyethylene on one side of the paper support and titanium oxide on the other side (the side on which the photographic constituent layers are coated) Coating each layer shown below on a support laminated with polyethylene containing
Sample 101 was prepared.

[0054]

[Table 1]

As a hardening agent, H-1 was added to the second layer.

H-1: 2,4-dichloro-6-hydroxy-S-triazine sodium Soluble sample 102 in the same manner except that Em-2 to Em-19 were used instead of Em-1 of sample 101. ~ 119 were made.

The performance of the sample thus obtained was evaluated by the following method, and the results are shown in Table 2.

(1) Sensitivity Wedge exposure with green light for 0.05 seconds and color development according to the following processing steps were followed by optical densitometer (PDA-manufactured by Konica).
Sensitometry using 65 type)
The sensitivity was determined by the logarithm of the reciprocal of the exposure dose required to obtain a high density of 0.8. Then, the sensitivity was displayed as a relative sensitivity when the sensitivity of the comparative sample 101 to which the iridium compound was not added was 100.

(2) Reciprocity law failure characteristic Wedge exposure was performed with green light for 10 seconds so that the exposure amount was the same as that of the above sensitometry, and sensitometry was performed in the same manner as above. Then, the reciprocity law failure characteristic is 10 when the sensitivity when exposed at 0.05 seconds is 100.
It was represented by the relative sensitivity of the second exposure sample. (If the value is closer to 100, there is no difference in sensitivity between 10 second exposure and 0.05 second exposure, that is,
It shows that the reciprocity law failure characteristic is excellent. ) (3) Latent image stability A sample that was wedge-exposed with green light for 0.05 seconds and developed 10 seconds after exposure (hereinafter referred to as sample A) and a sample that was developed 5 minutes after exposure (hereinafter referred to as sample) B)) was created. Optical densitometer (Konica PDA-65 type) using these two samples
Was used to measure the concentration. Then, the exposure amount corresponding to the density of Sample A, which is the density closest to 0.5, was examined. And
The density of the sample B corresponding to this exposure amount was examined, and the difference from the density of the sample A corresponding to this was determined. Then, this difference in concentration is shown as a value when the concentration of the sample A is 100. In addition, the exposure amount corresponding to the density of the sample A closest to the density of 2.0 was examined. Then, the density of the sample B corresponding to this exposure amount was examined, and the difference from the density of the sample A corresponding to this was obtained.
Then, this difference in concentration is shown as a value when the concentration of the sample A is 100. (The smaller the absolute value of these two values, the smaller the density difference between the sample developed 10 seconds after exposure and the sample developed 5 minutes after exposure, that is, the latent image stability is excellent. The processing conditions used for the evaluation are as follows.

Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30 to 34 ℃ 90 seconds Dry 60 to 80 ℃ 60 seconds Color developer Pure water 800 ml Triethanol Amine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-diphosphonate disodium salt 1.0g N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbenz sulfonic acid derivative) 1.0g Potassium carbonate 27g Water Is added to bring the total volume to 1 l, and the pH is adjusted to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 1 liter and add potassium carbonate or Adjust the pH to 5.7 with glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20 % Aqueous solution) 3.0g Optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.5g Add water to make a total volume of 1 liter and add sulfuric acid or potassium hydroxide.
Adjust to pH = 7.0.

[0063]

[Table 2]

As can be seen from Table 2, the sample using the iridium compound alone has an improved reciprocity law failure characteristic as compared with the sample not using the iridium compound. Cause deterioration. But the sample
By using at least two different kinds of iridium compounds as in No. 108 to 119, the reciprocity law failure characteristic is better than that without using the iridium compound, and the iridium compound alone is used. It was found that the latent image stability was improved (density fluctuation was suppressed) compared with the sample used in. It was unexpected and surprising that the latent image stability was improved by using two or more iridium compounds, which alone deteriorate the latent image stability, in combination. Further, in Sample Nos. 113 and 114 to which an iron compound or a gallium compound was added at the time of grain formation, latent image stability, reciprocity law failure, and sensitivity were further improved.

Example 2 During chemical sensitization of Em-1,2,3,5,6,8,9,10,12,13,17,18, sodium thiosulfate, sodium chloroaurate and SB-1 (* ) Was used, and emulsions prepared in the same manner were used as Em-21 to 32, respectively.

* SB-1: 1- (3-acetamidophenyl) -5-
Samples coated with mercaptotetrazole Em-21 to 32 in the same manner as Em-1
o.121 to 132. These samples were evaluated as in Example 1. The sensitivity is shown as a relative sensitivity when the sensitivity of Comparative Sample 121 to which the iridium compound is not added is 100.

[0067]

[Table 3]

In particular, a sample which has been subjected to sodium chloroaurate sensitization can achieve high sensitivity, but has the disadvantage that the latent image stability is further deteriorated by the iridium compound. However, this defect can be compensated by using at least two different kinds of iridium compounds as in Sample Nos. 126 to 132. Therefore, the present invention is particularly effective when gold sensitization is performed. I understood it.

Further, in the same manner as in Example 1, in Sample No. 132 to which an iron compound was added at the time of grain formation, latent image stability, reciprocity law failure and sensitivity were further improved.

Example 3 In the preparation of EMP-1 of Example 1, (solution A) and (solution B)
The average particle size is 0.71 μm (cubic one side length), the coefficient of variation is 0.0 by changing the addition time of (C liquid) and the addition time of (C liquid) and (D liquid).
7. A monodisperse cubic emulsion having a silver chloride content of 99.9 mol% was prepared and designated as EMP-2. To this emulsion, sodium thiosulfate; 0.8 mg / mol AgX, sodium chloroaurate: 1.5
mg / mol AgX, SB-1 (*): 6 × 10 ⁻⁴ mol / mol AgX and sensitizing dye BS-1 (*); using 4 × 10 ⁻⁴ mol / mol AgX 65
Optimally sensitized at ℃. The obtained emulsion is designated as Em-41.

An emulsion different in the preparation of EMP-2 was prepared by adding 1 × 10 ^-8 mol / mol AgX of iridium compound I-1 to the solution (solution C), which was designated as Em-42. Similarly, different emulsions were prepared only by adding 1 × 10 ⁻⁸ mol / mol AgX of the iridium compounds shown in Table 5, and these were each used as Em.
-43 to 49. The two iridium compounds used in each of the emulsions Em-44 to Em-49 were used in equal amounts, and the total amount was the same as that of Em-42.

Preparation of EMP-1 of Example 1 (solution A)
And (B solution) addition time and (C solution) and (D solution) addition
By changing the interval, the average particle size is 0.52μm (one side length of the cube
) Monodisperse standing with coefficient of variation of 0.07 and silver chloride content of 99.9 mol%
A square emulsion EMP-3 was prepared. For this emulsion,
Thorium; 2.0 mg / mol AgX, sodium chloroaurate 0.3 mg /
Molar AgX, SB-1 (*); 7 x 10^-FourMol / mol AgX and sensitized color
Elementary RS-1 (*); 7 × 10 ^-Five67 ° C using mol / mol AgX
I sensitized optimally. The obtained emulsion is designated as EMP-3.

* SB-1: 1- (3-acetamidophenyl) -5
-Mercaptotetrazole

[0074]

[Chemical 2]

An emulsion different from that of EMP-3 was prepared by adding 1 × 10 ⁻⁸ mol / mol AgX of the iridium compound (I-1) to the (C liquid), which was designated as Em-52. Similarly, the iridium compound shown in Table 5 was added at 1 × 10 ⁻⁸ mol / mol.
Emulsions differing only in the addition of AgX were prepared and designated Em-53-59, respectively. The two iridium compounds used in each of the emulsions Em-54 to Em-59 were used in equal amounts, and the total amount was the same as that of Em-52.

Next, polyethylene was laminated on one side of the paper support, and polyethylene containing titanium oxide was laminated on the other side (the side on which the photographic constituent layers were coated). A multilayer silver halide color photographic light-sensitive material sample 201 was prepared by coating. The coating liquid was prepared as follows. The values of mass and volume are values per 1 m ² of coating.

First layer coating solution Yellow coupler Y-1 (*); 0.80 g, dye image stabilizer S
T-1 (*); 0.30 g, ST-2 (*); 0.20 g, stain inhibitor H
Q-1 (*); 0.02g, Irradiation prevention dye AIY-1
(*); 0.01g and high boiling point organic solvent DNP; 0.20g, and add ethyl acetate 3.3ml to dissolve, and this solution is the surfactant SU-1
(*); 10% gelatin aqueous solution containing 0.4 ml (20% aq) 1
2 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. In addition, the antifungal agent F-
1 (*) was added. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 0.26 g of silver) prepared under the above conditions, and surfactants SU-2 (*) and SU-3 (*) were added as coating aids.
The surface tension was adjusted to prepare a coating liquid for the first layer.

Second layer coating liquid Hardener H-2 (*); 0.10 g, stain inhibitor HQ-2 (*); 0.0
3g, HQ-3 (*); 0.03g, HQ-4 (*); 0.05g, HQ-5
(*); 0.23 g, DIDP (*); 0.06 g, and add 3.3 ml of ethyl acetate to dissolve, and this solution is the surfactant SU-1 (*); 0.4 ml (2
A dispersion liquid was prepared by emulsifying and dispersing in 12 ml of 10% gelatin aqueous solution containing 0% aq) using an ultrasonic homogenizer.
The antifungal agent F-1 (*); 0.002 g was added to the dispersion. To this dispersion, surfactants SU-2 (*) and SU-3 are used as coating aids.
(*) Was added to adjust the surface tension to obtain a second layer coating solution.

Third layer coating solution Magenta coupler M-1 (*); 0.35 g, dye image stabilizer S
T-3 (*); 0.15g, ST-4 (*); 0.15g, ST-5 (*); 0.15
g, anti-irradiation dye AIM (*); 0.01 g and high boiling organic solvent DNP; 0.20 g, and add 3.9 ml of ethyl acetate to dissolve, and this solution is surfactant SU-1 (*); 0.4 ml (20% aq)
A magenta coupler dispersion was prepared by emulsifying and dispersing in 14 ml of a 10% gelatin aqueous solution containing ## STR1 ## using an ultrasonic homogenizer. A fungicide F-1 (*) was added to the dispersion. This dispersion was mixed with the green-sensitive silver halide emulsion (containing 0.17 g of silver) prepared under the above conditions, and surfactants SU-2 (*) and SU-3 (*) were added as coating aids. The surface tension was adjusted to prepare a coating solution for the third layer.

Fourth layer coating solution Hardener H-2 (*); 0.10g, UV absorber UV-1 (*); 0.28
g, UV-2 (*); 0.09g, UV-3 (*); 0.88g, stain inhibitor HQ-1 (*); 0.03g and high boiling organic solvent DNP; 0.40g
2.6 ml of ethyl acetate was added to and dissolved, and this solution was emulsified and dispersed in 9.4 ml of 10% gelatin aqueous solution containing surfactant SU-1 (*); 0.3 ml (20% aq) using an ultrasonic homogenizer. A dispersion was prepared. Surfactants SU-2 (*) and SU-3 (*) were added to this dispersion as coating aids to adjust the surface tension to obtain a fourth layer coating liquid.

Fifth layer coating solution Cyan coupler C-1 (*); 0.24 g, cyan coupler C-2
(*); 0.08 g, dye image stabilizer ST-1 (*); 0.20 g, stain inhibitor HQ-1 (*); 0.01 g and high boiling organic solvent HBS-
To 1 (*); 0.20 g, DOP (*); 0.20 g, add 3.5 ml of ethyl acetate and dissolve, and this solution is the surfactant SU-1 (*); 0.4 ml (2
A cyan coupler dispersion was prepared by emulsifying and dispersing in 13 ml of 10% gelatin aqueous solution containing 0% aq) using an ultrasonic homogenizer. A fungicide F-1 (*) was added to the dispersion. This dispersion was mixed with the red-sensitive silver halide emulsion (containing 0.21 g of silver) prepared under the above conditions, and the surfactants SU-2 (*) and SU-3 (*) were added as coating aids. Then, the surface tension was adjusted to prepare a coating solution for the fifth layer.

6th layer coating liquid UV absorber UV-1 (*); 0.10g, UV-2 (*); 0.04g, UV
-3 (*); 0.16 g, stain inhibitor HQ-1 (*); 0.01 g, anti-irradiation dye AIC-1 (*); 0.02 g and high boiling organic solvent DNP (*); 0.20 g, PVP ( *); 1.1 ml of ethyl acetate was added to 0.03 g and dissolved, and this solution was added to surfactant SU-1.
(*); 4 ml of 10% gelatin aqueous solution containing 0.1 ml (20% aq) was emulsified and dispersed using an ultrasonic homogenizer to prepare a dispersion liquid. Surfactants SU-2 (*) and SU-3 (*) were added to this dispersion as coating aids to adjust the surface tension to obtain a coating liquid for the sixth layer.

7th layer coating solution Hardener H-1 (*); 0.10 g of ethyl acetate 2.9 ml was added and dissolved, and this solution was used as surfactant SU-1 (*); 0.3 ml (20% aq)
A 10% gelatin aqueous solution containing 10 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a dispersion. Surfactants SU-2 (*) and SU-3 (*) were added to this dispersion as coating aids to adjust the surface tension to obtain a 7th layer coating liquid.

[0084]

[Table 4]

* SB-1: 1- (3-acetamidophenyl) -5
-Mercaptotetrazole ST-1: 2,4-di-t-pentyl- (4-hydroxy-3,5-di-t-butyl) benzoate ST-2: 2,4-di-t-pentyl-diethylcarbamoylmethoxy Benzene ST-3: 1,4-dibutoxy-2,5-di-t-butylbenzene ST-4: 4- (4-hexyloxyphenyl) thiomorpholine
-1-Dioxide ST-1: 1,1-bis (2-methyl-4-hydroxyl-5-t-butylphenyl) butane H-1: 2,4-dichloro-6-hydroxy-s-triazine-sodium H -2: Tetrakis (vinylsulfonylmethyl) methane HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec- Tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-s-hexyloxycarbamoylbutyl) hydroquinone HBS-1 : 1-dodecyl-4- (p-toluenesulfonamide) benzene DOP: Dioctyl phosphate TOP: Trioctyl phosphate DNP: Dinonyl phthalate DIDP: Di-i-decyl phthalate PVP: Polyvinylpyrrolidone SU-1: Disulfosulfosuccinate 2-Ethylhexyl) ester / sodium SU-2: Natri tri-i-propylnaphthalene sulfonate Um SU-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester sodium F-1: 2-methyl-5-chloro-4-isothiazoline-3 -on

[0086]

[Chemical 3]

[0087]

[Chemical 4]

[0088]

[Chemical 5]

In Sample 201, Samples 202 to 209 were prepared in the same manner as Sample 201 except that the emulsion used in the photosensitive silver halide layer was changed as shown in Table 5.

[0090]

[Table 5]

Using the sample thus obtained, exposure and treatment were carried out in the same manner as in Example 1 except that the filters at the time of exposure were changed to blue, green and red, and the same evaluation as in Example 1 was performed. Was done. The sensitivity is expressed as a relative sensitivity when the sensitivity of the sample 201 to which the iridium compound is not added is 100. The results obtained are shown in Table 6.

[0092]

[Table 6]

As can be seen from Table 6, the sample using the iridium compound alone has improved reciprocity law failure characteristics as compared with the sample not using the iridium compound, but the latent image stability is Deterioration. But the sample
Like No. 203 to 209, by using at least two different kinds of iridium compounds together, reciprocity law failure characteristics are better than those not using iridium compounds, and It was found that the latent image stability was improved (density fluctuation was suppressed) as compared with the sample used alone. Furthermore, in sample No. 209 to which an iron compound was added at the time of grain formation, latent image stability, reciprocity law failure, and further improvement in sensitivity were observed.

[0094]

According to the present invention, a silver halide photographic light-sensitive material having excellent reciprocity failure characteristics and latent image stability can be provided.

Claims (7)

[Claims] 1. The halogen composition of silver halide emulsion grains is
A silver halide photographic emulsion having a silver chloride content of 50 mol% or more, wherein the grains contain at least two different kinds of iridium compounds or a part thereof. 2. At least one of the iridium compounds
2. One for photographic silver halide according to claim 1, characterized in that one contains one or more bromine atoms and at least one other of said iridium compounds contains one or more chlorine atoms. emulsion. 3. The halogen composition of silver halide emulsion grains is
The silver halide photographic emulsion according to claim 1 or 2, wherein the silver chloride content is 95 mol% or more. 4. A silver halide photographic light-sensitive material containing the silver halide photographic emulsion according to claim 1, 2, or 3. 5. The halogen composition of silver halide emulsion grains is
A method for producing a silver halide photographic emulsion having a silver chloride content of 50 mol% or more, characterized in that the grains are produced in the presence of at least two different kinds of iridium compounds. Method. 6. At least one of the iridium compounds
6. The silver halide photographic material according to claim 5, wherein one of the iridium compounds contains one or more bromine atoms, and at least one of the iridium compounds contains one or more chlorine atoms. Emulsion production method. 7. The halogen composition of silver halide emulsion grains is
7. The method for producing a silver halide photographic emulsion according to claim 5, wherein the silver chloride content is 95 mol% or more.