JP2719540B2 - High sensitivity silver halide photographic material - Google Patents

Description

Description: 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 with improved illuminance failure and high sensitivity.

[Background of the Invention]

In the field of silver halide photographic light-sensitive materials, there has been a demand for light-sensitive materials having improved reciprocity failure such as low illuminance failure and high illuminance failure.

Conventionally, as a means for improving such illuminance failure, it has been known to add an iridium compound to a silver halide emulsion.For example, an iridium compound is added to an emulsion during the crystal growth of silver halide grains to provide an illuminance. Means for improving failure are known.

However, in the prior art, even when an iridium compound is added to a silver halide emulsion, illuminance failure can be improved, but this causes desensitization or the expected sensitization cannot be obtained, and the photographic material of the photosensitive material is not obtained. This was contrary to the demand for higher sensitivity.

[Object of the invention]

The present invention solves the above-mentioned problems of the prior art, achieves both high sensitivity and improved illuminance failure, a photosensitive material having high sensitivity and improved illuminance failure, and low fog. Another object of the present invention is to provide a silver halide light-sensitive material satisfying the requirement that desensitization due to dye adsorption or the like can be prevented.

[Means for solving the problem]

The present invention relates to a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing emulsions having different silver halide compositions, wherein the emulsion is formed by growing the silver halide grains contained in the emulsion. In at least one period, the silver halide grains grow in the presence of silver halide grains having a solubility product equal to or less than that of the silver halide grains contained in the emulsion, and iridium ions are removed from the silver halide grains. Characterized in that the emulsion is present at least after the start of grain growth (hereinafter, such an emulsion is appropriately referred to as “emulsion of the present invention”). The above object has been achieved.

That is, in the conventionally used emulsions, when the illuminance failure was improved by adding an iridium compound, desensitization sometimes occurred, whereas in the present invention, the specific silver halide as described above was used. By using the emulsion, the iridium ion was able to improve the illuminance failure and further exert the effect of sensitization.

In addition, according to the present invention, a low fog photosensitive material was obtained, and desensitization due to dye adsorption was prevented.

 Hereinafter, the present invention will be described in detail.

 First, the emulsion of the present invention will be described.

The emulsions of the present invention have different silver halide compositions. The fact that different silver halide compositions are mixed means that different silver halide compositions are mixed in the grains of the silver halide grains (for example, the silver halide composition is different between the inside of the grain and the other outer portion in the grain). Different types), and may be mixed by having different silver halide compositions between grains (for example, a mixture of grains having different silver halide compositions from each other). In some cases, both cases are satisfied. In the present invention, the silver halide composition may be mixed in any of the embodiments.

Further, the emulsion of the present invention may contain, during at least one period of the growth process of silver halide grains contained in the emulsion, silver halide grains contained in the emulsion (hereinafter referred to as “Ag
The silver halide grains are grown in the presence of fine silver halide grains (also called "AgX grains (2)") having a solubility product equal to or less than that of the "X grains (1)". .

When the solubility product is equal to or less than the solubility product, the solubility product of the AgX particles (2) is equal to or smaller than the solubility product of the AgX particles (1). Further, the solubility product in the present specification is in a normal chemical sense.

Although the AgX grains (1) have two or more silver halide compositions in the grains as described above,
Emulsions having different silver halide compositions may be mixed and mixed as an emulsion. However, when mixed within the grains, the mixed two or more silver halides are uniformly distributed in the grains. Or may be unevenly distributed.
In the present invention, a non-uniform case such as a core / shell type or an epitaxial type is preferable, and a core / shell type is particularly preferable.

The silver halide composition of the AgX grains (1) is not particularly limited, as long as the emulsions containing the AgX grains (1) have different silver halide compositions, and silver iodide, silver chlorobromide,
Silver chloroiodobromide is preferred, and silver iodide is particularly preferred. That is, for example, mixed crystal silver iodide, silver chlorobromide and the like can be used. Preferably, the core / shell having a silver iodide content of the core of 15 mol% or more and 40 mol% or less is used. Silver iodobromide having a structure is preferred.

The particle size of the AgX particles (1) is preferably not more than 3.0 μm in sphere equivalent diameter.

The AgX particles (1) may be polydisperse or monodisperse, but preferably monodisperse.

The term “monodisperse” as used herein means that 95% or more of all particles exist within a range of ± 40% of the average particle diameter.

The particle shape is not particularly limited, and may be, for example, any of a cube, an octahedron, a tetrahedron, a tabular grain, a potato-like grain, and the like.

The emulsion of the present invention containing the above AgX grains (1) may be used in at least one silver halide emulsion layer in the light-sensitive material. It is preferably used for.

Preferably, at least 30 mol% or more of all silver halide grains contained in the emulsion layer are AgX grains (1), and particularly preferably 60 mol% or more.

The emulsion of the present invention has the same solubility product of the AgX grains (1),
Or, the smaller solubility product of AgX particles (2)
The AgX particles (1) are present at least at one stage in the growth process of the gX particles (1), and the AgX particles (1) are grown in the presence of the AgX particles (2). Here, AgX particles (2) are AgX particles (1)
Grain growth elements (halogen ionic liquid, silver ionic liquid, etc.)
Can be used to grow AgX particles (1) by the end of the supply.

The AgX particles (2) are fine particles, where the fine particles mean that the solubility product is equal to or smaller than that of the AgX particles (1). Generally, the average particle size of the AgX particles (2) is smaller than the average particle size of the AgX particles (1), but may be larger in some cases. The AgX particles (2) generally have substantially no photosensitivity. The average particle size of the AgX particles (2) is 0.001 to 0.7.
μm, more preferably 0.01 to 0.3 μm, and particularly preferably 0.1 to 0.01 μm.

Hereinafter, regarding the embodiment in which the AgX particles (2) are present,
This will be described in detail together with the description of the particle growth step of gX (1).

A first method of growing AgX (1) is to use silver halide seed grains and grow the seed grains using a water-soluble silver salt solution and a water-soluble halogen solution as grain growth elements.
This is a method for obtaining particles (1). Further, the second method uses the above two solutions (in the present specification, without using seed particles).
This is called a grain growth element) to form silver halide nuclei and then grow the grains to obtain AgX grains (1). In terms of reproducibility of the particle size of AgX particles (1),
The first method is advantageous.

The AgX particles (2) are used as a suspension system for preparing AgX particles (1) at least at one stage in the growth process of the AgX particles (1), that is, at the latest at the end of the growth of the AgX particles (1). (Hereinafter referred to as mother liquor).

When silver halide seed grains are used, the AgX grains (2) may be present in the mother liquor before the seed grains, or may be added to the mother liquor containing the seed grains prior to the grain growth composition. It may be added during the addition of the grain growth element, or may be added in two or more of the above-mentioned addition times.

When grain growth is performed after silver halide nucleation without using seed grains, it is preferable to add AgX grains (2) after nucleation, and before or during the addition of the grain growth element. It may well be divided into two or more periods.

As a method for adding the AgX particles (2) and the particle growth element, they may be added all at once, or may be added continuously or intermittently.

The AgX particles (2) and the particle growth element are preferably added to the mother liquor by a multi-jet method such as a double jet method under conditions in which pH, pAg, temperature and the like are controlled at a rate suitable for the particle growth.

The AgX grains (2) and the silver halide seed grains may be prepared in the mother liquor, or may be prepared outside the mother liquor and then added to the mother liquor.

As the water-soluble silver salt solution used for preparing the AgX particles (2), an ammoniacal silver salt solution is preferable.

The halogen composition of the AgX grains (2) is, for example, when the AgX grains (1) are silver iodobromide, iodobromide having a higher iodine content than silver iodide or growing silver iodobromide grains. Silver is preferred. For example, when the AgX grains (1) are silver chlorobromide, silver bromide or silver chlorobromide having a higher bromine content than growing silver chlorobromide is preferred. When the AgX grains (1) are silver iodobromide, the AgX grains (2) are particularly preferably silver iodide.

When AgX (1) is silver iodobromide or silver chloroiodobromide, it is preferable that all iodine used for grain growth be supplied as AgX grains (2), but this does not impair the effects of the present invention. Part of the range may be supplied as an aqueous halogen solution.

The AgX particles (2) preferably have good monodispersibility.

Various silver halide seed grains such as silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, silver bromoiodide, and silver chloroiodobromide may be used as desired. Can be.

In the step of preparing the AgX particles (1), the temperature of the mother liquor is preferably 10 to 70 ° C, more preferably 20 to 60 ° C, and pAg
Is preferably 6 to 11, more preferably 7.5 to 10.5, and the pH is preferably 5 to 11, more preferably 7 to 10.

In the emulsion of the present invention, iridium ions are present at least after the start of the grain growth of the AgX grains (1).

Iridium ions can be present by adding a water-soluble iridium salt.

The water-soluble iridium salt used in the present invention is not particularly limited, and examples thereof include the following. For example, Na ₂ IrCl ₆ , K ₃ IrCl ₆ , K ₂ IrCl ₆ , (NH ₄ ) ₂ IrCl ₆ , Na ₂ IrCl
₆ and so on.

These compounds can be used in any combination.

These iridium compounds can be used after being dissolved in water or a suitable solvent. As a commonly used method for stabilizing the solution of iridium compound,
Hydrogen halide aqueous solution (eg, HCl, HBr, HF) or alkali halide (eg, KCl, NaCl, KBr, NaBr)
Can be used.

The amount of iridium ion used in the present invention is 1 × 10 ^-4 per mol of all silver halide finally formed.
Molar or less is preferred. 1 × 10 ⁻⁵ mol or less is more preferable, and 1 × 10 ⁻⁷ mol or less is particularly preferable.

The iridium ions need only be present after the start of the grain growth, and may be at the start of the growth, during the growth, or after the growth of the grains. Regarding the method of adding iridium ions, the total amount may be added at an arbitrary point in time when the AgX particles (1) are formed, or the iridium ions may be added in a plurality of portions or continuously.

It is also possible to add a mixture with an aqueous halide solution, which is a silver halide grain growth element.

At this time, the iridium ion is 70% of the final particle size.
After the above is formed, it is preferable to add it before chemical ripening.

The position of iridium in the AgX particles (1) is considered to depend on the time of addition of iridium ions during the particle growth process. However, iridium may be contained in any position of the particles, and may be unevenly distributed in the center of the particles. , At the surface or throughout, but from the surface of the particle
It is particularly preferred that an iridium-containing layer is present at 0 °. That is, it is most preferable that iridium is present in a layer immediately inside the surface layer of the crystal of the AgX particles (1), particularly preferably in a layer of about several hundred degrees from the surface.
Immediately before the completion of crystal grain growth, iridium ions are added,
Thereafter, the particles may be grown for about several hundred degrees.

When preparing the emulsion of the present invention or other emulsions used in combination as necessary (including the preparation of a seed emulsion)
In addition, a substance other than gelatin having adsorptivity to silver halide grains may be added. Such adsorbents are useful, for example, compounds or heavy metal ions used in the art as sensitizing dyes, antifoggants or stabilizers. Specific examples of the adsorptive substance are described in JP-A-62-7040.

It is preferable to add at least one of an antifoggant and a stabilizer among the adsorptive substances at the time of preparing the seed emulsion from the viewpoint of reducing the fog of the emulsion and improving the stability over time.

Among the antifoggants and stabilizers, heterocyclic mercapto compounds and / or azaindene compounds are particularly preferred. Specific examples of more preferred heterocyclic mercapto compounds and azaindene compounds are described in detail in JP-A-63-41848, and these can be used.

The addition amount of the heterocyclic mercapto compound and the azaindene compound is not limited, but is preferably 1 × 10 ^{−5 to} 3 × 10 ⁻² per mol of silver halide, and more preferably 5 × 10 ^{−2.
-5 to} 3 × 10 ^-3 mol. This amount is appropriately selected depending on the production conditions of the silver halide grains, the average particle size of the silver halide grains, and the type of the compound.

The finished emulsion having the predetermined grain conditions is desalted by a known method after silver halide grains are formed. As desalting methods, Japanese Patent Application Nos. 62-81373 and 63-904
No. 7, the aggregated gelatin agent used for desalting the particles as the seed particles may be used, or a Noudel water washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions For example, a coagulation method using sodium sulfate, an anionic surfactant, or an anionic polymer (for example, polystyrene sulfonic acid) may be used.

The silver halide grains thus desalted are redispersed in gelatin to prepare an emulsion.

The emulsion used in the present invention can be chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization using gold or another noble metal compound. Sensitivity and the like can be used alone or in combination.

As the chemical sensitizer, for example, a chalcogen sensitizer can be used, and among them, a sulfur sensitizer and a selenium sensitizer are preferable.

Examples of the sulfur sensitizer include thiosulfate, allyl thiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine. In addition, U.S. Patent Nos. 1,574,944 and 2,410,689
No. 2,278,947, 2,728,668, 3,501,313,
No. 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-24937, and JP-A-55-45016 can also be used.

The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as the pH and the size of the silver halide grains, but as a guide, the amount is from 10 ^-7 mol to 10 ^-1 mol per mol of silver halide. The degree is preferred.

As selenium sensitizers, aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas,
Selenoketones, selenoamides, selenocarboxylates and esters, selenophosphates, diethyl selenides, selenides such as diethyl dilenide can be used, and specific examples thereof are described in U.S. Pat.
No. 4, No. 1,602,592 and No. 1,623,499.

Further, reduction sensitization can be used in combination. Examples of the reducing agent include stannous chloride, thiourea dioxide, hydrazine, polyazine and the like.

A noble metal compound other than gold, for example, a palladium compound can also be used in combination.

The AgX particles (1) in the present invention preferably contain a gold compound. As the gold compound preferably used in the present invention, the oxidation number of gold may be +1 or +3,
Various gold compounds are used. Representative examples are chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric azide,
Examples include ammonium aurothiocyanate, pyridyltrichlorogold, gold sulfide, and gold selenide.

The gold compound may be used to sensitize the particles,
A method that does not substantially contribute to sensitization may be used.

The amount of the gold compound to be added varies depending on various conditions, but as a guide, it is from 10 ^-8 mol to 10 ^-1 per mol of silver halide.
Preferably it is 10 ^-7 to 10 ^-2 mol. These compounds may be added at any time during the formation of AgX particles, during physical ripening, during chemical ripening, and after the completion of chemical ripening.

The emulsion can be spectrally sensitized to a desired wavelength region by using a sensitizing dye. The sensitizing dyes may be used alone or in combination of two or more.

A dye which does not have a spectral sensitizing effect with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. Is also good.

The silver halide photographic light-sensitive material of the present invention can be used as any light-sensitive material. Color negative film, color reversal film, color paper, etc.).

Further, it can be used as a photosensitive material for diffusion transfer (for example, a color diffusion transfer element, a current salt diffusion transfer element) and a heat development photosensitive material (black and white, color).

In the case of a multicolor photographic light-sensitive material, yellow,
Each of the blue-sensitive, green-sensitive and red-sensitive AgX emulsion layers containing magenta and cyan couplers and, if necessary, a non-photosensitive layer is laminated on a support in an appropriate number and order of layers. However, the number of layers and the order of the layers may be appropriately changed depending on the priority performance and the purpose of use.

The photographic light-sensitive material of the present invention includes an antifoggant, a hardener,
Additives such as a plasticizer, a latex, a surfactant, a color antifoggant, a matting agent, a lubricant, and an antistatic agent can be optionally used.

The photographic light-sensitive material of the present invention can form an image by performing various black-and-white developing processes or color developing processes.

As the color developing agent used in the color developing process, aminophenol-based and p-phenylenediamine-based derivatives widely used in various color photographic processes can be used.

The color developing solution applied to the processing of the photographic light-sensitive material includes:
In addition to the primary aromatic amine color developing agent, a known developer component compound can be added. It can also be processed in a system that does not contain benzyl alcohol, which has a problem in pollution load.

The pH value of the color developer is usually 7 or more, most usually about 10-13.

Color development temperature is usually 15 ° C or higher, generally 20 ° C
In the range of ~ 50 ° C. For rapid development, it is preferably carried out at 30 ° C. or higher. In the case of conventional processing, the time is 3 to 4 minutes, but if an emulsion for rapid processing is assembled, the color development time is generally in the range of 20 to 60 seconds, and further in the range of 30 to 50 seconds. Is also possible.

When the photographic light-sensitive material of the present invention is subjected to color development processing, generally, a color developing solution, bleaching processing and fixing processing are performed. The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

Next, the present invention will be described with reference to examples. However, needless to say, the present invention is not limited by the following examples.

 First, the preparation of each emulsion used in the examples will be described.

Preparation of Seed Emulsion N-1 (Formulation Example 1) To 500 ml of a 2.0% aqueous gelatin solution at a temperature of 40 ° C. was added
According to the method described in No. 45437 4M-AgNO ₃ aqueous solution 250 ml and 4
250 ml of aqueous solution of M-KBr-KI [KBr: KI = 98: 2 (molar ratio)]
, 9.0 pAg by controlled double jet method,
The addition was done over 35 minutes while controlling the pH to 2.0 (where M is molar). The pH of the aqueous gelatin solution containing the silver halide grains obtained above was adjusted to 5.5 with a potassium carbonate aqueous solution, and 364 ml of a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. as a precipitant, and sulfuric acid as a polyvalent ion were used as the precipitating agent. 244 ml of 20% magnesium aqueous solution was added to cause coagulation,
After settling by settling and decanting the supernatant, distilled water 1,
400 ml was added and dispersed again. 36.4 ml of a 20% aqueous solution of magnesium sulfate was added and coagulated again. The sedimented supernatant was decanted and the total amount was reduced to 4 with an aqueous solution containing 28 g of ossein gelatin.
A seed emulsion was prepared by dispersing the mixture in 25 ml at 40 ° C. for 40 minutes.

This seed emulsion is designated as N-1. N-1 was a monodisperse emulsion having an average particle size of 0.093 μm as a result of observation with an electron microscope.

Preparation of Seed Emulsion N-2 (Formulation Example 2) In the same manner as in Formulation Example 1, the average particle size was 0.27 μm.
An AgBrI seed emulsion N-2 having a silver iodide content of 2 mol% was prepared.

Emulsion Production Example 1 Four types of emulsions EM-1 were prepared using the following six types of solutions.
~ 4 were created. The grains in the emulsion EM-1 had an average grain size of 0.38
μm and a core / shell type silver iodobromide having an average AgI content of 8.46 mol%.

(Solution A-1) Ossein gelatin 28.78 g 10% ethanol solution of 1700 pronone (manufactured by NOF CORPORATION) 16.5 ml KI 146.5 g distilled water 5287 ml (solution B-1) Seed emulsion N-1 AgX 0.1552 mol equivalent 4-hydroxy-6-methyl-1,3 , 3a, 7-Tetrazaindene (hereinafter referred to as TAI) 247.5 mg 56% acetic acid aqueous solution 72.6 ml 28% aqueous ammonia 97.2 ml Make up to 1020 ml with distilled water.

(Solution C-1) 1774 g of AgNO ₃ 1447 ml of 28% aqueous ammonia Make up to 2983 ml with distilled water.

(Solution D-1) Ossein gelatin 50 g KBr 2082.5 g TAI 2.535 g Make up to 5000 ml with distilled water.

(Solution E-1) Required amount of pAg adjustment for 20% aqueous KBr solution (Solution F-1) Required amount of pH adjustment for 56% acetic acid aqueous solution At 40 ° C., mixing and stirring described in JP-A-57-92523 and JP-A-57-92524. Solution A-1 was added to Solution A-1 using a vessel.
Was added over 1 minute to produce AgI particles. AgI
As a result of observation with an electron microscope, the particles had a particle size of about 0.05 μm. The AgI particles correspond to the silver halide fine particles (AgX (2)) in this example. Solution B-1 was added following the formation of the AgI particles.

Next, the pAg, pH and the flow rates of the solution C-1 and the solution D-1 were determined by the simultaneous mixing method using the solution C-1 and the solution D-1.
Was added while controlling as shown in FIG. If only the solution C-1 and the solution D-1 are mixed at the same time, silver bromide is produced. At this time, since AgI particles are already present, grain growth in the presence of the AgI particles results in iodine. Silver bromide grows. When the addition is continued and the AgI particles are consumed, silver bromide grows. Thus, the resulting grains have different silver halide compositions, with silver iodobromide as the core and silver bromide as the shell.

The control of pAg and pH during the simultaneous mixing was carried out by changing the flow rates of the solution E-1 and the solution F-1 by using a variable flow rate roller tube pump. Two minutes after the completion of the addition of the solution C-1, the pAg was adjusted to 10.4 by the solution E-1 and further to pH 6.0 by the solution F-1 two minutes later.

Then, desalinated water washing is carried out in the usual manner, and ossein gelatin is used.
After dispersing in an aqueous solution containing 197.4 g, the total amount is
It was adjusted to 00 ml to obtain emulsion EM-1.

 Emulsions EM-2 to EM-4 were prepared as follows.

EM-2 performs exactly the same grain growth as EM-1, and the amount of added silver is 98.5% of the total amount of silver added by the end of crystal growth.
In addition the position of, and the K ₂ IrCl ₆ was added 6.5 × 10 ^-6 mol / mol AgX.

EM-3 performs exactly the same grain growth as EM-2, and K ₂ IrCl ₆ is added at 6.5 × 10 ⁻⁸ at the addition position where the amount of added silver is 98.5% of the total amount of silver added before the completion of crystal growth. Mol / mol AgX was added.

EM-4 performs exactly the same grain growth as EM-3, and K ₂ IrCl ₆ is added at 6.5 × 10 ⁻⁸ at the addition position where the added silver amount is 90.0% of the total silver amount added by the end of crystal growth. Mol / mol AgX was added.

Emulsion Production Example 2 (Comparative Emulsion)
Silver / iodobromide emulsions of core / shell type having an AgI content of mol%, 5 mol% and 3 mol%, an average grain size of 0.38 μm and an average AgI content of 8.46 mol% were prepared. Although the silver iodide content is different in each part, each part of the grains uses an aqueous solution of halogen and is comparative.

(Solution A-5) Ossein gelatin 28.6 g Pronone (10% ethanol solution) 16.5 ml TAI 247.5 mg 56% acetic acid aqueous solution 72.6 ml 28% aqueous ammonia solution 97.2 ml Seed emulsion N-1 AgX 0.1552 mol equivalent amount Distilled water to 600 ml I do.

(Solution B-5) Ossein gelatin 13 g KBr 460.2 g KI 113.3 g TAI 665 mg Make up to 1300 ml with distilled water.

(Solution C-5) Ossein gelatin 17 g KBr 672.6 g KI 49.39 g TAI 870 mg Make up to 1700 ml with distilled water.

(Solution D-5) Ossein gelatin 8 g KBr 323.2 g KI 13.94 g TAI 409 mg Make 800 ml with distilled water.

(Solution E-5) 1773.6 g of AgNO ₃ 28% ammonia water 1470 ml Make up to 2983 ml with distilled water.

(Solution F-5) 20% KBr aqueous solution pAg adjustment required amount (Solution G-5) 56% acetic acid aqueous solution pH adjustment required amount -5 and the solution B-5 were added by the simultaneous mixing method, and C-5 was added at the same time as the completion of the B-5 addition.
D-5 was added at the same time as the addition of C-5 was completed. Control of pAg and pH during simultaneous mixing and solution E-5, solution B-5, solution C
The addition rates of -5 and solution D-5 were as shown in Table-2.

The control of pAg and pH was performed by changing the flow rates of the solution F-5 and the solution G-5 using a roller tube pump having a variable flow rate.

After the addition of the solution E-5 was completed, the pH and p were adjusted in the same manner as in Production Example 1.
Ag adjustment, desalination water washing, and redispersion were performed.

 This emulsion is designated as EM-5.

Further, an emulsion EM-6 was prepared as follows. That is,
EM-6 grows grains under exactly the same growth conditions as EM-5. When 98.5% of the total silver added, K ₂ IrCl ₆ is added to 6.5 ×
It was prepared by adding 10 ^-8 mol / mol AgX.

Emulsion Production Example 3 In the same manner as in Production Example 1, AgX particles (core / shell type AgBrI) having an average particle size of 0.65 μm and an average AgI content of 7.16 mol% were prepared.

(Solution A-3) Ossein gelatin 45 g KI 116.8 g Pronone (10% ethanol solution) 30 ml Make up to 9191 ml with distilled water.

(Solution B-3) Seed emulsion N-2 AgX 0.759 mol equivalent 56% acetic acid aqueous solution 112.5 ml 28% ammonia water 175.5 ml TAI 600 mg Make up to 2608 ml with distilled water.

(Solution C-3) AgNO ₃ 1671 g 28% ammonia water 1363 ml Distilled water is made 2810 ml.

(Solution D-3) Ossein gelatin 50 g KBr 2082.5 g TAI 5.338 g Make up to 5000 ml with distilled water.

(Solution E-3) Same as Solution E-1 (Solution F-3) Same as Solution F-1 At 40 ° C., add 201 ml of Solution C-3 to Solution A-3.
Minutes. Others were the same as in Production Example 1. pH, p
Ag and flow rate are shown in Table-3. EM-
7 is assumed. The grains contained in this emulsion are also of a mixed composition having silver iodobromide as a core and silver bromide as a shell.

Further, growth was performed in exactly the same manner as in EM-7, and K ₂ IrCl ₆ was added at 6.5 × 10 ⁻⁸ mol / mol Ag at a position of 98.5% of the total amount of silver added.
X was added. The resulting emulsion is designated as EM-8.

Emulsion Production Example 4 (Comparative Emulsion) With reference to Production Example 2, 15 mol%
A silver iodobromide emulsion (comparative) having a core / shell structure having an AgI content of 5 mol% and 3 mol% and an average AgI content of 7.1 mol% was prepared. This emulsion is called EM-9.

Further, the same growth as EM-9 was performed, and the total added silver amount was 9%.
An emulsion was prepared by adding 6.5 × 10 ⁻⁸ mol / mol AgX of K ₂ IrCl ₆ at the 8.5% position, and was referred to as EM-10.

Emulsion Production Example 5 (Comparative Emulsion) With reference to Production Example 4, an octahedral monodispersed comparative emulsion EM-11 having a silver iodide content of 2 mol% and an average grain size of 0.65 μm was prepared.

Further, the same grain growth as EM-11 was performed, and the total added silver amount
An emulsion was prepared by adding 6.5 × 10 ⁻⁸ mol / mol AgX of K ₂ IrCl ₆ at the 98.5% position to prepare EM-12.

Example 1 For each of EM-1 to EM-6 described in Production Examples 1 and 2,
Gold sulfur sensitization was optimally performed to obtain six chemically sensitized emulsions. Further separately, EM-1 described in Production Examples 1 and 2 and
Using two kinds of emulsions of EM-5, K ₂ IrCl ₆ was used for EM-1.
Of 6.5 × 10 ⁻⁶ mol / mol AgX, 6.5 × 10 ⁻⁸ mol / mol
Two emulsions with mol AgX added and two emulsions with EM-5 added in the same manner were obtained and ripened for 30 minutes. Thereafter, gold ion sensitization was performed to obtain four types of sensitized emulsions. For spectral sensitization, 350 ml of the following sensitizing dye (I) and 350 mg of the sensitizing dye (II) were added per mole of Ag, and the mixture was spectrally sensitized to blue sensitivity. Then TAI and 1-phenyl-5-
Stabilization was achieved by adding mercaptotetrazole. A coating solution was prepared by adding a general photographic additive such as a spreading agent and a hardening agent to each of the above 10 types of emulsions, coated and dried on a subbed film base by a conventional method, and dried. From No.10
It was created.

The yellow coupler (Y-1) shown below was dissolved in ethyl acetate and dioctyl phthalate in the same weight as the coupler and emulsified and dispersed in an aqueous solution containing gelatin, and then added to each of the above emulsions. And dried in the same manner as in No. 10 to obtain Sample Nos. 11 to 20.

To each of Sample Nos. 1 to 20 through a blue filter, 8
Wedge exposure was performed under three types of exposure conditions of 1 second, 12.5 seconds, and 1 × 10 ^-4 seconds. Of the samples after exposure, sample Nos. 1 to 10
Using a KX-500 automatic developing machine manufactured by Konica Corporation, processing was performed for 90 seconds with the following developing solution in the following processing step (I) to determine the sensitivity.

Processing step (I) (35 ° C) Current 25 seconds Fixed 25 seconds Rinse 25 seconds Dry 15 seconds The composition of the processing solution used in each processing step is shown below.

<Developer> Potassium sulfite 55.0 g Hydroquinone 25.0 g 1-Phenyl-3-pyrazolidone 1.2 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Methylbenzotriazole 0.07 g 5-Nitroindazole 0.14 g 1-phenyl -5-Mercaptotetrazole 0.015 g Glutaraldehyde bisulfite 15.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylenetetramine hexaacetic acid 2.5 g Finished to 1 with water and adjusted to pH = 10.20.

<Fixing solution> Ethylenediaminetetraacetic acid disodium salt 5.0 g Tartaric acid 3.0 g Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Sodium acetate trihydrate 25.8 g Aluminum sulfate 18 hydrate 14.6 g Sulfuric acid (50 wt%) 6.77 g Add water to make 1 and adjust to pH = 4.20.

Samples No. 11 to No. 20 were exposed in the same manner as Samples No. 1 to No. 10, and processed according to the following processing step (II).

Processing step (II) (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in the process is shown below.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Potassium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

<Bleaching liquid> Iron ammonium diaminediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Potassium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to adjust the pH to 1, and the pH is adjusted to 6.0 using aqueous ammonia.

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to 1 and adjust to pH 6.0 with acetic acid.

<Stabilizing solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

Table 4 shows the results of fog (Dmin) and sensitivity at each exposure.

In Table 4, the sensitivities of the cases where the coupler was not added and where the coupler was added were respectively fog density +0.1.
The reciprocal of the amount of exposure that gives
Sample No. 1 is shown with relative sensitivity assuming the sensitivity of 1 / 12.5 second exposure as 100.Sample Nos. 11 to 20 are shown with relative sensitivity assuming that sample No. 11 has sensitivity of 1 / 12.5 second exposure as 100. .

As shown in Table 4, samples Nos. 1 to 10 to which no coupler was added and Samples Nos. 2 to 4 using emulsions doped with iridium of the present invention inside the crystal were used.
Is a comparative sample in which iridium is not doped into the crystal.
It can be seen that the fogging is lower and the sensitivity is higher than that of Comparative Sample No. 6, which uses No. 1, No. 5, and an emulsion doped with iridium inside the crystal. Further, as is clear from the results of Sample Nos. 7 to 10, iridium was added after the crystal growth was completed, and Samples Nos. 7 to 8 of the present invention were added with iridium after the completion of crystal growth. From Comparative Sample Nos. 9 to 10, it was found that the fogging was low and the sensitivity was high, and the same effect as in the case where iridium was doped inside the crystal was obtained.

Here, the sample using the emulsion according to the present invention has higher sensitivity than the comparative sample even at low illuminance and at high illuminance, and thus the present invention has the effect of improving the illuminance failure, but simply means that. You can see that it is not.

Also, in samples Nos. 11 to 20 to which the coupler was added, the same effect as in the case where no coupler was added was obtained, and it was shown that the sample of the present invention had low fog and high sensitivity.

Example 2 EM-7 to EM-10 described in Production Examples 3 and 4, respectively.
Was subjected to chemical sensitization and spectral sensitization in the same manner as in Example 1 to prepare a green-sensitive emulsion, and a magenta coupler was added as shown in Table 5 to prepare Sample Nos. 21 to 26. However, the sensitizing dye used for the spectral sensitization was the following sensitizing dye (II
I) was 300 mg per mole of Ag and sensitizing dye (IV) was 30 mg per mole of Ag.

Each of Sample Nos. 21 to 26 prepared above was exposed and developed in the same manner as in Example 1. However, the exposure was carried out using a blue and yellow filter for 1 / 12.5 seconds, and the processing was performed using the processing step (II) shown in Example 1.

The results are shown in Table-5. The sensitivity is the reciprocal of the exposure that gives the fog density +0.1, and the blue sensitivities of sample Nos. 21 to 26 are relative values with the blue sensitivity of sample No. 21 before adding the spectral sensitizing dye as 100. And the yellow sensitivity is
It is represented by a relative value with the yellow sensitivity of Sample No. 21 being 100.

As shown in Table 5, in Sample No. 22 using the emulsion of the present invention in which iridium was doped inside the crystal, the decrease in the intrinsic portion sensitivity before and after the addition of the dye and the spectral sensitization showed a decrease in the comparative emulsion. On the other hand, it is small, the sensitivity in the spectral sensitizing unit is high, and the fog is low.

Furthermore, it can be seen from Samples No. 25 and No. 26 that the effect of the present invention by the iridium compound is small in the silver iodobromide emulsion having a uniform halide composition.

Sample No. 1 was obtained regardless of whether an emulsion in which iridium was uniformly doped into grains under completely the same growth conditions as EM-8 or an emulsion in which iridium was added at 98.5% or less of the total silver content was used. As in the case of 22, the effect of the present invention was obtained.

Example 3 A multilayer color light-sensitive material No. 27 having an upper and lower layer constitution having the following composition was formed on a cellulose acetate support subjected to an undercoating process.

The amount coated amount was expressed in terms of silver for silver halide and colloidal silver in the unit of g / m ^2, also the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye The couplers and couplers are shown as moles per mole of silver halide in the same layer.

The emulsion contained in each color-sensitive emulsion layer was optimally sensitized in the same manner as in Example 1.

Further, Sample Nos. 28 to 30 were prepared as described below.

For sample No. 28, replace EM-1 of sample No. 27 with EM-3,
This sample was prepared and produced in exactly the same manner as Sample No. 27 except that -7 was changed to EM-8.

For sample No. 29, replace EM-1 of sample No. 27 with EM-5,
This sample was prepared and produced in exactly the same manner as Sample No. 27 except that -7 was changed to EM-9.

For sample No. 30, replace EM-1 of sample No. 27 with EM-6,
This sample was prepared in exactly the same manner as Sample No. 27 except that EM-10 was used instead of -7.

Each of the obtained samples was exposed to white light and developed. Thereafter, the relative sensitivity was measured.

The relative sensitivities were measured from yellow, magenta, and cyan densities according to a conventional method.

 Table 6 shows the results.

As is clear from Table-6, Sample No. 28 using the silver halide emulsion according to the present invention has higher sensitivity than Comparative Samples Nos. 27, 29 and 30, and a single phase It was shown that the same effect as the sample was obtained.

[Effects of the Invention] As described above, the silver halide photographic light-sensitive material of the present invention is a light-sensitive material having high sensitivity and improved illuminance failure, and also has low fog and desensitization due to dye adsorption and the like. This has the effect that it can be prevented.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiroshi Otani 1st Sakuramachi, Hino-shi, Tokyo Konica Corporation (72) Inventor Shoji Matsuzaka 1st Sakuramachi, Hino-shi, Tokyo Konica Corporation (56) References JP-A-1-105940 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing emulsions having different silver halide compositions, wherein said emulsion is formed by growing silver halide grains contained in said emulsion. During at least one period of the process, the silver halide grains grow in the presence of silver halide fine grains having a solubility product equal to or less than that of the silver halide grains contained in the emulsion, and iridium ions are converted to silver halide grains. A silver halide photographic material characterized by being present at least after the start of grain growth.