JPH0329938A - Silver halide photographic sensitive material having high sensitivity - Google Patents

Abstract

PURPOSE:To provide low fogging and to prevent the desensitization by dye stuff adsorption, etc., by forming the above material in such a manner that the particle growth of silver halide particles is executed in the presence of the fine silver halide particles having the solubility product equal to or lower than the solubility product of silver halide particles contained in an emulsion and that iridium ions exist at least after the start of the particle growth of the silver halide particles. CONSTITUTION:The particle growth of the silver halide particles is executed in the presence of the fine silver halide particles having the solubility product equal to or lower than the solubility product of the silver halide particles contained in the emulsion in at least one period of the growth process of the silver halide particles contained in the emulsion. In addition, the iridium ions are made to exist at least after the start of the particle growth of the silver halide particles to form the emulsion. The prevention of an illumination failure by the iridium ion is attained and further the effect of sensitization is exhibited by using such specific silver halide particles. The low fogging photosensitive material is obtd. in this way and the desensitization by the dye stuff adsorption is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved illuminance failure and high sensitivity.

[Background of the invention]

In the field of silver halide photographic light-sensitive materials, there is a need for light-sensitive materials that have improved reciprocity failures such as low-illuminance failure and high-illuminance failure.

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

However, in the conventional technology, even if an iridium compound is added to a silver halide emulsion, the illuminance failure can be improved, but this either causes desensitization or the expected sensitization cannot be obtained, and the photosensitive material This was contrary to the request for higher sensitivity.

[Purpose of the invention]

The present invention solves the above-mentioned problems of the prior art, achieves both high sensitivity and improved illuminance failure, and provides a photosensitive material with high sensitivity and improved illuminance failure, as well as low fog. It is an object of the present invention to provide a silver halide photosensitive material that satisfies the requirements of being able to prevent desensitization due to dye adsorption and the like.

[Means for solving problems]

The present invention provides a silver halide photographic abrasive material having at least one silver halide emulsion layer containing an emulsion having a mixture of different silver halide compositions, wherein the emulsion contains silver halide grains contained in the emulsion. During at least one period of the growth process, silver halide grains are grown in the presence of silver halide fine grains having a solubility product equal to or lower than that of the silver halide grains contained in the emulsion, and iridium ions are halogenated. The present invention is characterized in that it is an emulsion that exists at least after the start of grain growth of silver grains (hereinafter, such an emulsion will be appropriately referred to as "the emulsion of the present invention"), and such a structure By doing so, the above objective was achieved.

That is, in conventionally used emulsions, when an iridium compound was added to improve illuminance failure, this sometimes caused desensitization. By using silver oxide emulsion,
Iridium ions were able to improve illuminance failure and further enhance sensitization.

Moreover, according to the present invention, a photosensitive material with low fog can be obtained,
It was also possible to prevent desensitization due to dye adsorption.

The present invention will be explained in detail below.

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

The emulsions of the present invention mix different silver halide compositions.

Mixing different silver halide compositions means that different silver halide compositions are mixed within the grains of silver halide grains (for example, the silver halide compositions are different between the inside of the grain and other outer parts within the grain). are different)
In some cases, there are cases where grains have different silver halide compositions, resulting in mixing (for example, grains with different silver halide compositions are mixed together), and in both cases, In some cases, both appear to be imposing. In the present invention, silver halide compounds may be mixed in any embodiment.

Further, the emulsion of the present invention is characterized in that during at least one period of the growth process of the silver halide grains contained in the emulsion, the silver halide grains contained in the emulsion (rAg
Silver halide grains are grown in the presence of silver halide fine grains (referred to as "Ag be.

The solubility product being equal or lower means that the solubility product of AgX particles (2) is equal to or smaller than the solubility product of AgX particles (1). In addition, the solubility product in this specification is
In the ordinary chemical sense.

Although the AgX grains (1) contain two or more types of silver halide compositions as described above, they cannot be used as an emulsion due to the mixture of grains with different silver halide compositions. It may be mixed, but when mixed inside the particle,
The two or more types of silver halides mixed may be uniformly distributed in the grains or may be non-uniformly distributed. In the present invention, non-uniform cases such as core/shell type and epitaxial type are preferred, and core/shell type is particularly preferred.

There is no particular limitation on the silver halide composition of the AgX grains (1), as long as the emulsion containing the AgX grains (1) has a different silver halide composition, but silver iodobromide, silver chlorobromide, ,
Silver chloroiodobromide is preferred, and silver iodobromide is particularly preferred. That is, for example, mixed crystals such as silver iodobromide and silver chlorobromide can be used, but it is preferable to use a core having a silver iodide content of 15 mol% or more and 40 mol% or less. Silver iodobromide with a shell structure is preferable.

Furthermore, the particle size of the AgX particles (1) is preferably 3.0 μm or less in equivalent sphere diameter.

The AgX particles (1) may be polydispersed or monodispersed, but preferably monodispersed.

Monodisperse herein means that 95% or more of all particles are within a range of ±40% of the average particle diameter.

Further, the shape of the particles is not particularly limited, and may be any shape such as cubes, octahedrons, tetradecahedrons, tabular grains, and potato-shaped grains.

The emulsion of the present invention containing AgX grains (1) may be used in at least one silver halide emulsion layer in a light-sensitive material, but if there are two or more emulsion layers, all emulsion layers are used. It is preferably used for.

It is preferable that AgX grains (1) account for at least 30 mol % of all the silver halide grains contained in the emulsion layer, particularly preferably 60 mol % or more.

The emulsion of the present invention has a solubility product equivalent to that of AgX grains (1),
AgX particles (2) having a solubility product or smaller solubility product are present during at least one period of the growth process of AgX particles (1), and the growth of AgX particles (1) is performed in the presence of the AgX particles (2). Here, AgX particles (2) are made to exist until the supply of grain growth elements (halogen ion liquid, silver ion liquid, etc.) of AgX particles (1) is completed, and Ag
It can be used to grow X particles (1).

The AgX particles (2) are fine particles, and the term fine particles here means 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 in some cases it may be larger. Moreover, the AgX particles (2) generally have substantially no photosensitivity. This AgX particle (2
) has an average particle size of 0.001 to 0. It is preferably <7 pm, more preferably 0.01 to 0.3 μm, and particularly preferably 0.1 to 0.01 μm.

Hereinafter, regarding the mode of making AgX particles (2) exist,
The particle growth process of AgX (1) will be explained in detail along with an explanation.

The first method for 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, which are grain enhancing factors.
This is a method for obtaining gX particles (1). In addition, the second method involves shaping silver halide nuclei with the above two solutions (herein referred to as grain lengthening elements) without using seed grains, and then lengthening the grains. This is a method for obtaining AgX particles (1). The first method is advantageous in terms of reproducibility of the particle size of AgX particles (1).

The AgX particles (2) grow at least once during the growth process of the AgX particles (1), that is, at the latest when the AgX particles (1) grow.
It is necessary to make the AgX particles (1) exist in a suspension system (hereinafter referred to as mother liquor) which serves as a place for preparing them by the time the growth of the AgX particles (1) is completed.

When using silver halide seed grains, AgX grains (2
) may be present in the mother liquor before the seed particles,
It may be added to the mother liquor containing the seed particles prior to the particle growth compound, it may be added during the addition of the particle growth elements, or it may be added at two or more of the above-mentioned addition times. It may be added in portions.

When silver halide nucleus formation or post-grain growth is performed without using seed grains, it is preferable to add AgX grains (2) after the nucleus formation. It may be done midway, or it may be divided into two or more periods.

Furthermore, the AgX particles (2) and the particle growth elements may be added all at once, continuously, or intermittently.

It is preferable that the AgX particles (2) and the particle growth element are added to the mother liquor by a multiple Gesoto method such as a double Gesoto method under conditions where pH, pAg, temperature, etc. are controlled at a rate suitable for particle growth.

The AgX grains (2) and silver halide seed particles 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 particles (2) is, for example, Ag
When the X grains (1) are silver iodobromide, silver iodobromide having a higher iodine content than silver iodide or growing silver iodobromide grains is preferable; for example, if the AgX grains (1) are When silver bromide is used, silver chlorobromide having a higher bromine content than silver bromide or growing silver chlorobromide is preferred. When the AgX grains (1) are silver iodobromide, it is particularly preferable that the AgX grains (2) are silver iodide.

When AgX (1) is silver iodobromide or silver chloroiodobromide, all the iodine used for grain growth becomes 8QX grains (2
), but part of it may be supplied as an aqueous halogen solution as long as the effects of the present invention are not impaired.

It is preferable that the AgX particles (2) have good monodispersity.

The composition of the silver halide seed grains is silver chloride, silver bromide,
Various materials such as silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used as desired.

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.
°C, 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 AgX grains (1
) has existed at least since the start of grain growth.

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

Water-soluble iridium salts used in the present invention are not particularly limited, but include the following. For example, Na31rfJa. K+TrlJ6, Kzlr
lJ6. (NH4.)zIrCL, , Na2Ir
There are Clb, etc.

Moreover, these compounds can also be used in arbitrary combination.

These iridium compounds can be used after being dissolved in water or a suitable solvent. A commonly used method for stabilizing solutions of iridium compounds is
Hydrogen halide aqueous solution (e.g. HIJ, HBr, H
F), or alkali halides (e.g. KCe
．． A solution to which NaCe, KBr, NaBr) is added can also be used.

The amount of iridium ion added used in the present invention is preferably 11 12 IXIO-' mol or less per 1 mol of total silver halide finally formed. It is more preferably 1 x 10 to 5 mol or less, and particularly preferably IXIO-' mol or less.

Iridium ions need only be present after the grain growth starts, and may be present at the time of grain growth, during grain growth, or after grain growth. For information on how to add iridium ions,
AgX particles (type 1) may be added in full at any time during the preparation, or may be added in multiple portions or continuously.

It is also possible to add it by mixing it with an aqueous halide solution which is a silver halide grain growth factor.

Also, at this time, iridium ions account for 70% of the final particle size.
It is preferable to add it after the above is established and before chemical ripening.

The location of iridium in the AgX particles (1) is thought to depend on the timing of addition of iridium ions during the grain growth process, but iridium may be contained in any location of the grain, even if it is unevenly distributed in the center of the grain. , may be contained on the surface or throughout the particle, but approximately several 1 from the particle surface.
Particularly preferred is the presence of an iridium-containing layer at 0.00. That is, it is most preferable that iridium exists in a layer immediately inside the surface layer of the crystal of the AgX particle (1), particularly preferably in a layer of about 100 layers from the surface. It is sufficient to add iridium ions immediately before the addition of iridium ions, and then grow particles for about several hundred people.

When preparing the emulsion of the present invention or other emulsions to be used together as necessary (including when preparing the seed emulsion), substances other than gelatin that have adsorption properties to silver halide grains are added. You can.

Such adsorbing substances are useful, for example, compounds or heavy metal ions used in the art as sensitizing dyes, antifoggants or stabilizers. The above-mentioned adsorbent substance is JP-A-62-
Specific examples are described in No. 7040.

Among the adsorbent substances, it is preferable to add at least one of an antifoggant and a stabilizer at the time of preparing the seed emulsion in order to reduce fog and improve stability over time of the emulsion.

Among the antifoggants and stabilizers, heterocyclic mercabuto 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, which can be used.

The amount of the above-mentioned heterocyclic mercabuto compound and azaindene compound added is not limited, but is preferably IXIO-5 to 3X10-2, more preferably 5X10-5 to 3X10-3 mol per mol of silver halide. . This amount is appropriately selected depending on the manufacturing conditions of the silver halide grains, the average grain size of the silver halide grains, and the type of the above-mentioned compound.

The finished emulsion that has been provided with predetermined grain conditions is converted into silver halide grains and then desalted using a known method.

As a method of desalination, Japanese Patent Application No. 6281373 and No. 63
- Agglomerated gelatin agents used for desalting particles as seed particles described in No. 9047 may be used, or the Nudel water washing method performed by gelatinizing gelatin may be used, or an inorganic gelatin agent consisting of polyvalent anions may be used. Coagulation methods using salts such as sodium sulfate, anionic surfactants, and anionic polymers (eg, polystyrene sulfonic acid) may also 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 conventional methods. In other words, sulfur sensitization using active gelatin or compounds containing sulfur that can react with silver ions, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensitive methods and the like can be used alone or in combination.

For example, a chalcogen sensitizer can be used as a chemical sensitizer, and sulfur sensitizers and selenium sensitizers are particularly preferred.

Examples of sulfur sensitizers include thiosulfate. Allylthiorubazide, thiourea, allyl isothiocyanate. Examples include cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patent No. 15 16 No. 1,574,944, No. 2,410,689, No. 2,278,947, No. 2,728,668, No. 3
, No. 501,313, No. 3+656,955, West German Application Publication (○LS) No. 1,422,869, Japanese Unexamined Patent Publication No. 5
Sulfur sensitizers described in No. 6-24937, No. 55-45016, etc. can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, size of silver halide grains, etc., but as a guideline, it is 10 -/1 mole of silver halide.
The amount is preferably about 7 mol to 10 −1 mol.

Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoacids, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, and diethyl selenium sensitizers. Selenides such as gyrenide can be used, specific examples of which are described in U.S. Patent No. L574;
No. 944, No. 1,602, No. 592, L623,4
It is described in No. 99.

Furthermore, reduction sensitization can also be used together. Examples of the reducing agent include stannous chloride, thiourea dioxide, hydrazine, and voriazine.

Moreover, noble metal compounds other than gold, such as palladium compounds, etc. can also be used in combination.

It is preferable that the AgX particles (1) in the present invention contain a gold compound. As the gold compound preferably used in the present invention, the oxidation number of gold may be +1 or +3,
A wide variety of gold compounds are used. Representative examples include chlorauric acid salts, potassium chloroaurate, aurisoctotrichloride, and potassium aurisocthiocyanate. Potassium iodooleate, tetracyanoohlic azide.
Examples include ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, and gold selenide.

The gold compound may be used to sensitize the particles, or may be used so as not to substantially contribute to sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guideline it is from 10<-8> to 10<-1> mol, preferably from 10<-7> to 10<-2> mol per mole of silver halide. The timing of addition of these compounds may be in the form of AgX particles, during physical training, during chemical training, or at any step after chemical training is completed.

Emulsions can be spectrally sensitized to a desired wavelength range using sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more.

Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide photographic material of the present invention can be used as any photosensitive material, such as black and white silver halide photographic material (for example, X-ray, lithium type sensitive material, negative film for black and white photography, etc.)
It can be used for color photographic materials (for example, color negative films, color reversal films, color pavers, etc.).

Additionally, photosensitive materials for diffusion transfer (e.g. color diffusion transfer elements,
silver salt spreading transfer element), heat-developable photosensitive material (black and white, color)
It can also be used for

In the case of multicolor photographic materials, in order to perform subtractive color reproduction, blue-sensitive, green-sensitive and red-sensitive AgX emulsions containing yellow, magenta and cyan couplers are usually used as photographic couplers. It has a structure in which layers and, if necessary, a non-photosensitive layer are laminated on a support in an appropriate number and order of layers, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use. You can.

The photographic material of the present invention may optionally contain additives such as anti-capri agents, hardeners, plasticizers, latex, surfactants, anti-color fog agents, capping agents, lubricants, and antistatic agents. can.

Further, the photographic light-sensitive material of the present invention can be subjected to various black-and-white development treatments or color development treatments to form images.

The color developing agents used in color development processing include
Nophenolic and p-phenylenediamine derivatives can be used.

In addition to the primary aromatic amine color developing agent, known developer compounds can be added to the color developing solution applied to the processing of the photographic light-sensitive material.

It is also possible to treat systems that do not contain benzyl alcohol, which poses a problem in terms of pollution load.

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

Color development temperature is usually 15°C or higher, generally 20°C.
It is in the range of °C to 50 °C. For rapid development, it is preferable to carry out the process at 30°C or higher. In addition, conventional processing takes 3 minutes or more.
4 minutes, but if an emulsion is made for rapid processing, the color development time is generally 20 seconds to 60 seconds, and even 30 seconds to 5 minutes.
A range of 0 seconds is also possible.

When the photographic light-sensitive material of the present invention is subjected to color development processing, bleaching treatment and fixing treatment are generally performed after color development. Bleaching treatment may be performed simultaneously with fixing treatment.

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 explained by examples. However, it goes without saying that the present invention is not limited to the following examples.

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

Seed N-1 (person 1) in a 2.0% gelatin aqueous solution 500+nZ at a temperature of 40℃,
250 m7 of 4M-8g No3 aqueous solution and 4M-KBr-Kl according to the method described in JP-A No. 50-45437
[KBr:KI=98:2 (molar ratio) aqueous solution 250-
, pAg was reduced to 9 by controlled double jet method.
．． It was added for 35 minutes while controlling the pH to 0 and 2.0 (M is the molar concentration). After adjusting the pH of the aqueous gelatin solution containing the silver halide grains obtained above in the total amount of added silver to 5.5 with an aqueous potassium carbonate solution, 364 ml of a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. was added as a precipitant.
and a 20% aqueous solution of magnesium sulfate as a polyvalent ion 24
4- was added to cause coagulation, allowed to settle by standing, and the supernatant was decanted, then 1,400 ml of distilled water was added and the mixture was again dispersed. Add 36.4 parts of a 20% aqueous solution of magnesium sulfate to coagulate again, decant the precipitated supernatant, and add an aqueous solution containing 28 g of ossein gelatin to a total volume of 425 ml.
A seed emulsion was prepared by dispersing at 40° C. for 40 minutes.

This seed emulsion is designated as N-1. As a result of electron microscopic observation, N-1 was found to be a monodisperse emulsion with an average grain size of 0.093 μm.

An 8 g Br I type emulsion N2 having an average grain size of 0.27 μm and a silver iodide content of 2 mol % was prepared in the same manner as in Preparation Example 1 of rl-2.

Ball 1B row week production pond = 4 types of emulsion EM-1 using the 6 types of solutions shown below
~4 was created. The grains in emulsion EM-1 have an average grain size of 0.38 μm and an average Agl content of 8.46 mol%.
It is a core/shell type silver iodobromide.

(Solution A-1) Ossein gelatin 28. 78
gIO + CI{zcHJ + '÷CHCLO +'+
CJIzCHzQ÷System Cll3 Average molecular weight 1700 Pronone (manufactured by NOF) 10% ethanol solution 16.5mlKI
146.5 g distilled water 5287mZ (solution B
-1) Seed emulsion N-1 ^gX O. 1552 mol equivalent amount 4-hydroxy-6-methyl-1.3.3a,7tetrazaindene (hereinafter referred to as TAI) 247.5■
56% acetic acid aqueous solution 72.6ml
28% ammonia water 97.2m
/ Make up to 1020ml with distilled water.

(?8 liquid C-1) ng! io3 17
74 g28% ammonia water 14
Make 2983mf with 47-distilled water.

(Solution D-1) 23 24 Ossein gelatin 50gKBr
2082.5 gT
AI 2.535g
Make 5000 companies with distilled water.

(Solution E-1) 20% KBr aqueous solution pAg adjustment required amount (Solution F-1) 56% acetic acid aqueous solution p} {Required adjustment amount 40
℃, JP-A-57-92523, JP-A-57-92
Using the mixer shown in No. 524, 252 J of solution C-1 was added to solution A-1 over 1 minute to stir the AgI particles. As a result of electron microscopy observation, the AgI particles had a particle size of about 0.05 μm. This Agl grain corresponds to the silver halide fine grain (AgX (21) mentioned above) in this example. Solution B-1 was added following the Agl grain preparation.

Next, solution C-1 and solution D-1 were mixed by simultaneous mixing method,
pAg+ pH and solution C-1, solution wI. D1 was added while controlling the flow rate as shown in Table 1. Solution C-
1. If only solution I)-1 is simultaneously mixed, silver bromide will grow, but since AgI grains are already present at this time, as a result of grain growth in the presence of the 8g1 grains, iodine will grow. Silver bromide grows. As the addition continues and the Agl particles are consumed, silver bromide grows. Therefore, the grown grains have a mixture of different silver halide compositions, with silver iodobromide as the core and silver bromide as the shell.

During simultaneous mixing, pAg+pi-1 is controlled by a roller tube pump with variable flow rate.
This was done by changing the flow rate of -1.

Two minutes after the addition of solution C-1 was completed, the pA was adjusted by solution E-1.
g to 10.4 and after another 2 minutes pH with solution F-1.
It was adjusted to 6.0.

Next, wash with desalinated water in a conventional manner, and use ossein gelatin 1.
After dispersing in an aqueous solution containing 97.4 g, the total volume was adjusted to 3000 ml with distilled water to obtain emulsion EM-1.

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

EM-2 performs exactly the same grain growth as Et-1, and the amount of added silver is KzlrC (l
6.5XIO-6 mol/mol 8gX of b was added.

EM-3 performs exactly the same grain growth as EM-2, and the amount of added silver is 98.9% of the total amount of silver added by the end of crystal growth.
At the 5% addition position, KzlrC j! 6 to 6.5×1
0-8 mol/mol AgX was added.

EM-4 performs exactly the same grain growth as EM-3, and the amount of added silver is 90.9% of the total amount of silver added by the end of crystal growth.
At the addition position of 0%, K21rC46 was added at 6.5×Table-1 Grain growth conditions (EM 1) 15 sequentially from inside
Cores with AgI content of mol%, 5 mol% and 3 mol%/
A shell-type silver iodobromide emulsion having an average grain size of 0.38 μm and an average AgI content of 8.46 mol % was prepared.

Although the silver iodide content differs in each part, a halogen aqueous solution was used in each part of the grain, so it is for comparison.

(Solution A-5) Ossein gelatin 28.6g Pronone (10% ethanol solution?&) 16,
s mtTAI
247.5 ■ 56% acetic acid aqueous solution
72. 6 +n128% ammonia aqueous solution
97.2d seed emulsion N-I Ag
XO. Make up to 6600 ml with distilled water equivalent to 1552 mol.

(Solution B-5) Ossein gelatin 13 gKB
r 460.2gK
1 113.3
gT8■ Dilute to 1300- with distilled water.

(Solution C-5) ossein gelatin KBr XI TAI Make the volume up to 1700m7 with distilled water.

(Solution D~5) ossein gelatin KBr KI TAI Adjust to 800 mZ with smoked water.

(Solution E-5) AgNO3 28% ammonia water Bring to 2983+nZ with distilled water.

(Solution F-5) 20% KBr aqueous solution 665 mg 17 g 672.6 g 49.39 g 870 ■ 8 g 323.2 g 13.94 g 409 ■ 1773.6 g 1470 +n1 pAg adjustment required amount 30 (Solution G-5) 56% Acetic acid aqueous solution p} {Required amount for adjustment 40
Using the same mixing stirrer as in Preparation Example 1 at ℃, solution A
Solution E-5 and solution B-5 were added to solution E-5 and solution B-5 by the simultaneous mixing method, and C-5 was added at the same time as the addition of B-5 was completed.
D5 was added at the same time as the addition of D5 was completed. p during simultaneous mixing
Control of Ag+ pH and addition rate of solution E-5, solution B-5, solution C-5, and solution D-5 were performed as shown in Table-2.

1) Ag and pH were controlled by changing the flow rates of solution F-5 and solution G-5 using a variable flow rate roller tube pump.

After the addition of solution E-5, the pH was adjusted to + in the same manner as in Production Example 1.
pAg adjustment, desalting, washing with water, and redispersion were performed.

This emulsion is designated as EM-5.

Margin below Further, emulsion EM-6 was prepared as follows.

That is, EM-6 is grown under exactly the same growth conditions as EM-5, and when 98.5% of the total amount of silver added is K2.
1rC (16, 6.5X10-I1 mol/mol/L
/A8X was added to improve the effect.

"Milk A 1%" 1 Same as Production Example 1, average particle size 0.65 μm, average Ag
gX particles (core/shell type 8 gBr I ) with an I content of 7.16 mol % were prepared.

(Solution A-3) Ossein gelatin 45gKI
116.8 g Pronone (10% ethanol solution) 30m/919 in distilled water
Make the volume to 1ml.

(Solution B-3) Seed emulsion N-2 8 gX 0.759 mole equivalent 56% acetic acid aqueous solution 112.5
m728% ammonia water 175.
5mITAT
Make up to 2608ml with 600W smoked water.

(Solution C-3) AgNO3
1671 g28% ammonia water
Make the volume up to 2810m7 with 1363ml smoked water.

(Solute fflD-3) Ossein gelatin 50gKBr
2082.5 g
T^I 5.338
g Adjust to 5000 mZ with distilled water.

(?Liquid E-3) Dissolved? Same as &E-1 (solution F-3) Same as solution F-1 At 40°C, 201 parts of solution C-3 were added to melt &A-3 over 1 minute. The rest was the same as Production Example 1.

The pH, pAg, and flow rate are shown in Table 3. The emulsion thus obtained was designated as EM-7. The grains contained in this emulsion also have a mixed composition of silver iodobromide as a core and silver bromide as a shell.

33 34 Table-3 Grain growth conditions (EM-7) Furthermore, growth was performed in exactly the same manner as EM-7, and 6.5% of K2IrC 12 6 was added at a position of 98.5% of the total amount of silver added.
5×10 −8 mol/mol AgX was added. The obtained emulsion was designated as EM-8.

舅'劃Q4 4 Examples] Yu (comparative emulsion) Referring to Production Example 2, 15 mol% from the inside of the grain,
It has a core/shell structure with an AgI content of 5 mol% and 3 mol%, with an average particle size of 0.65 μm and an average AgI content of 7,
A 16 mol % silver iodobromide emulsion (comparison) was prepared. This emulsion is called EM-9.

Furthermore, growth was performed in exactly the same way as EM-9, and 9 of the total amount of added silver was grown.
K2IrC j! at 8.5% position! 6 to 6.5 x 1
An emulsion containing 0-8 mol/mol AgX was prepared and
It was set as 10.

1 (comparative emulsion) Referring to Production Example 4, a comparative emulsion EM- of octahedral monodisperse with a silver iodide content of 2 mol % and an average grain size of 0.65 μm was prepared.
He created 11.

Further, grain growth was performed in exactly the same manner as in EM-11, and KzlrCA6 was added at 6.5 x 1 at a position of 98.5% of the total added silver amount.
Create emulsion with 0-8 mol/mol A F,X added or EM
-12.

Example 1 Each of EM-1 to EM-6 described in Production Examples 1 and 2 was optimally subjected to gold-sulfur sensitization to obtain six types of chemically sensitized emulsions. Furthermore, separately, EM-1 described in Production Examples 1 and 2
Using two types of emulsions:
mol AgX, 2 emulsions with 6.5 x 10-8 mol/mol Ag
A seed emulsion was obtained and aged for 30 minutes. Thereafter, gold-sulfur sensitization was performed to obtain four types of sensitized emulsions. For spectral sensitization, the following sensitizing dye (1) is added at 35% per mole of Agl.
0 ■ and 350 ■ of sensitizing dye (II) were added to spectral sensitize to blue sensitivity.

TAI and 1-phenyl-5-mercaptotetrazole were then added for stabilization. Common photographic additives such as spreading agents and hardeners are added to each of the above 10 types of emulsions to create a coating solution, which is coated onto the subbed film base using a conventional method and dried. I created NalO from

In addition, yellow coupler (Y-1) shown below was dissolved in ethyl acetate and dioctyl phthalate in an equal weight of the coupler, emulsified and dispersed in an aqueous solution containing gelatin, and then added to each of the above emulsions. [20 was obtained from sample N[111] by coating and drying in the same manner as L10.

Sensitizing dye (1) Sensitizing dye (II) Y-1 r ρ 37 38 Sample No. 1 to 20 for 8 seconds each through a blue filter. 1/12.5 seconds, IXIO-'3 seconds
Wafer and wafer exposures were performed under various exposure conditions. Among the samples after exposure, sample No. 1 to 10 are KX- made by Konica ■
Using a 500 automatic processor, processing was performed for 90 seconds with the following developing solution in the following processing step (1), and the sensitivity was determined.

Treatment process (1) (35°C) Developing 25 seconds Fixation 25 seconds Wash with water 25 seconds Drying 15 seconds The composition of the treatment liquid used in each treatment step is shown below.

<Developer> Potassium sulfite 55.0 g Hydroquinone 25.0 gI-
Phenyl-3-byradulide 7 1.2g boric acid
10.0 g sodium hydroxide 21. O g triethylene glycol 17.5 g 5-Methylhenzotriazole 5-nitroindazole]-phenyl-5-mercaptote 1-razole Glutaraldehyde Bisulfite Glacial acetic acid Potassium bromide Triethylenetetraξn Hexaacetic acid Add water to 1 liter Finish to pH = 10.20.

<Fixer> Ethylenediaminetetraacetic acid, 2-sodium salt tartrate, ammonium thiosulfate, anhydrous sodium sulfite, 1-lium boric acid, acetic acid (90 L%), sodium acetate, trihydrium sulfate, argonium sulfate 18-hydroxide, 5.0 3. 0 130.9 7.3 7.0 5.5 25.8 14.6 0.07g 0. 14 g 0.015 g 15.0 g 16.0 g 4.0 g Adjust to 2.5 g QQ 40 Sulfuric acid (50wt%) 6.77 g Add water to finish to 142, adjust to pH = 4.20 do.

Sample No. 11 to no. Regarding sample No. 20.
1 to No. It was exposed in the same manner as in 10 and processed according to the processing step (II) shown below.

Treatment step (II) (38°C) Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water wash 3 minutes 15 seconds Fixed arrival time: 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds drying The composition of the treatment liquid used in each treatment step is shown below.

<Color developer> 4-AξNo3-methyl-N-edyl N-(β-hydroxyethyl) monoaniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxyluagon A
Sulfate 2.0g Anhydrous potassium carbonate
37.5 g potassium bromide
1.3 g 21.Lilo 1.Liacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make up to 1 liter.

<Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Potassium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and dilute with ammonia water to +11H6
．． Adjust 8 times around O.

Fixer> Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g 41 42 Sodium metasulfite 2.3 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using acetic acid for 8 cycles.

<Stabilizing liquid> Formalin (37% aqueous solution) 1.5m
l Konidax (manufactured by Konica Corporation) 1.5ml
Add water for 1I! ．． shall be.

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

43 In Table 4, the sensitivity is determined by fog density + 0.1 for the case where coupler is not added and the case where coupler is added.
Take the reciprocal of the exposure amount giving Sample No. 1 to 10
Until then, sample no. The relative sensitivity is shown with the sensitivity of 1/12.5 second exposure of Sample No. 1 as 100. 11 to 20
Up to sample no. The relative sensitivity is expressed with the sensitivity of 1/12.5 second exposure of No. 11 as 100.

As shown in Table 4, among the samples No. 1 to No. 10 to which no coupler was added, sample No. 1 using the emulsion doped with iridium of the present invention inside the crystal. 2
4 is comparative sample No. 4 in which iridium is not doped inside the crystal. 1, No. Comparative sample No. 5 using an emulsion doped with iridium inside the crystal. It can be seen that the fog is lower and the sensitivity is higher than that of No. 6. Furthermore,
Sample No. 7 to sample no. As is clear from the results of Sample No. 10, samples No. 7 to No. 8 of the present invention in which iridium was added after the completion of crystal growth were different from sample No. 7 to No. 8 of the present invention. 1 and comparative sample No. 1 to which iridium was added after the completion of crystal growth. 9 to 10, it was found that the fog was low and the sensitivity was high, and the same effect as when doping iridium inside the crystal was obtained.

Here, the sample using the emulsion according to the present invention has higher sensitivity than the comparative sample both at low illuminance and at high illuminance, and therefore, although the present invention has the effect of improving illuminance failure, it does not mean only that. It turns out that there is not.

In addition, sample No. to which coupler was added. In samples No. 11 to No. 20, the same effect as when no coupler was added was obtained, indicating that the samples of the present invention had low fog and high sensitivity.

Example 2 EM-7 to EM- described in Production Examples 3 and 4, respectively
Sample No. 10 was subjected to chemical sensitization and spectral sensitization in the same manner as in Example 1 to produce a green-sensitive emulsion, and a magenta coupler was added as shown in Table 5. 21 to 26 were created. However, the sensitizing dyes used for spectral sensitization were 300 mg of the following sensitizing dye (III) per mole of Ag and 30 mg of sensitizing dye (IV) per mole of Ag.

Example 4
Exposure and development were carried out in the same manner as h461. However, the exposure was done at 1/12.5 seconds using blue and yellow filters.
The treatment was performed using the treatment step (II) shown in Example 1.

Sensitizing dye (III) Sensitizing dye (IV) The results are shown in Table-5. Sensitivity represents the reciprocal of the exposure amount that gives fog density +0.1, and the blue sensitivity of samples No. 21 to No. 26 is the same as that of sample No. 2 before adding the spectral sensitizing dye.
Table 47 Table 5 As shown in Table 5, sample No. 21 using the emulsion doped with iridium inside the crystal of the present invention is expressed as a relative value with the blue sensitivity of No. 21 as 100. Emulsion No. 22 is characterized by a smaller decrease in proper part sensitivity than comparative emulsions before and after spectral sensitization with the addition of a dye, high sensitivity in the spectral sensitized part, and low fog. I know what you're doing.

Furthermore, sample No. 25, No. 26, in a silver iodobromide emulsion with a uniform halide composition, the yellow sensitivity is 1
Expressed as a relative value set to 00.

Margin below 48 It can be seen that the effect of the present invention is small.

Furthermore, even if an emulsion in which grains are uniformly doped with iridium is used under exactly the same growth conditions as EM-8, or an emulsion in which iridium is added to less than 98.5% of the total silver content, the sample Similar to N022, the effects of the present invention were obtained.

Example 3 Multilayer color photosensitive material No. 3 was prepared on a subbed cellulose acetate support with an upper and lower layer structure having the composition shown below. 27 was created.

Coating amounts are expressed in g/M as silver for silver halides and colloidal silver, in g/rrr for additives and gelatin, and in g/rrr for sensitizing dyes and couplers. For silver halide in the same layer
Expressed in moles per mole.

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

50 Sensitizing dye (1) 55 C1 1 M 1 Y1 1 57 Sensitizing dye (5) Sensitizing dye (7) 56 CC 1 CM 1 UV 1 58 UV AS 2 ■ Furthermore, sample No. 2 8 to 30 were created as follows.

Sample No. 28 is sample No. 2 7 EM-1 to E
Sample No. M-3 was used, and EM-7 was replaced with EM-8. This is a sample obtained in exactly the same manner as No. 27.

Sample No. 29 is sample No. 2 7 EM-1 to E
Sample No. 1 was used except for replacing M-5 with EM-9 and replacing EM-7 with EM-9. This is a sample obtained in exactly the same manner as No. 27.

Sample No. 30 is sample No. 2 7 EM-1 to E
Except for replacing M-6 with EM-7 and replacing EM-10 with EM-10.
Sample No. This is a sample prepared in exactly the same manner as No.27.

Each of the obtained samples was exposed to white light and developed. Relative sensitivity was then measured.

Relative sensitivity was measured using yellow, magenta, and cyan densities according to a conventional method.

The results are shown in Table 6.

59 60 Table 6 It is a light-sensitive material, and has the effects of low fog and being able to prevent desensitization due to dye adsorption, etc.

B: Blue-sensitive emulsion layer G: Green-sensitive emulsion layer R: Red-sensitive emulsion layer The sensitivities of B, G, and R are respectively sample No. The relative sensitivity is expressed with the sensitivity of 27 being 100.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing an emulsion containing a mixture of different silver halide compositions, wherein the emulsion is composed of silver halide contained in the emulsion. During at least one period of the grain growth process, silver halide grains are grown in the presence of silver halide fine grains having a solubility product equal to or lower than that of the silver halide grains contained in the emulsion, and iridium ions are A silver halide photographic light-sensitive material characterized in that silver halide grains are present at least after the start of grain growth.