JPH11174605A - Halogenated silver photographic emulsion, production thereof, and halogenated silver photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the fogging level while lowering residual quantity of the unreacted reducing agent and fogging inside and on surfaces of particles by performing the reducing sensitization in the condition that a reaction rate of the added reducing agent reaches a specified value within the predetermined time. SOLUTION: Reducing sensitization is performed in the condition that reaction of the reducing agent added at the time of forming halogenated silver particles reaches 50% in 0.2-60 minutes. In the case of continuously growing the halogenated silver particles from the nucleation, reducing sensitization is performed after a nuclear is generated, and in the case of using a seed particle, reducing sensitization is performed in a process before the desalinization after completion of the crystal growing and physical aging of the halogenated silver particles in relation to the seed particle, and after crystal growing of the halogenated silver particles and physical aging are completed. At the time of reducing sensitization, well-known reducing sensitizing agent can be used, but the reducing agent is desirably used. Desalinization is desirably performed on the way of forming the halogenated silver particles or after forming, and desalinization is performed by, for example, a method stated in the second paragraph of Research Dish lodger 17693.

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 emulsion, a method for producing the same, and a silver halide photographic material using the same.

[0002]

2. Description of the Related Art Conventionally, photographing devices such as cameras have become increasingly popular, and opportunities for photographing using silver halide photographic materials have been increasing. Demands for higher sensitivity and higher image quality are increasing.

One of the dominant factors in increasing the sensitivity and image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide grains aiming at higher sensitivity and higher image quality. Particle development has traditionally been pursued in the art.

However, the sensitivity tends to decrease as the size of silver halide grains is reduced to improve image quality, as is generally practiced. To achieve both high sensitivity and high image quality. Had limitations.

Needless to say, in order to achieve higher sensitivity and higher image quality, techniques for improving the sensitivity / grain size ratio per silver halide grain have been studied. As an example, a technique using tabular silver halide grains is disclosed in
8-111935, 58-111936, 58
-111937, 58-113927, 59-
99433 and the like. When these tabular silver halide grains are compared with so-called normal silver halide grains such as octahedral, tetrahedral, or hexahedral grains, when the silver halide grains have the same volume, the surface area increases, and thus Many sensitizing dyes can be adsorbed on the silver particle surface, and there is an advantage that the sensitivity can be further increased.

JP-A-6-230491, JP-A-6-235
988, 6-258745, 6-289516
And the like have also studied using tabular silver halide grains having a higher aspect ratio than before.

Further, Japanese Patent Application Laid-Open No. 63-92942 discloses a technique for providing a core having a high silver iodide content inside tabular silver halide grains, and Japanese Patent Application Laid-Open No. 63-163541 discloses a technique for forming a core between twin planes. A technique using tabular silver halide grains having a ratio of grain thickness to long distance of 5 or more is disclosed, and shows effects on sensitivity and graininess, respectively.

Further, Japanese Patent Application Laid-Open No. 63-106746 discloses that
Tabular silver halide grains having a substantially layered structure in a direction parallel to two opposite main planes are disclosed in
No. 279237 has a layered structure separated by a plane substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide of the whole silver halide grains. It describes a technique using tabular silver halide grains at least 1 mol% higher than the content.

Japanese Patent Application Laid-Open No. 3-121445 discloses a silver halide grain composed of an interface layer having parallel twin planes and regions having different iodine contents from each other.
No. 305343 discloses a tabular silver halide grain having a development start point near the vertex.
Silver halide grains having a (0) plane and a (111) plane are disclosed.

[0010] In addition, JP-A-1-183644 describes that
A technique using tabular silver halide grains, characterized in that the silver iodide distribution of silver halide containing silver iodide is completely uniform is disclosed.

Further, there is disclosed a technique for controlling carriers by metal doping, that is, a technique for improving photographic characteristics by mainly including a polyvalent metal oxide in silver halide grains.

JP-A-3-196135 and JP-A-3-189
No. 641 and the like disclose a silver halide emulsion produced in the presence of an oxidizing agent for silver, and the effect on sensitivity and fog when a silver halide photographic material using the same is used.

Further, for example, Japanese Patent Application Laid-Open No. 63-220238
In Japanese Patent Application Laid-Open No. Hei 3-175440, a technique using a silver halide emulsion containing tabular silver halide grains in which the positions of dislocation lines are defined is disclosed in JP-A-3-175440. A technique using a silver halide emulsion containing silver halide grains is disclosed in Japanese Patent Publication No. 3-186.
No. 95 discusses a technique using silver halide grains having a clear core / shell structure, and Japanese Patent Publication No. 3-31245 discusses a technique relating to silver halide grains having a core / shell three-layer structure. It has been studied as a sensitivity enhancement technique.

JP-A-6-11781 and 6-1178
No. 2, No. 6-27564, No. 6-250309, No. 6-250310, No. 6-250311, No. 6-2
Nos. 50313, 6-242527, etc., realize high sensitivity and improved fog / pressure resistance by using an iodide ion releasing compound in forming silver halide grains.

On the other hand, regarding reduction sensitization,
Of Photographic Science (Journal
of Photographic Science)
Vol. 25, 19-27 (1977) and Photographic Science and Engineering (Pho
graphical Science and Eng
23, pp. 113-117 (197
9 years), a properly applied reduction sensitization nucleus is a photographie correspondence (Photo)
ogrephische Korrespondenz)
Vol. 1, 20- (1957) and Photographic Science and Engineering (Photo)
graphic Science and Engin
As described by Mitchell and Lowe in the report of Vol. 19, pp. 49-55 (1975), it has been considered that the compound contributes to sensitization through a reaction represented by the following formula at the time of exposure.

AgX + hν → e ⁻ + h ⁺ (1) Ag ² + h ⁺ → Ag ⁺ + Ag (2) Ag → Ag ⁺ + e ⁻ (3) Here, h ⁺ and e ⁻ are free holes and free electrons generated by exposure. , Hν indicates a photon, and Ag ² indicates a reduction sensitization nucleus.

However, Photographic Science and Engineering (Photographi)
c Science and Engineerine
g) Volume 16, pages 35-42 (1971) and Ibid.
According to Vol. 3, pp. 113-117 (1979), the reduction sensitization nucleus has the property of trapping not only holes but also electrons, and it cannot be explained by the above theory alone. It is the current situation.

Furthermore, unlike the above-described photosensitive region specific to silver halide grains, the spectral sensitized silver halide grains in the form actually used in a silver halide photographic light-sensitive material are used in the color sensitized region. The function of reduction sensitization was very difficult to predict due to the complexity of the photosensitizing process.

Generally, in a spectrally sensitized silver halide emulsion, a dye absorbs light differently from the intrinsically sensitive region, and the initial stage of exposure is (4) instead of formula (1).
It has been considered to be indicated by a formula.

Dye + hν → Dye ⁺ + e ⁻ (4) Whether the dye holes (Dye ⁺ ) and electrons (e ⁻ ) shown on the right side are transmitted to the silver halide grains largely depends on the properties of the dye. When focusing on the holes, it has generally been considered that the sensitization efficiency is better when the dye holes are not transmitted to the inside of the grains.

This means that, for example,
Science and Engineering (Photog
raphic science and engineering
ering) Vol. 24, pp. 138-143 (1980)
Are discussed in connection with the oxidation potential (Eox) of the dye.

However, the International Congress of Photographic Science (Inter)
national Congress of Photo
Ogric Science) Abstracts, 159-
162 (1978) and Photographic Science and Engineering (Photograph)
phic science and engineer
ing, Vol. 17, pp. 235-244 (1973). A sensitizing dye in which dye holes (Dye ⁺ ) generated during exposure remain on the surface of a silver halide grain has a fogging nucleus or a reduction sensitizing nucleus on the surface. This suggests bleaching, and it is expected that in the most common surface latent image type emulsions, the latent image on the surface is bleached, rather leading to desensitization.

As described above, in the spectrally sensitized system, whether reduction sensitization should be performed on the surface or inside of the silver halide grains, and what kind of dye is used, the effect is exhibited. Ruka is not yet fully known.

As a method of actually using such reduction sensitization in a silver halide emulsion, a method of applying the reduction sensitization to a surface of a silver halide grain, a method of applying the reduction sensitization during the growth of a silver halide grain, or a method of using a seed crystal for grain growth, A method of preliminarily subjecting the seed crystal to reduction sensitization is disclosed in JP-A-3-24537.
3-288145, 4-156448, 5-
No. 31282, No. 3-21944, No. 3-1945
No. 42, No. 3-194538, No. 3-194538
Nos. 3-194439, 3-194542, 6-266039, 7-146525, and 7-2
19093 and 7-225438.

The method of applying to the grain surface is undesirable when used in combination with other sensitization methods (for example, a gold compound or a sulfur compound), and is not suitable for practical use. The method of performing reduction sensitization is
There is also a report that the above-mentioned disadvantages do not occur even when used in combination with other sensitization methods. For example, such a method is disclosed in JP-A-48-87.
825 and JP-A-57-179835.

However, these publications report an improvement in the intrinsic sensitivity of silver halide, but do not mention a system which has been spectrally sensitized.

Japanese Patent Application Laid-Open No. 58-127920 describes that the spectral sensitization was improved in a system which had been subjected to reduction sensitization inside grains in a system which had been subjected to spectral sensitization. It is said that the effect is limited to a dye having an oxidation potential Eox of more than 0.5 V of the sensitizing dye, which has practical limitations.

In the above-mentioned prior art, there is a limit in achieving both high sensitivity and high image quality, and it is insufficient to satisfy the recent demand for photosensitive materials, and the development of more excellent technology is desired. Was.

In particular, in reduction sensitization, an increase in fog,
Technical development for suppressing deterioration of storage stability is required, and conventional studies in this field have not sufficiently responded to this demand.

[0030]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion, a method for producing the same and a silver halide photographic light-sensitive material, and more particularly, to reducing sensitization of a silver halide photographic emulsion under appropriate reduction conditions. By reducing the residual amount of the unreacted reducing agent at the end of the formation of silver halide grains, and further reducing the fog inside and on the surface of silver halide grains, a halogen which has been improved in sensitivity and fog level which cannot be achieved by the prior art. An object of the present invention is to provide a silver halide photographic emulsion, a method for producing the same, and a silver halide photographic light-sensitive material using the same.

Conventionally, there has been a recognition in the art that a method using a reducing agent is advantageous for adjusting the reduction sensitization level. However, the present inventors have proposed a method for reducing sensitization using a reducing agent. In order to effectively form a hole trap while suppressing the formation of electron traps, appropriate reduction conditions with an added reducing agent are necessary, and the reactivity of the added reducing agent is increased to form silver halide grains. It is effective to reduce the residual unreacted reducing agent after the fogging on the surface of silver halide grains, to suppress fog during chemical sensitization and color sensitization, and to use any silver halide after the start of reduction sensitization. In the grain formation step, if necessary, use an acidic environment to control silver nucleation inside and on the surface of the silver halide grains to further reduce fog on the silver halide grain surface, chemical sensitization, and color sensitization. Effective fog control It has been found that can be performed.

[0032]

The above object is attained by adopting the following constitution.

(1) A silver halide photographic emulsion characterized in that reduction sensitization is performed under the condition that the reaction rate of a reducing agent added at the time of forming silver halide grains reaches 50% in 0.2 to 60 minutes. Manufacturing method.

(2) A method for producing a silver halide photographic emulsion, which comprises a step of adjusting the pH in the presence of a reducing agent to 6.1 or more and less than 7.0 when silver halide grains are formed and performing reduction sensitization.

(3) A reduction sensitization is carried out at the time of silver halide grain formation, and the pH is 1.8 or more and less than 4.0 at the time of silver halide grain formation after the start of reduction sensitization. A method for producing a silver halide photographic emulsion.

(4) The method for producing a silver halide photographic emulsion according to any one of (1) to (3), wherein the reduction sensitization is carried out at 60 ° C. or more and 90 ° C. or less.

(5) In a silver halide photographic emulsion containing a dispersion medium and reduction sensitized silver halide grains, the ratio of the unreacted reducing agent in the silver halide photographic emulsion before desalting is reduced during reduction sensitization. A silver halide photographic emulsion, wherein the amount of the reducing agent is 30% or less.

(6) A silver halide photographic emulsion produced by the method for producing a silver halide photographic emulsion according to any one of (1) to (4) and / or a silver halide photographic emulsion according to (5). Is contained in at least one silver halide emulsion layer on a support.

Hereinafter, the present invention will be described specifically.

In the method for producing a silver halide photographic emulsion according to claims 1 to 4 and the silver halide photographic emulsion according to claim 5, reduction sensitization is performed during the formation of silver halide grains.

In the present invention, the term "at the time of forming silver halide grains" is defined as follows.

In the case of producing silver halide grains in the silver halide photographic emulsion according to the present invention without using seed grains and continuously growing the silver halide grains from the nucleation, after the nuclei are formed. This is a step from the completion of crystal growth and physical ripening of the silver halide grains to the start of desalting after the completion of crystal growth and physical ripening of the silver halide grains. When seed grains are used for producing silver halide grains in the silver halide photographic emulsion according to the present invention, crystal growth and physical ripening of the silver halide grains with respect to the seed grains are completed, and the silver halide grains are used. After the completion of the crystal growth and physical ripening until the start of desalting.

In the present invention, desalting is an operation performed for the purpose of removing unnecessary salts from a silver halide photographic emulsion and / or concentrating the silver halide photographic emulsion. A flocculant is added to the silver halide photographic emulsion, or the precipitation of silver halide grains in the silver halide photographic emulsion starts, or the silver halide photographic emulsion starts to be concentrated, or It means that water-soluble salts start to be excluded from the silver halide photographic emulsion.

In the method for producing a silver halide photographic emulsion according to the first to fourth aspects of the present invention, desalting is preferably performed during or after the formation of silver halide grains. In the method of the present invention for producing a silver halide photographic emulsion, desalting is required.

Desalting can be carried out, for example, by the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643 No. II.

More specifically, in order to remove unnecessary soluble salts from a precipitate product or an emulsion after physical ripening,
A Noudel water washing method in which gelatin is gelled may be used, and inorganic salts, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin) may be used. The precipitation method used can be used.

In addition, desalination using membrane separation described in Chemical Engineering Handbook, Revised 5th Edition (edited by the Society of Chemical Engineers, Maruzen), pages 924 to 954, etc., can be more preferably used.

Regarding the method of membrane separation, RD No. 102, 10208 and 131, 13122, JP-B-59-43727 and JP-B-6-27008, and JP-A-6-27008
2-113137, 57-209823, 59
-43727, 62-11137, 61-2
No. 19948, No. 62-23035, No. 63-401
No. 37, No. 63-40039, JP-A-3-14094
6, No. 2-172816, No. 2-172817,
The method described in JP-A-4-22942 and the like can also be referred to.

In the method for producing a silver halide photographic emulsion according to claim 3 of the present invention, reduction sensitization can be carried out by a reduction sensitization technique known in the art. More specifically, the method of reduction sensitization is referred to as silver ripening in the art, a method of ripening and growing at a low pAg by supplying silver ions to silver halide grains, or increasing the pH using an alkaline compound or the like. Any method or a combination of these methods can be used, such as a method of ripening and growing, and adding a reducing agent, but a method using a reducing agent is preferable.

In the method for producing a silver halide photographic emulsion according to the first and second aspects of the present invention and the silver halide photographic emulsion according to the fifth aspect, of the reduction sensitization methods, reduction sensitization using a reducing agent is performed. It is characterized by performing.

The method for producing a silver halide photographic emulsion according to claims 1 and 2 of the present invention and the case of producing the silver halide photographic emulsion of claim 5 or the production of the silver halide photographic emulsion of claim 3 of the present invention When a reducing agent is used in the method, examples of the reducing agent include thiourea dioxide, ascorbic acid and its derivatives, stannous salts, borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines and polyamines. And sulfites can be used, and these can be used in combination.
Preferably, thiourea dioxide, ascorbic acid and its derivatives, and stannous salts are used, and more preferably, thiourea dioxide is used.

The addition amount of the reducing agent is preferably from 10 ^-2 to 10 ^-8 mol per mol of silver halide, more preferably from 10 ^-3 to 10 ^-7 mol.

The reducing agent may be a solid or a method known in the art for adding a photographic additive to a silver halide photographic emulsion, for example, by dissolving it in a solvent such as water, alcohols, esters and glycols. Can be added alone during the formation of silver halide grains, for example, or together with an aqueous solution containing water-soluble silver ions or halide ions or silver halide fine particles.

The addition of the reducing agent may be carried out while growing the silver halide grains, or may be carried out by temporarily suspending the growth of the silver halide grains.

The addition position of the reducing agent and the position of performing the reduction sensitization during the formation of the silver halide grains are arbitrary, and they may be partially or layered in the silver halide grains. Is preferably inside the silver halide grains excluding the silver halide grains, and from the reduction-sensitized silver halide phase in the silver halide grains to the surface of the silver halide grains, the silver halide not subjected to reduction sensitization of 5 lattices or more is provided. More preferably, a phase is present. Reduction sensitization in the present invention can also be carried out by adding reduction sensitized silver halide fine grains prepared in advance.

In the method for producing a silver halide photographic emulsion according to the second aspect of the present invention, the step of reducing the pH in the presence of a reducing agent to 6.1 to less than 7.0 during the formation of silver halide grains is performed. It is characterized by including. The pH
Is preferably 6.3 or more and less than 7.0.

In the method for producing a silver halide photographic emulsion according to claim 3 of the present invention, when reduction sensitization is carried out by a method other than using the above-mentioned reducing agent, for example, the following method can be used.

When the reduction sensitization is performed by using a low pAg condition for an aqueous protective colloid solution in which silver halide grains are grown in the art, which is referred to as silver ripening, a silver salt is added to the aqueous protective colloid solution. After adjusting the pAg to an appropriate value, the silver halide grains are preferably ripened or grown. The silver salt is preferably a water-soluble silver salt, and particularly preferably an aqueous solution of silver nitrate. The above pAg is preferably 7.0 or less, more preferably 2.0 to 5.0.

When the reduction sensitization is carried out by adjusting the pH of the aqueous solution of protective colloid in which silver halide grains are grown, an alkaline compound is added to the aqueous solution of protective colloid to obtain an appropriate pH. The silver halide grains are preferably ripened or grown.

As the alkaline compound, for example, potassium hydroxide, sodium hydroxide, ammonia and ammonium compounds can be used, but it is preferable to use compounds other than ammonia and ammonium compounds.
The pH is 7.0 or more, preferably 7.5 or more and 1 or more.
1.0 or less, more preferably 8.0 or more and 10.0 or more
It is as follows.

In the present invention, the temperature at which reduction sensitization is performed is 5
The temperature is preferably from 0 ° C to 95 ° C, more preferably from 60 ° C to 95 ° C.
The temperature is from 90 ° C to 90 ° C, more preferably from 70 ° C to 90 ° C.

In the method for producing a silver halide photographic emulsion according to the first aspect of the present invention, the reducing agent added during the formation of silver halide grains is reduced under the conditions that the reaction rate reaches 50% in 0.2 to 60 minutes. It is characterized by performing sensitization. More preferably, the reaction rate of the added reducing agent reaches 50% in 0.5 to 40 minutes.

The reaction of the reducing agent can be adjusted by pH, temperature, aging pAg, or the like. For example, when the reducing agent is thiourea dioxide, the pH is 50 at pH 6.1 to 8.0.
% Or more in 0.2 to 60 minutes.
At 6.3 to 7.5, at a temperature of 65 ° C. to 90 ° C., a condition is obtained in which 50% or more reacts in 0.5 to 40 minutes.

In the silver halide photographic emulsion according to the fifth aspect of the present invention, a silver halide photographic emulsion containing a dispersion medium and reduction-sensitized silver halide grains is preferably used in the silver halide photographic emulsion before desalting. The ratio of unreacted reducing agent is 30% or less of the amount of reducing agent added at the time of reduction sensitization.

The proportion of the unreacted reducing agent is more preferably at most 20%, most preferably at most 10%.

In the present invention, the relationship between the reaction rate of the reducing agent and the reaction time during the formation of silver halide grains and the ratio of unreacted reducing agent in the silver halide photographic emulsion before desalting are determined by the ratio of the silver halide grains. The silver halide photographic emulsion sampled in the course of the above was centrifuged, and the amount of reducing agent in the supernatant solution (A)
And the amount of reducing agent added during silver halide grain formation (B)
Is determined by the following formula using To determine the amount (A) of the reducing agent in the supernatant solution,
For example, in the case of ascorbic acid, high performance liquid chromatography (HPLC) using ninhydrin coloring
Can be used, and in the case of thiourea dioxide, it is preferable to determine it by amino acid analysis.

Unreacted reducing agent ratio (%) = (A / B) × 100 Reducing agent reaction rate (%) = (1− (A / B)) × 100 In the present invention, the dispersion medium is a protective colloid. It is a substance that can be constituted, and it is preferable to use gelatin.

In the present invention, when gelatin is used as the dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin, and the like can be used. Gelatin having an adenine content of 0.2 ppm or less described in U.S. Pat. For details on the gelatin production method, see Arthur Weiss, "The Macromolecular Chemistry of
Gelatin "(Academic Press, 1964)
And so on.

Examples of substances that can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfate. Cellulose derivatives such as sodium alginate, starch derivatives, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. Examples include various types of synthetic or semi-synthetic hydrophilic high-molecular substances such as mono- or copolymers.

In the method for producing a silver halide photographic emulsion according to the third aspect of the present invention, reduction sensitization is performed at the time of forming silver halide grains, and the pH is adjusted to 1. It is characterized by including a step of not less than 8 and less than 4.0. The pH is more preferably
2.0 or more and less than 3.5.

The position where the pH is in the above range during the formation of silver halide grains is arbitrary as long as it is after the start of reduction sensitization, and may be accompanied by the growth of silver halide grains or the growth of silver halide grains. It may be temporarily suspended, or after the formation of silver halide grains, and ripening may be performed if necessary. After the pH is adjusted to the above range, the pH may be increased to 4.0 or more as necessary. These operations may be performed twice or more at an arbitrary position.

In the method for producing a silver halide photographic emulsion according to claim 3 of the present invention, it is preferable that the pH is in the above-mentioned range after silver halide grain formation and before desalting. It is. When dislocation lines are introduced during the formation of silver halide grains, reduction sensitization is performed before the introduction of the dislocation lines, the pH is adjusted to the above range, and ripening is performed as necessary, and then the dislocation lines are introduced. Is also one of the preferred embodiments. In this case, the reduction sensitization may be carried out again after the introduction of the dislocation lines, but in that case, it is preferable that the pH is again in the above range after the silver halide grains are formed and before desalting.

In producing the silver halide photographic emulsion of the present invention, an oxidizing agent known in the art can be used.
Examples of the oxidizing agent include hydrogen peroxide (water) and an adduct _{thereof: H 2 O 2, NaBO 2} , H 2 O 2 -3H 2 O, 2NaC
_{O 3 -3H 2 O 2, Na} 4 P 2 O 7 -2H 2 O 2, 2Na 2 SO 4 -
Such as H ₂ O ₂ -2H ₂ O. Peroxy acid salt: K ₂ S ₂ O ₃ , K
_{2 C 2 O 3, K 4} P 2 O 3, K 2 (Ti (O) 2 C 2 O 4) -3H
Examples include ₂ O, peracetic acid, ozone, and thiosulfonic acid compounds.

In the production of the silver halide photographic emulsion of the present invention, the above reduction sensitization and the addition of an oxidizing agent can be carried out in combination.

The method of adding the oxidizing agent may be used as it is,
For example, water, alcohols, esters, by using a method known in the art to add a photographic additive to a silver halide photographic emulsion, such as by diluting or dissolving with a solvent such as a glycol, for example, silver halide grains. Can be added alone or together with an aqueous solution containing water-soluble silver ions or halide ions or silver halide fine particles.

The oxidizing agent may be added while growing the silver halide grains, or may be temporarily interrupted during the growth of the silver halide grains.

The silver halide grains contained in the silver halide photographic emulsion according to the present invention may have a regular crystal structure such as cubic, octahedral or tetradecahedral, or may have a spherical or plate-like shape. Tabular silver halide grains are preferred, although they may have such an irregular crystal form. In these particles, the ratio between the (100) plane and the (111) plane can be arbitrarily used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed. Twin silver halide grains having two opposing parallel twin planes can also be used, but in such a case, tabular silver halide grains are preferred.

The twin is a silver halide crystal having one or more twin planes in one grain, and the form of the twin is classified according to Klein and Moiser. Spondents (Photographi)
she Korrespondentz) Volume 99
Page 100, p. 57.

When tabular silver halide grains are used in the present invention, 50% or more of the total projected area of the silver halide grains contained in the silver halide photographic emulsion of the present invention is tabular silver halide grains. Preferably, it is 60% or more, more preferably 80% or more.

When tabular silver halide grains are used in the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the main plane is 60% or more in terms of the number of silver halide grains. And more preferably 70
%, More preferably 80% or more.

In the present invention, tabular silver halide grains are silver halide grains having an aspect ratio (ratio of diameter to thickness of silver halide grains) of 1.3 or more. The aspect ratio is preferably from 3.0 to 100, and more preferably from 5.0 to 50.

To determine the aspect ratio, first, the silver halide grain diameter and thickness are determined by the following method. A latex ball having a known particle size as an internal standard and a sample coated such that the main plane was oriented parallel to the support were prepared on the support, and shadowing was performed by a carbon deposition method from a certain direction. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. In this case, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The twin plane of the silver halide grains can be observed with a transmission electron microscope. The specific method is as follows. First, a sample is prepared by coating a silver halide emulsion on a support so that the main plane of the tabular silver halide grains is oriented substantially parallel to the support. This is cut using a diamond cutter to a thickness of 0.1μ.
Obtain a thin section of about m. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

In the present invention, the average grain size of the silver halide grains is preferably from 0.2 to 10 μm, more preferably from 0.3 to 7.0 μm.
Is more preferable, and 0.4 to 5.0 μm is most preferable.

In the present invention, the average particle diameter refers to the particle diameter ri.
The arithmetic mean of However, three significant figures and the least significant figure are rounded off, and the number of measured particles is indiscriminately 1,000 or more.

In the case of tabular silver halide grains, the grain size ri is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane into a circular image having the same area. In the case of silver halide grains having a shape other than tabular silver halide grains, the diameter is obtained by converting a projected image of the silver halide grains into a circular image having the same area.

The grain size ri can be obtained by photographing a silver halide grain with an electron microscope at a magnification of 10,000 to 70,000, and actually measuring the grain diameter or projected area of the print.

In the present invention, any silver halide photographic emulsion such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution is used, but a monodisperse emulsion is preferable.

The monodisperse emulsion has a particle size distribution of less than 20%, more preferably less than 16%, as defined by the following formula.

Particle size distribution (%) = (standard deviation of particle size / average particle size) × 100 The average particle size and standard deviation are determined from the particle size ri defined above.

In the present invention, the silver halide photographic emulsion may contain any silver halide such as silver iodobromide, silver iodochlorobromide and silver iodochloride. However, silver iodobromide and silver iodochlorobromide are particularly preferred.

In the present invention, the average silver iodide content of the silver halide grains contained in the silver halide photographic emulsion is 0.5.
To 40 mol%, more preferably 1 to 40 mol%.
~ 20 mol%.

In the present invention, the average silver iodide content of silver halide grains is determined by an EPMA method (Electron Pro).
be Micro Analyzer). Specifically, a sample in which silver halide grains were well dispersed so as not to contact each other was prepared, and -1 was prepared with liquid nitrogen.
By irradiating an electron beam while cooling to below 00 ° C. and determining the characteristic X-ray intensity of silver and iodine emitted from each silver halide grain, the silver iodide content of each silver halide grain is reduced. This can be determined and measured for at least 50 silver halide grains and their average determined.

In the present invention, core / shell type grains can be preferably used as the silver halide grains contained in the silver halide photographic emulsion. The core / shell type particles are particles composed of a core and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell are preferably different from each other.

The silver halide grains in the silver halide photographic emulsion of the present invention preferably have dislocation lines therein. There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain. The introduction position of the dislocation lines in the silver halide grains is preferably 50% or less, more preferably 60% or less, of the total silver content of the silver halide grains.
More preferably, it is introduced in an amount of at least 85%. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines, more preferably 50% or more, and further preferably 80% or more. preferable. In each case, the number of dislocation lines in one grain is preferably 10 or more, more preferably 20 or more, and 3 or more.
More preferably, the number is zero or more.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci.
Eng. 11 (1967) 57 and T.I. Shiozaw
a. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out from the emulsion without paying enough pressure to generate new dislocation lines on the grains are placed on a mesh of an electron microscope to prevent damage (printout, etc.) by the electron beam. The specimen is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass through, so that a clearer observation can be obtained by using a high-pressure electron microscope. From the grain photograph obtained by such a method, the position and number of dislocation lines in each silver halide grain can be determined.

The method for introducing dislocation lines into silver halide grains is not particularly limited. For example, a method in which an aqueous solution of an iodide ion such as potassium iodide and a water-soluble silver salt solution are added by a double jet, silver iodide A method of adding fine particles, a method of adding only an iodine ion solution, and JP-A-6-11781.
A dislocation line of a desired position and amount can be introduced into a silver halide grain by a known method such as a method using an iodide ion-releasing compound described in No.

In the production of the silver halide photographic emulsion of the present invention, various methods well-known in the art can be used for forming silver halide grains. That is, a single jet method, a double jet method, a triple jet method, a silver halide fine particle supply method, or the like can be used in any combination. Further, a method of controlling the pH and pAg in the liquid phase in which silver halide is formed in accordance with the growth rate of silver halide can also be used. The formation of silver halide grains is preferably performed under conditions close to the critical growth rate.

For the production of the silver halide photographic emulsion of the present invention, a seed emulsion can also be used. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, the (100) plane and the (11) plane
1) Any ratio of planes can be used. The silver halide grains in the seed emulsion used may be a composite of these crystal forms, and grains of various crystal forms may be mixed. Twin silver halide grains having twin planes are used. And particularly preferred are twin silver halide grains having two opposing parallel twin planes.

In the present invention, regardless of whether a seed emulsion is used or no seed emulsion is used, the conditions for silver halide nucleation and ripening are those known in the art. Can be.

For the production of the silver halide photographic emulsion of the present invention, a silver halide solvent known in the art can be used. Preferably, a silver halide solvent is used at the time of forming base tabular grains. Should be avoided except for ripening after each formation. Examples of silver halide solvents include:
(A) U.S. Pat. Nos. 3,271,157 and 3,531,
Nos. 289 and 3,574,628, JP-A-54-10
No. 19, 54-158917, and JP-B-58-3
Organic thioethers described in No. 0571 and the like, (b)
Thiourea derivatives described in JP-A-53-82408, JP-A-55-29829 and JP-A-57-77736;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A-53-144319, and (d) JP-A-54-10
No. 0717, imidazole, (e) sulfite, (f) thiocyanate, (g) ammonia,
(H) ethylenediamines substituted with hydroxylalkyl described in JP-A-57-196228 and the like;
(I) substituted mercaptotetrazoles described in JP-A-57-202531, etc., (j) water-soluble bromide,
(K) Benzoimidazole derivatives described in JP-A-58-54333 and the like.

For the production of the silver halide photographic emulsion of the present invention, any of an acidic method, a neutral method and an ammonia method can be used, but the acidic method or the neutral method is preferred.

In the production of the silver halide photographic emulsion of the present invention, a halide ion and a silver ion may be mixed simultaneously, or one of them may be mixed in the presence of the other. Also, considering the critical growth rate of silver halide crystals,
PAg and pH in a mixing vessel containing halide ions and silver ions
And can be added sequentially or simultaneously. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

In the production of the silver halide photographic emulsion of the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt) is formed in the step of forming and / or growing silver halide grains. ), Rhodium salts (including complex salts), salts of iron and other Group VIII metals (including complex salts)
Metal ions can be added using at least one selected from the above, and these metals can be contained inside silver halide grains and / or on the surface of the grains.

In the present invention, when silver halide fine grains are used, the silver halide fine grains may be prepared before the preparation of the silver halide grains according to the present invention, or may be prepared. May be prepared in parallel. When the latter is prepared in parallel, JP-A No. 1-18
As described in JP-A Nos. 3417, 2-44335 and the like, silver halide fine particles can be produced by using a mixer separately provided outside a reaction vessel in which silver halide grains according to the present invention are formed. Although it is possible to provide a preparation container separately from the mixer, the silver halide fine particles once prepared in the mixer can be arbitrarily selected so as to be suitable for a growth environment in a reaction container in which the preparation of the silver halide particles concerned is performed. It is preferable to supply the mixture to the reaction vessel after the preparation.

The method for preparing the silver halide fine particles is preferably an acidic to neutral environment (pH ≦ 7).

To produce the silver halide fine particles, a water-soluble silver salt containing silver ions and an aqueous solution containing halide ions may be mixed while appropriately controlling the supersaturation factor.
Regarding control of the supersaturation factor, see JP-A-63-92942.
And JP-A-63-31244 can be referred to.

PAg for producing the silver halide fine particles
Is preferably at least 3.0, more preferably at least 5.0, even more preferably at least 8.0 in order to suppress the generation of reduced silver nuclei in the silver halide fine grains themselves. .

The temperature for producing the silver halide fine particles is as follows:
The temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and most preferably 35 ° C. or lower.

As the protective colloid used for producing the silver halide fine particles, the above-mentioned protective colloid-forming substance used for producing the silver halide particles according to the present invention can be used.

When silver halide fine particles are formed at a low temperature, coarsening of the particle size due to Ostwald ripening after the formation of the silver halide fine particles can be suppressed. However, at a low temperature, gelatin is easily coagulated. 2-16642
It is preferable to use low molecular weight gelatin described in No. 2, etc., a synthetic molecular compound having a protective colloidal action on silver halide grains, or a natural high molecular compound other than gelatin. The concentration of the protective colloid is preferably at least 1% by weight, more preferably at least 2% by weight, even more preferably at least 3% by weight.

The particle size of the silver halide fine particles is 0.1 μm.
Or less, more preferably 0.05 μm or less.

The silver halide fine grains can contain the above-described reduction sensitization and optionally metal ions, if necessary.

It is preferable that the silver halide fine grains are desalted by using the above-mentioned method.

In the production of the silver halide photographic emulsion of the present invention, conditions other than those described above are described in JP-A-61-66.
No. 43, No. 61-14630, No. 61-112142
No. 62-157024, No. 62-18556,
63-92942, 63-151618, 6
Nos. 3-163451, 63-220238, 63
-311244, RD 365, 36544, 367
Appropriate conditions can be selected with reference to Vol. 36736, Vol.

In constructing a color photographic material using the silver halide photographic emulsion of the present invention, the silver halide emulsion is
Use those that have been subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD176
43, page 23, section III to page 24, section VI-M, RD1871
6,648-649 and RD308119,996
It is described in Sections III-A to VI-M on page 1000.

Known photographic additives that can be used in the present invention are also RD17643, page 25, VIII-A to page 27.
Section XIII, RD18716, pages 650 to 651, RD30
8119, page 1003, paragraphs VIII-A to 1012, XXI-E
Those described in the section can be used.

Various couplers can be used in the color light-sensitive material. Specific examples thereof are RD17643, 25
Page VII-C to G, RD308119, page 1001 VII-
It is described in sections C to G.

The additive used in the present invention is RD3081
19, page 1007, section XIV.

In the present invention, the aforementioned RD17643,
The supports described in page 28, section XVII, RD18716, pages 647 to 648 and RD308119, page 1009, section XVII can be used.

The photosensitive materials include the aforementioned RD308119,1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

The silver halide photographic emulsion of the present invention can be used for various color light-sensitive materials typified by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Can be preferably applied.

The light-sensitive material according to the present invention uses the above-mentioned RD17
643, pages 28 to 29, section XIX, RD18716, 651
And RD 308119, pages 1010 to 1011, section XIX.

[0125]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Seed Emulsion T-1) Seed emulsion T-1 having two parallel twin planes was prepared by the following method.

(A-1 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g 34.0 L with water (B-1 solution) Silver nitrate 810.0 g with water 3815 mL (C-1 solution) Potassium bromide 567. 315 mL with water 3815 mL (D-1 solution) Ossein gelatin 163.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9. 77) 10% methanol solution 5.5 mL 3961 mL with water (E-1 solution) Sulfuric acid (10%) 91.1 mL (F-1 solution) 56% acetic acid aqueous solution Required amount (G-1 solution) Ammonia water (28% 105.7 mL (H-1 solution) Potassium hydroxide aqueous solution (10%) Required amount (I-1 solution) Potassium bromide 208.3 g 1000 mL with water Using a stirrer described in JP-A-62-160128, 3
Solution E-1 was added to solution A-1 which was vigorously stirred at 0 ° C., and then solution B-1 and solution C-1 were added at a constant rate of 279 mL each for 1 minute by a double jet method to obtain silver halide nuclei. Was generated.

Thereafter, the solution D-1 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-1 was further added, the pH was adjusted to 9.3 with the solution H-1, and 6.5 minutes. Aging was performed. Thereafter, the pH was adjusted to 5.8 with the F-1 solution, and then the remaining B-1 solution and the C-1 solution were subjected to double jet method to 37
Min, and desalted immediately by a conventional method. When this seed emulsion was observed with an electron microscope, two parallel
Average grain size with two twin planes (projected area circle equivalent grain size)
This was a monodisperse tabular seed emulsion having a particle size distribution of 72 μm and a particle size distribution of 16%.

(Preparation of Comparative Emulsion Em-1) Seed Emulsion T-1
And a solution shown below was used to prepare a comparative emulsion Em-1.

(A-2 solution) Ossein gelatin 519.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) Of 10% methanol solution 4.5 mL seed emulsion T-1 5.3 mol equivalent 18.0 L with water (B-2 solution) 3.5N silver nitrate aqueous solution 2787 mL (C-2 solution) Potassium bromide 1020 g Potassium iodide 29 0.1 g with water 2500 mL (solution D-2) Potassium bromide 618.5 g potassium iodide 8.7 g with water 1500 mL (solution E-2) Potassium bromide 208.3 g with water 1000 mL (solution F-2) 56% acetic acid Aqueous solution required (solution G-2) Potassium bromide 624.8 g 1500 mL with water (solution H-2) Fine grain emulsion consisting of 3.0% by weight of gelatin and silver iodide fine particles (average particle size 0.05 μm) 0 The preparation method is shown below.

4. containing 0.254 mol of potassium iodide
To 9942 mL of a 0% gelatin solution, 3092 mL of an aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide were added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of fine particles was controlled at 40 ° C, and the pH,
EAg was not adjusted.

(I-2 solution) 100 mL of an aqueous solution containing 5 × 10 ⁻⁶ mol of thiourea dioxide per mol of silver halide (solution J-2) 1 × 10 ⁻ mol of sodium ethylthiosulfonate per mol of silver halide Aqueous solution containing ⁴ mol 100 mL (K-2 solution) 10% aqueous potassium hydroxide solution Required amount A-2 solution is added to the reaction vessel, and while stirring vigorously at 55 ° C, pAg is 9.4 and pH is 5. Adjust to 0 and I
Solution-2 was added, and solution B-2, solution C-2 and solution D-2 were prepared as shown in Table 1.
Were added by the double jet method according to the combination shown in Table 1 to grow seed crystals to prepare tabular silver halide emulsions.

[0133]

[Table 1]

Here, the addition rates of the liquids B-2, C-2, and D-2 are changed in a function with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 55 ° C., the pAg to 9.4, and the pH to 5.0. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 15 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06 at 40 ° C., pH 5.0.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (grain size in terms of projected area circle) of 1.55 μm and a grain size distribution of 16% and an average aspect ratio of 8.0 was used. Monodispersed silver halide grains.

The sample was sampled during the formation of the particles for 60 minutes after the addition of the solution I-2, and the supernatant solution was collected by centrifugation and analyzed for amino acids. As a result, the conversion of the reducing agent was 20%.

(Preparation of Emulsion Em-2 of the Present Invention) In the preparation of Comparative Emulsion (Em-1), Solution A-2 was added to a reaction vessel, and while stirring vigorously, the pAg was 8.1 and the pH was 6 2.0, the solution I-2 was added, and the mixture was aged for 30 minutes. Thereafter, the emulsion of the present invention was prepared in the same manner except that the pAg was adjusted to 9.4, the pH was maintained at 6.0, and the first addition was performed. (Em-
2) was prepared.

[0140] Sampling was performed during the formation of particles, and the supernatant solution was collected by centrifugation and analyzed for amino acids.
30 minutes after the addition of the I-2 solution, the reaction rate of the reducing agent was 50%.

(Preparation of Emulsion Em-3 of the Present Invention) In the preparation of Comparative Emulsion (Em-1), Solution A-2 was added into a reaction vessel, and while stirring vigorously, the pAg was changed to 8.7 and the pH to 6 0.0, the solution I-2 was added, the mixture was aged for 15 minutes, then the pAg was adjusted to 9.4, the pH was maintained at 5.5, and the first addition was carried out except that the first addition was carried out. (Em-
3) was prepared.

[0142] Sampling was performed during the formation of particles, and the supernatant solution was collected by centrifugation and analyzed for amino acids.
The reaction rate of the reducing agent was 50% 50 minutes after the addition of the I-2 solution.

(Preparation of Comparative Emulsion Em-4)
In the preparation of m-1), the A-2 solution was added to the reaction vessel, and the pAg was set to 8.1 and the pH was set to 8. while stirring vigorously.
5 and the solution I-2 was added and aged for 30 minutes.
A comparative emulsion (Em-4) was prepared in the same manner except that the Ag was adjusted to 9.4, the pH was maintained at 8.5, and the first addition was performed.

[0144] Sampling was performed during particle formation, and the supernatant solution was collected by centrifugation and analyzed for amino acids.
0.1 minute after the addition of the I-2 solution, the reaction rate of the reducing agent was 50%.

(Preparation of Emulsion Em-5 of the Invention) Solutions A-2 to K-2 in the preparation of comparative emulsion (Em-1) were used. Solution A-2 was added to the reaction vessel, and while vigorously stirring at 70 ° C., the pAg was adjusted to 8.1 and the pH was adjusted to 6.0, and the solution I-2 was added and aged for 30 minutes. Was adjusted to 8.9, and solution B-2, solution C-2, and solution D-2 were adjusted as shown in Table 2.
Was added by the double jet method according to the combination shown in (1) to grow seed crystals to prepare Emulsion Em-5 of the present invention.

[0146]

[Table 2]

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 70 ° C., the pAg to 8.9, and the pH to 6.0. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (grain size in terms of projected area circle) of 1.60 μm, a grain size distribution of 14%, and an average aspect ratio of 8.0 was used. Monodispersed silver halide grains.

[0150] Sampling was performed during particle formation, and the supernatant solution was collected by centrifugation and analyzed for amino acids.
10 minutes after the addition of the I-2 solution, the reaction rate of the reducing agent was 50%.

Emulsions Em-1 to Em-5 were each used in the following sample formulation, indicated as silver iodobromide g in the tenth layer. These emulsions Em-1 to Em-5 were used after being optimally subjected to color sensitization and chemical sensitization by the method described in the following sample formulation.

(Preparation of Color Photosensitive Material) On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare multilayer color photographic material samples 101 to 105. . The amount of each material added is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 Ultraviolet Absorber UV-1 0.3 Colored Magenta Coupler CM-1 0.123 Colored Cyan Coupler CC-1 0.044 High Boiling Solvent OIL-1 0.167 Gelatin 1.33 Second layer (intermediate layer) Stain inhibitor AS-1 0.16 High boiling point solvent OIL-1 0.20 Gelatin 0.69 Third layer (Low sensitivity red-sensitive layer) Silver halide a 0.12 silver iodobromide b 0.29 sensitizing dye SD-1 2.37 × 10 ^-5 sensitizing dye SD-2 1.2 × 10 ^-4 sensitizing dye SD-3 2.4 × ^10-4 sensitizing dye SD-4 2.4 × ^10-6 Cyan coupler C-1 0.32 Colored cyan coupler CC-1 0.038 High boiling point solvent OIL-2 0.28 Stain inhibitor AS-2 0.0. 002 Gelatin 0.73 4th layer Medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 Sensitizing dye SD-1 4.5 × 10 ^-5 Sensitizing dye SD-2 2.3 × 10 ^-4 Sensitizing dye SD-3 4.5 × 10 ^-4 Cyan coupler C-2 0.52 Colored cyan coupler CC-1 0.06 DIR compound DI-1 0.047 High boiling point solvent OIL-2 0.46 Antifouling agent AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 Sensitizing dye SD-1 3.0 × 10 ^{− 5} Sensitizing dye SD-2 1.5 × 10 ^-4 Sensitizing dye SD-3 3.0 × 10 ^-4 Cyan coupler C-2 0.047 Cyan coupler C-3 0.09 Colored cyan coupler CC-10 0.036 DIR compound DI-1 0.024 High boiling point solvent OIL-2 0.27 Stain inhibitor S-2 0.006 Gelatin 1.28 6th layer (intermediate layer) High boiling point solvent OIL-1 0.29 Stain inhibitor AS-1 0.23 Gelatin 1.00 7th layer (Low sensitivity green color sensitive layer) ) Silver iodobromide a 0.19 Silver iodobromide b 0.062 Sensitizing dye SD-4 3.6 × 10 ^-4 Sensitizing dye SD-5 3.6 × 10 ^-4 Magenta coupler M-1 18 Colored magenta coupler CM-1 0.033 High boiling solvent OIL-1 0.22 Stain inhibitor AS-2 0.002 Stain inhibitor AS-3 0.05 Gelatin 0.61 Eighth layer (intermediate layer) High boiling point Solvent OIL-1 0.26 Antifouling agent AS-1 0.054 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 Sensitization dyes SD-6 3.7 × 10 sensitized ^-4 dye SD-7 7.4 × 10 ^-5 sensitization Containing SD-8 5.0 × 10 ^-5 Magenta coupler M-1 0.17 Magenta Coupler M-2 0.33 Colored magenta coupler CM-1 0.024 Colored magenta coupler CM-2 0.029 DIR compound DI-2 0.024 DIR compound DI-3 0.005 High boiling point solvent OIL-1 0.73 Stain inhibitor AS-2 0.003 Stain inhibitor AS-3 0.035 Gelatin 1.80 10th layer (high sensitivity green feeling) Color layer) Silver iodobromide g 1.19 Sensitizing dye SD-6 4.0 × 10 ^-4 Sensitizing dye SD-7 8.0 × 10 ^-5 Sensitizing dye SD-8 5.0 × 10 ^{− 5} magenta coupler M-1 0.065 colored magenta coupler CM-1 0.022 colored magenta coupler CM-2 0.026 DIR compound DI-2 0.003 DIR compound DI-3 0 003 High boiling solvent OIL-1 0.19 High boiling solvent OIL-2 0.43 Stain inhibitor AS-2 0.014 Stain inhibitor AS-3 0.017 Gelatin 1.23 11th layer (yellow filter layer) Yellow Colloidal silver 0.05 High boiling point solvent OIL-1 0.18 Stain inhibitor AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide a 0.08 Iodobromide Silver b 0.22 sensitizing dye SD-9 6.5 × 10 ^-4 sensitizing dye SD-10 2.5 × 10 ^-4 yellow coupler Y-1 0.77 DIR compound DI-4 0.017 high boiling point solvent OIL-1 0.31 Antifouling agent AS-2 0.002 Gelatin 1.29 13th layer (highly sensitive blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 Sensitizing dye SD-9 4.4 × 10 ^-4 sensitizing dye SD-10 .5 × 10 ^-4 Yellow coupler Y-1 0.23 High-boiling solvent OIL-1 0.10 antifouling agent AS-2 0.004 Gelatin 1.20 14th layer (first protective layer) Silver iodobromide j 0.30 UV absorber UV-1 0.055 UV absorber UV-2 0.110 High boiling point solvent OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) Polymer PM-1 0.15 Polymer PM-2 0.04 Slip agent WAX-1 0.02 Dye D-1 0.001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (the average particle size is:
It refers to the length of one side of a cube of the same volume).

Emulsion No. Average grain size (μm) Average AgI content (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 Silver iodobromide b 0.40 8.0 1.4 Silver iodobromide c 0.60 7.0 3.1 Silver iodobromide d 0.74 7.0 5.0 Silver iodobromide e 0.60 7.0 4,1 Silver iodobromide f 0.65 8.7 6. 5 Silver iodobromide h 0.65 8.0 1.4 Silver iodobromide i 1.00 8.0 2.0 2.0 Silver iodobromide j 0.05 2.0 1.0 The preferred halogen of the present invention Production examples of silver iodobromide d and f will be described below as examples of forming silver iodide grains. Regarding silver iodobromide j, JP-A-1-183417 and 1-1.
No. 83644, No. 1-183645, No. 2-1664
It was prepared with reference to the description relating to No. 42.

First, seed crystal emulsion-1 was prepared.

(Preparation of Seed Emulsion-1) JP-B-58-58
No. 288 and No. 58-58289, a silver nitrate aqueous solution (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide) were added to the following solution A1 adjusted to 35 ° C. 2 mol%) was added over 2 minutes by a double jet method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, and the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
2 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio (maximum side ratio of each grain) of 90% or more of the total projected area of silver halide grains. The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

(Solution A1) Ossein gelatin 24.2 g Potassium bromide 10.8 g 10% ethanol solution of surfactant (EO-1) 6.78 ml 10% nitric acid 114 ml Water 9657 ml (silver iodide fine grain emulsion SMC-1 Preparation) A 5% aqueous solution of 6.0% by weight gelatin containing 0.06 mol of potassium iodide was vigorously stirred while vigorously stirring a 7.06 mol aqueous solution of silver nitrate and a 7.06 mol aqueous solution of potassium iodide, 2 l each. Was added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

(Preparation of silver iodobromide d) A solution containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of a surfactant (SU-1) was prepared. 700 ml of the active gelatin aqueous solution was kept at 75 ° C., and the pAg was 8.
4. After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 3.093 mol of an aqueous silver nitrate solution and
287 mol of SMC-1 and aqueous potassium bromide solution were added to p
Ag was added while keeping the pH at 8.4 and the pH at 5.0.

2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 9.8 and the pH at 5.0.

Throughout the particle formation, each solution was added at an optimum rate so as to prevent the formation of new nuclei and the Ostwald ripening between particles.

After the completion of the addition, the mixture was washed with water at 40 ° C. using a usual flocculation method, and then gelatin was added to redisperse the mixture. The pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.75 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%.

(Preparation of silver iodobromide f) In the preparation of silver iodobromide d, in step 1), pAg was 8.8, the amount of silver nitrate added was 2.077 mol, and the amount of SMC-1 was 0. .218
Silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol. .

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.65 μm, an average aspect ratio of 6.5, and a silver iodide content of 2 / 9.5 / X / 8 mol% (where X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes have been added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate are added to optimize the fog-sensitivity relationship. Chemical sensitization was applied.

Silver bromoiodides a, b, c, e, g, h and i were also subjected to spectral sensitization and chemical sensitization in accordance with the above-mentioned silver bromoiodides d and f.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinyl pyrrolidone, weight average molecular weight: 1,100,000), inhibitor AF-3,
AF-4, AF-5, hardeners H-1, H-2 and preservative Ase-1 were added.

The structure of the compound used in the above sample is shown below.

SU-1: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK SU-2: C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃
Br ^- SU-3: sodium di (2-ethylhexyl) sulfosuccinate SU-4: sodium tri-i-propylnaphthalenesulfonate ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-2: Adenine AF-3: 1-Phenyl-5-mercaptotetrazole AF-4: 1- (4-Carboxyphenyl) -5-mercaptotetrazole AF-5: 1- (3- acetamidophenyl) -5-mercaptotetrazole H-1: _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2
CH ₂ CH _{2] 2 NCH 2 CH 2 SO 3 K} H-2: 2,4- dichloro-6-hydroxy -s- triazine sodium OIL-1: tricresyl phosphate OIL-2: Di (2-ethylhexyl) Phthalate AS-1: 2,5-bis (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone AS-2: Dodecyl gallate AS-3: 1,4-bis (2-tetradecyloxycarbonylethyl) Piperazine

[0173]

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[0174]

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[0175]

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[0177]

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[0178]

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The samples 101 to 105 obtained were subjected to the following color development processing.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution and color developing replenisher Developer replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make up to 1 liter. The color developing solution was adjusted to pH 10.06 using potassium hydroxide or 20% sulfuric acid, and the replenisher was adjusted to pH 10.6. Adjust to 18.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water To 1 liter, and the pH of the bleaching solution is adjusted to pH 4 using aqueous ammonia or glacial acetic acid. In 4, adjust the replenisher to pH 4.0.

Fixing Solution and Fixing Replenisher Fixing Solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g The fixing solution was adjusted to pH 6.2 using aqueous ammonia or glacial acetic acid. After adjusting the pH of the replenisher to 6.5, add water to make 1 liter.

Stabilizing solution and stabilizing replenishing solution water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC 0.1 g ammonia water 0.5 ml Water was added to make up to 1 liter, and then the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

<< Evaluation of Fog and Sensitivity >> Samples 101 to 10
5, after performing a step wedge exposure for 1/200 second and 3.2 CMS using white light, immediately perform the above color development processing to obtain a characteristic curve, and obtain green fog and green sensitivity (density of fog density + 0.10). Sample 1)
The values are shown as relative values with the value of 01 being 100.

Table 3 shows the evaluation results of the samples 101 to 105.

[0188]

[Table 3]

Table 3 shows that the emulsions Em-2 and Em-3 of the present invention were obtained.
And 102, 103 and 10 using Em-5
Sample No. 5 exhibited excellent fog and sensitivity to the coated samples 101 and 104 using the comparative emulsions Em-1 and Em-4.

Example 2 (Preparation of Comparative Emulsion Em-11) A comparative emulsion (Em-1) was prepared in the same manner as in Example 1 except that the pH at the time of the first addition was maintained at 5.5. Emulsion (Em
-11) was prepared.

(Preparation of Emulsion Em-12 of the Invention) Example 1
In the preparation of Comparative Emulsion (Em-1), an emulsion of the present invention (Em-12) was prepared in the same manner except that the pH during the first addition was maintained at 6.7.

(Preparation of Emulsion Em-13 of the Invention) Example 1
In the preparation of the comparative emulsion (Em-1), the pH at the time of the first addition was maintained at 6.3, and the following solutions I-3 and J-3 were used instead of the solutions I-2 and J-2, respectively. An emulsion of the present invention (Em-13) was prepared in the same manner except that the liquid was used.

(I-3 solution) 100 mL of an aqueous solution containing 1.5 × 10 ⁻⁵ mol of thiourea dioxide per mol of silver halide (solution J-3) 3 × of sodium ethylthiosulfonate per mol of silver halide 100 mL of an aqueous solution containing 10 ^-4 mol (Preparation of Comparative Emulsion Em-14) In the preparation of Comparative Emulsion (Em-1) in Example 1, except that the pH during the first addition was maintained at 8.0. Comparative emulsion (Em
-14) was prepared.

(Preparation of Emulsion Em-15 of the Present Invention) Example 1
The solutions A-2 to K-2 in the preparation of the comparative emulsion (Em-1) were used. Add solution A-2 into the reaction vessel,
While vigorously stirring at 70 ° C., pAg was adjusted to 8.9, pH
Was adjusted to 6.7, solution I-2 was added, solution B-2 and solution C-
Solution 2 and Solution D-2 were added by the simultaneous mixing method in accordance with the combination shown in Table 2 above to grow a seed crystal, thereby preparing Emulsion Em-5 of the present invention.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 70 ° C., the pAg to 8.9, and the pH to 6.7. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles are formed, desalting is carried out according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average particle size (particle size in terms of projected area circle) of 1.55 μm and a particle size distribution of 15% and an average aspect ratio of 8.0 was used. Monodispersed silver halide grains.

Using the emulsions Em-11 to Em-15, multilayer color light-sensitive material samples 111 to 115 were prepared and evaluated in the same manner as in Example 1. Table 4 shows the results.

[0199]

[Table 4]

Table 4 shows that the emulsions Em-12 and Em-
The coated samples 112, 113 and 115 using the emulsions No. 13 and Em-15 showed excellent fog, compared to the coated samples 111 and 114 using the comparative emulsions Em-11 and Em-14.
Sensitivity was indicated.

Example 3 (Preparation of Comparative Emulsion Em-21) A comparative emulsion (Em-1) was prepared in the same manner as in Example 1 except that the pH at the time of the first addition was maintained at 6.8. Emulsion (Em
-21) was prepared.

(Preparation of Emulsion Em-22 of the Invention) Example 1
In the preparation of the comparative emulsion (Em-1), the pH at the time of the first addition was maintained at 6.8, and after the grain formation,
% Nitric acid at 50 ° C. to adjust the pH to 3.5 and aging for 20 minutes, and then to pH 5.0 with a 10% aqueous potassium hydroxide solution.
The emulsion of the present invention (Em-22) was prepared in the same manner as above except that the salt was adjusted and then desalted.

(Preparation of Emulsion Em-23 of the Present Invention) Example 1
In the preparation of the comparative emulsion (Em-1), the pH at the time of the first addition was maintained at 6.8, and after the grain formation,
The pH was adjusted to 2.5 at 50 ° C. with 50% nitric acid and ripened for 30 minutes, and then the pH was adjusted to 5.0 with a 10% aqueous potassium hydroxide solution.
The emulsion of the present invention (Em-23) was prepared in the same manner as above except that the salt was adjusted and then desalted.

(Preparation of Emulsion Em-24 of the Invention) Example 1
The solutions A-2 to K-2 in the preparation of the comparative emulsion (Em-1) were used. Add solution A-2 into the reaction vessel,
While vigorously stirring at 70 ° C., pAg was adjusted to 8.9, pH
Was adjusted to 6.8, solution I-2 was added, solution B-2 and solution C-
Solution 2 and solution D-2 were added by the simultaneous mixing method in accordance with the combination shown in Table 2 above to grow a seed crystal.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 70 ° C., the pAg to 8.9, and the pH to 6.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the formation of the particles, p is added at 50 ° C. with 10% nitric acid.
After adjusting the H to 2.5 and aging for 30 minutes, the pH was adjusted to 5.0 with a 10% aqueous potassium hydroxide solution, and then desalting was performed according to the method described in JP-A-5-72658. Thereafter, gelatin is added and dispersed, and at 40 ° C., p
The emulsion of the present invention having an Ag of 8.06 and a pH of 5.8 (Em-24)
I got

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average particle size (particle size in terms of projected area circle) of 1.55 μm and a particle size distribution of 15% and an average aspect ratio of 8.0 was used. Monodispersed silver halide grains.

(Preparation of Comparative Emulsion Em-25) In the preparation of Comparative Emulsion (Em-1) in Example 1, the pH at the time of the first addition was maintained at 6.8, and 10%
The pH was adjusted to 1.6 at 50 ° C. with nitric acid, and the mixture was aged for 30 minutes. Thereafter, the pH was adjusted to 5.0 with a 10% aqueous potassium hydroxide solution.
To prepare a comparative emulsion (Em-25).

(Preparation of Emulsion Em-26 of the Present Invention) Example 1
The solutions A-2 to K-2 in the preparation of the comparative emulsion (Em-1) were used. Add solution A-2 into the reaction vessel,
While vigorously stirring at 70 ° C., pAg was adjusted to 8.9, pH
Was adjusted to 6.8, solution I-2 was added, solution B-2 and solution C-
Solution 2 and solution D-2 were added by the simultaneous mixing method in accordance with the combination shown in Table 2 above to grow a seed crystal.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 70 ° C., the pAg to 8.9, and the pH to 6.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the pH was adjusted to 2.5 at 50 ° C. with 10% nitric acid, and the mixture was aged for 20 minutes. The pH was adjusted to 5.0 with a 10% aqueous potassium hydroxide solution, and J-2 solution was added. In 30 minutes, the temperature of the solution in the reaction vessel was lowered to 40 ° C., the pAg was adjusted to 10.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. In the second addition, the solution temperature in the reaction vessel was 40 ° C., the pAg was 10.3,
The pH was controlled at 5.0, and the rest of the solution B-2 was added. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles have been formed, p is added at 50 ° C. with 10% nitric acid.
After adjusting the H to 2.5 and aging for 30 minutes, the pH was adjusted to 5.0 with a 10% aqueous potassium hydroxide solution, and then desalting was performed according to the method described in JP-A-5-72658. Thereafter, gelatin is added and dispersed, and at 40 ° C., p
The emulsion of the present invention having an Ag of 8.06 and a pH of 5.8 (Em-26)
I got

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (grain size in terms of projected area circle) of 1.55 μm and a grain size distribution of 15% and an average aspect ratio of 8.0 was used. Monodispersed silver halide grains.

(Preparation of Emulsion Em-27 of the Invention) Example 1
The solutions A-2 to K-2 in the preparation of the comparative emulsion (Em-1) were used. Add solution A-2 into the reaction vessel,
While vigorously stirring at 70 ° C., pAg was adjusted to 8.9, pH
Was adjusted to 6.8, solution I-2 was added, solution B-2 and solution C-
Solution 2 and solution D-2 were added by the simultaneous mixing method in accordance with the combination shown in Table 2 above to grow a seed crystal.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 70 ° C., the pAg to 8.9, and the pH to 6.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the pH is adjusted to 2.5 at 50 ° C. with 10% nitric acid, the mixture is aged for 20 minutes, the pH is adjusted to 5.0 with a 10% aqueous potassium hydroxide solution, and the solution in the reaction vessel is adjusted for 30 minutes. The temperature was lowered to 40 ° C. and the pAg was reduced to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately started. Three minutes after the start of the second addition, the pH was adjusted to 6.5 with a 10% aqueous potassium hydroxide solution, and the following solution I-4 was added. The solution temperature is 4
At 0 ° C., the pAg was controlled at 10.3, and the pH was controlled at 6.5, and the rest of the solution B-2 was added. The solution J-2 was added 5 minutes before the addition of the solution B-2. pAg and pH
For control of E-2 solution and F-2 as needed
Solution and K-2 solution were added.

After the formation of the particles, p is added at 50 ° C. with 10% nitric acid.
After adjusting the H to 2.5 and aging for 30 minutes, the pH was adjusted to 5.0 with a 10% aqueous potassium hydroxide solution, and then desalting was performed according to the method described in JP-A-5-72658. Thereafter, gelatin is added and dispersed, and at 40 ° C., p
The emulsion of the present invention having an Ag of 8.06 and a pH of 5.8 (Em-27)
I got

(I-4 Solution) 100 mL of an aqueous solution containing 5 × 10 ⁻⁶ mol of thiourea dioxide per mol of silver halide was observed by an electron microscope for silver halide grains in the emulsion. 1.50μ
m, and hexagonal tabular monodisperse silver halide grains having a particle size distribution of 16% and an average aspect ratio of 8.2.

Using the emulsions Em-21 to Em-27, multilayer color light-sensitive material samples 121 to 127 were prepared and evaluated in the same manner as in Example 1. The evaluation was performed immediately after the sample was prepared and after the prepared sample was stored under the conditions of 40 ° C. and 80% RH for one week. Table 5 shows the results. Note that both fog and sensitivity are shown as relative values with the value of sample 121 immediately after sample preparation being 100.

[0218]

[Table 5]

Table 5 shows that the emulsions Em-22 to Em- of the present invention were obtained.
24, Coated sample 12 using Em-26 and Em-27
2-124, 126 and 127 are comparative emulsions Em-21
As compared with the coating samples 121 and 125 using Em-25 and Em-25, both excellent fog sensitivity and improved storage stability were exhibited.

Example 4 (Preparation of Comparative Emulsion Em-31) Solutions A-2 to K-2 of Preparation of Comparative Emulsion (Em-1) in Example 1 were used. Solution A-2 was added to the reaction vessel, pAg was adjusted to 9.1, pH was adjusted to 5.8 while stirring vigorously at 65 ° C., solution I-2 was added, and the mixture was aged for 30 minutes. -2 liquid, C
Solution-2 and Solution D-2 were added by the simultaneous mixing method in accordance with the combinations shown in Table 6 to grow seed crystals to prepare Emulsion Em-5 of the present invention.

[0221]

[Table 6]

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 65 ° C., the pAg to 9.1, and the pH to 5.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles are formed, desalting is carried out according to the method described in JP-A-5-72658, and gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (equivalent grain size in projected area circle) of 1.55 μm and a grain size distribution of 15% and an average aspect ratio of 8.5 was used. Monodispersed silver halide grains.

After the particles were formed and before desalting, sampling was performed, and the supernatant solution was collected by centrifugation and analyzed for amino acids. As a result, the ratio of the unreacted reducing agent was 50%.

(Preparation of Emulsion Em-32 of the Present Invention) Example 1
In the preparation of the comparative emulsion (Em-31) in
An emulsion of the present invention (Em-32) was prepared in the same manner except that the pH during the addition of the second solution to the first addition was maintained at 6.5.

Sampling after particle formation and before desalting,
When the supernatant solution was collected by centrifugation and analyzed for amino acids, the unreacted reducing agent ratio was 25%.

(Preparation of Emulsion Em-33 of the Present Invention) Example 1
In the preparation of the comparative emulsion (Em-31) in
An emulsion of the present invention (Em-33) was prepared in the same manner except that the pH during the addition of the second solution to the first addition was maintained at 6.8.

Sampling after particle formation and before desalting,
The supernatant solution was collected by centrifugation and subjected to amino acid analysis. As a result, the unreacted reducing agent ratio was 10%.

(Preparation of Emulsion Em-34 of the Invention) Example 1
The solutions A-2 to K-2 in the preparation of the comparative emulsion (Em-1) were used. Add solution A-2 into the reaction vessel,
With vigorous stirring at 75 ° C., pAg was adjusted to 8.7, pH
Was adjusted to 6.8, solution I-2 was added, and the mixture was aged for 30 minutes. Then, solution B-2, solution C-2 and solution D-2 were added by the simultaneous mixing method according to the combination shown in Table 7. Then, a seed crystal was grown to prepare Emulsion Em-5 of the present invention.

[0231]

[Table 7]

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 75 ° C., the pAg to 8.7, and the pH to 6.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average particle size (particle size in terms of projected area circle) of 1.55 μm and a particle size distribution of 15% and an average aspect ratio of 8.0 was used. Monodispersed silver halide grains.

After the particles were formed and before desalting, sampling was performed, and the supernatant solution was collected by centrifugation and analyzed for amino acids. As a result, the ratio of the unreacted reducing agent was 5%.

Using the emulsions Em-31 to Em-34, multilayer color light-sensitive material samples 131 to 134 were prepared and evaluated in the same manner as in Example 1. Table 8 shows the results.

[0237]

[Table 8]

Table 8 shows that the emulsions Em-32 to Em- of the present invention
Coating samples 132 to 134 using the Comparative Emulsion Em.
Excellent fog and sensitivity were exhibited with respect to the coated sample 131 using -31.

[0239]

According to the present invention, in the reduction sensitization of a silver halide photographic emulsion, under appropriate reduction conditions, a reduction in the residual amount of an unreacted reducing agent at the end of the formation of silver halide grains, a reduction in the inside of the silver halide grains, By reducing surface fog,
It is possible to provide a silver halide photographic emulsion, a method for producing the same, and a silver halide photographic light-sensitive material using the same, which have improved sensitivity and fog level which could not be achieved by the prior art.

Claims (6)

[Claims] 1. A silver halide photographic emulsion characterized in that reduction sensitization is carried out under the condition that the reaction rate of a reducing agent added during the formation of silver halide grains reaches 50% in 0.2 to 60 minutes. Production method. 2. A method for producing a silver halide photographic emulsion, comprising a step of adjusting the pH in the presence of a reducing agent to 6.1 or more and less than 7.0 when silver halide grains are formed and performing reduction sensitization. 3. A process comprising performing reduction sensitization at the time of forming silver halide grains and having a pH of 1.8 or more and less than 4.0 at the time of forming silver halide grains after the start of reduction sensitization. Of producing a silver halide photographic emulsion. 4. The method for producing a silver halide photographic emulsion according to claim 1, wherein the reduction sensitization is carried out at 60 ° C. or more and 90 ° C. or less. 5. In a silver halide photographic emulsion containing a dispersion medium and reduction sensitized silver halide grains, the ratio of an unreacted reducing agent in the silver halide photographic emulsion before desalting is added during reduction sensitization. A silver halide photographic emulsion, wherein the amount of the reducing agent is 30% or less. 6. A silver halide photographic emulsion produced by the method for producing a silver halide photographic emulsion according to claim 1 and / or a silver halide photographic emulsion according to claim 5 as a support. A silver halide photographic material, which is contained in at least one of the silver halide emulsion layers.