JPH04110934A - Silver halide photographic emulsion and production thereof - Google Patents

Abstract

PURPOSE:To obtain a high sensitivity and to decrease fogging by executing a part or the whole of a nucleus formation and/or crystal growth process in the presence of a hardly gelatinizable dispersion medium having a protective colloidal property and executing a hardly gelatinizable dispersion medium removal treatment after the end of the crystal growth of silver halide particles. CONSTITUTION:The silver halide particles are prepd. by executing the nucleus formation and/or crystal growth process in the presence of the hardly gelatinizable dispersion medium having the protective colloidal property. The silver halide particles are subjected to a washing treatment by a dialysis method or coagulation method, etc., after the end of the crystal growth of these particles, by which a part or the whole of the hardly gelatinizable dispersion medium is removed. Other dissolved matter mainly consisting of salts is preferably removed simultaneously with the hardly gelatinizable dispersion medium by executing this treatment. A high-polymer flocculating agent is preferably used in the hardly gelatinizable dispersion medium removal treatment by the coagulation method. The decreased fogging and the higher sensitivity are sufficiently attained in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic emulsion, and particularly to a silver halide photographic emulsion that has high sensitivity, low fog, and excellent processability and storage stability, and a method for producing the same.

[Prior Art] Gelatin has been used as a dispersion medium for silver halide grains in photographic silver halide emulsions.

The general manufacturing method for photographic gelatin is described, for example, in "Fundamentals of Photographic Engineering - Silver Salt Photography Edition" edited by the Photographic Society of Japan (Corona Publishing) 12
Pages 2 to 124 are described in detail.

In general, when classified by molecular weight, seratin consists of a polymer component with a molecular weight of 300,000 or more, a γ component with a molecular weight of around 300,000, and a γ component with a molecular weight of around 200,000.
β component with a molecular weight of around 100,000, σ component with a molecular weight of around 100,000, molecular weight l
Although it can be roughly divided into low molecular weight components of 0,000 or less, the molecular weight distribution varies greatly depending on manufacturing conditions such as raw materials, solubilization treatment, and extraction conditions.

The gelatin used for photography is either a mixture of these ingredients with various molecular weights, or it is generally lime-treated cow bone and cow skin that has an average molecular weight of 70,000 to 130,000. There is.

In addition, various synthetic polymer compounds having protective colloid properties for silver halide grains are also being investigated as dispersion media other than gelatin. Regarding this, for example, "Behavior of hydrophilic polymers as protective colloids of silver halide (Part 1), (Part 2)" Journal of the Photographic Society Vol. 29, No. 1 (1962), You can refer to ``Fundamentals of Photographic Engineering - Silver Halide Photography Edition'', etc.

It is well known that in the physical ripening process of silver halide grains, the dispersion medium used has an influence on the formation and growth of six layers of silver halide grains (see the above-mentioned documents, etc.). This is thought to be related to the molecular weight and structure of the dispersion medium, or impurities contained in the dispersion medium.

For example, as a technique related to the molecular weight of gelatin, JP-A-1-158426 discloses a method of nucleating silver halide grains using low molecular weight gelatin as a dispersion medium during the preparation of a silver halide emulsion.

This technique is thought to focus on the relationship between adsorption to silver halide grains and gelatin molecular weight, and aims to increase the ratio of tabular grains and hexagonal tabular grains by using low molecular weight gelatin.

In addition, we focused on the gelling properties of the dispersion medium (gelatin and synthetic polymer compounds);
In this issue, fine-sized silver halide grains used for crystal growth of silver halide grains are treated with low-molecular-weight gelatin or synthetic polymer compounds that have a protective colloid effect on silver halide grains, and natural polymers other than gelatin. A method is disclosed in which a dispersion medium selected from molecular compounds is prepared and used for nucleation and/or crystal growth.

This technology makes it possible to obtain extremely fine-sized silver halide grains at low temperatures, resulting in low fog, high sensitivity, and improved graininess, sharpness, and covering power. Another object of the present invention is to provide a negative-working silver halide photographic light-sensitive material having excellent storage stability and pressure characteristics, and a method for producing the light-sensitive material.

In this way, the dispersion medium used during silver halide preparation is appropriately selected depending on the purpose.

On the other hand, the dispersion medium of the silver halide emulsion also has an influence on chemical ripening. This is thought to be due to impurities contained in the dispersion medium and the structure of the dispersion medium. Many studies have been conducted on the effects of impurities and the structure of dispersion media, and there are many literatures (for example, the aforementioned ``Fundamentals of Photographic Engineering: Silver Salt Edition'').

However, there are few reports on the influence of molecular weight on chemical ripening, and much remains unclear. For example, in the example of JP-A-1-158426 using low molecular weight gelatin, there is no mention of the effect on photographic sensitivity.

Furthermore, in the examples of JP-A-2-166442 using low molecular weight gelatin or synthetic polymer compounds, the solubility and particle size distribution of fine particles were only confirmed, and the evaluation of various photographic performances was not carried out. .

The present inventors investigated the influence of gelatin molecular weight on photographic performance and found that when low molecular weight gelatin is used during nucleation and/or growth of silver halide grains, it has negative effects on photographic performance such as decreased sensitivity and increased fog. It was found that

This tendency is also seen when a synthetic polymer compound with protective colloidal properties is used instead of low molecular weight gelatin, which has a lower gelling property than general photographic gelatin (molecular weight of 70,000 or more). It has become clear that this is a common problem in many cases where a low-quality dispersion medium (referred to as a non-gelling dispersion medium in the present invention) is used during the preparation of silver halide emulsions. That is, in the prior art as mentioned above, which uses a gelatin-resistant dispersion medium such as low molecular weight gelatin, there are potential problems such as a decrease in sensitivity and an increase in fog, as described above, or there is no way to solve them. No effective means have been found.

[Objective of the Invention 1 The object of the present invention is to improve the deterioration of photographic performance that occurs when a non-gelling dispersion medium is used during nucleation and/or crystal growth of silver halide grains, The aim is to maximize the effects obtained by using

That is, a silver halide emulsion prepared using a non-gelling dispersion medium during nucleation and/or crystal growth of silver halide grains has high sensitivity and low fog, and has good processability and storage stability. An object of the present invention is to provide a silver halide photographic emulsion and a method for producing the emulsion.

"Structure of the Invention" As a result of extensive studies, the present inventors found that a silver halide prepared by carrying out the nucleation and/or crystal growth process of silver halide grains in the presence of a kelp-resistant dispersion medium. By subjecting the emulsion to a treatment with a gelling-resistant dispersion medium after the completion of crystal growth, it is possible to improve the decrease in sensitivity and increase in fog observed in emulsions prepared in the presence of a gelling-resistant dispersion medium. It became clear.

That is, the object of the present invention was achieved for the first time as follows.

(1) Dispersion medium and photosensitivity/-In a silver halide emulsion consisting of silver halide grains, a part or all of the silver halide grains are difficult to gel with protective colloidal properties during the nucleation and/or crystal growth process. 1. A silver halide emulsion, which is treated in the presence of a gelatinizing dispersion medium, and is treated with a removable gelatinizing dispersion medium after the crystal growth of the silver halide grains is completed.

(2) Photosensitivity in the silver halide emulsion/A part or all of the nucleation and/or crystal growth process of silver halide grains is prepared in the presence of a gelling-resistant dispersion medium having protective colloidal properties. The silver halide photographic emulsion according to (1), characterized in that the photographic silver halide emulsion is carried out by supplying a silver halide emulsion containing minute silver halide grains.

(3) In a method for producing a photographic silver halide emulsion comprising a dispersion medium and photosensitive silver halide grains, a part or all of the nucleation and/or crystal growth process of the silver halide grains has protective colloidal properties. 1. A method for producing a silver halide photographic emulsion, which is carried out in the presence of a gelling-resistant dispersion medium, and is treated with a gelling-resistant dispersing medium after the crystal growth of the silver halide grains is completed.

(4) Part or all of the nucleation and/or crystal growth process of photosensitive silver halide grains in a silver halide emulsion is carried out using microscopic particles prepared in the presence of a gelling-resistant dispersion medium having protective colloidal properties. (3) by supplying a silver halide emulsion containing silver halide grains of
A method for producing a silver halide emulsion as described above.

The "gelling-resistant dispersion medium" as used in the present invention is a dispersion medium that is difficult to gel (coagulate) compared to general photographic gelatin (molecular weight of 70,000 or more) and that is compatible with silver halide grains. (A) low molecular weight gelatin, which has protective colloidal properties against
(B) Refers to synthetic polymer compounds and natural polymer compounds other than gelatin.

(A): Average molecular weight is 50,000 or less, preferably 50
0-30000, more preferably 1000-20000
Low molecular weight gelatin The low molecular weight gelatin used in the present invention can be produced by a conventional method.

Gelatin, which is generally used for photography and has an average molecular weight of about 100,000, is dissolved in water, and a gelatin-degrading enzyme is added to enzymatically decompose the gelatin molecules.

This method is described by R.J. Cox, Photog
rapicGeratin II, Academy
c Press, London, 1976, 2
The descriptions on pages 33-251 and 335-346 can be referred to.

In this case, since the bonding positions that the enzyme decomposes are fixed, it is possible to obtain low molecular weight gelatin with a relatively narrow molecular weight distribution, and the molecular weight can be adjusted by adjusting the enzymatic decomposition time (the longer the time, the lower the molecular weight). preferable.

Other methods include a method of heating and hydrolyzing in a low pH (1 to 3) or high pH (10 to 12) atmosphere, and a method of cutting crosslinks by ultrasonic irradiation. Note that, in addition to commonly used gelatin, modified gelatin or the like may be used for production.

The molecular weight distribution and average molecular weight of gelatin can be determined by common methods such as gel filtration chromatography (GPC),
It can be determined by the core solvage/gin method.

(B): Synthetic polymer compound a, polyacrylamide polymer Acrylamide homopolymer US Patent 2,5414
Copolymer of polyacrylamide and imidized polyacrylamide shown in No. 74, West German Patent No. 1202.13
Copolymer of acrylamide and methacrylamide shown in No. 2, partially aminated acrylamide polymer shown in U.S. Pat. No. 3,284,207.
Substituted acrylamide polymers such as those shown in U.S. Pat. No. 5-14031, U.S. Pat. No. 3,713,834, U.S. Pat.

b, Amino Bolima - U.S. Pat. No. 3,345,346, No. 3,706, 50
No. 4, No. 4.350759, West German Patent No. 2,138,8
Aminopolymer shown in No. 72 British Patent No. 1,413
Polymers with quaternary amines as shown in U.S. Pat. No. 3,511,81;
A polymer having an amine group and a carboxyl group as shown in No. 8. A polymer as shown in US Pat. No. 3,832,185.

C, polymers having thioether groups U.S. Pat. Nos. 3,615,624 and 3,860,428
3,706, 564, and the like.

d. Polyvinyl alcohol Homopolymer of vinyl alcohol US Pat. No. 3,000.
Organic acid monoesters of polyvinyl alcohol shown in No. 741, maleic acid esters shown in US Pat. No. 3,236,653, copolymers of polyvinyl alcohol and polyvinylpyridine shown in US Pat. No. 3,479,189, and the like.

e, acrylic acid polymer acrylic acid homopolymer U.S. Patent 3,832,185
Acrylic acid ester polymer having an amine group shown in US Pat. No. 3,852,073 U.S. Pat.
Halogenated acrylic ester polymers shown in US Pat. No. 4,120.727/anoalkyl acrylic esters, etc.

f, Polymers with Hydroxyquinoline U.S. Patent 4,
Polymers having hydroxyquinoline as shown in No. 030,929 and No. 4,152,161.

g, cellulose, starch British Patent No. 542,704, British Patent No. 551,659, U.S. Patent No. 2゜127.573, British Patent No. 2,311,086,
Derivatives of cellulose or starch shown in No. 2, No. 322, Cj85.

h, acetal U.S. Pat. No. 2,358.836, U.S. Pat. No. 3,003,879
No. 2,828.204, British Patent No. 771,155
Polyvinyl acetals shown in No.

l, homopolymer of polyvinylpyridinehinylpyrrolidone, Buddhist patent 2゜031
．． Copolymers of acrolein and pyrrolidone shown in No. 396, etc.

J. Polystine, polystyrylamine polymers shown in U.S. Pat. No. 4,315.071, halogenated styrene polymers shown in U.S. Pat. No. 3,861,918, and the like.

k, Ternary Polymer Special Publication No. 43-7561, German Patent No. 2,012,095
terpolymer copolymers of acrylamide, acrylic acid, and vinylimidazole shown in No. 2012.970.

1. Other vinyl polymers having azaindene groups as shown in JP-A No. 59-8604 U.S. Pat. No. 2,976,150
Polyalkylene oxide derivatives shown in No. 2, polyhinylamine imide polymers shown in U.S. Pat. No. 4,022,623, U.S. Pat.
Polymer shown in 89.688 U.S. Pat.
Polyvinylpyridine as disclosed in No. 4.456, hinyl polymer having an imidazole group as shown in U.S. Patent No. 3,520.857, hinyl polymer having a triazole group as shown in Japanese Patent Publication No. 60-658, Journal of the Photographic Society of Japan Vol. 29, No. 1 Polyamide-2-methylimitazole and acrylamide-imidazole copolymer shown on p. Alkylene aminotriazoles.

"Removable gelling-resistant dispersion medium treatment" refers to a silver halide emulsion prepared by carrying out the nucleation and/or crystal growth process of silver halide grains in the presence of a gelling-resistant dispersion medium. This refers to washing with water by dialysis, coagulation, or the like after the completion of crystal growth of silver oxide particles to remove part or all of the carp gelatinizing dispersion medium. One of the preferred embodiments is to perform this treatment to simultaneously remove the gelling-resistant dispersion medium and other dissolved substances, mainly salts.

The removal rate of the gelling-resistant dispersion medium by this treatment (i [amount of gelling-resistant dispersion medium remaining in the emulsion after treatment/amount of gelling-resistant dispersion medium contained in the emulsion before treatment]) There is no special limit, preferably 70 or more, more preferably 80
% or more, more preferably 1'i90% or more. Moreover, the process may be performed only once or several times.

In the treatment with a non-gelling dispersion medium using a coagulation method, a polymer flocculant can be preferably used.

The polymer flocculant used in the present invention refers to a polymer substance capable of coagulating silver halide grains together with a protective colloid.

As a polymer flocculant, 50% of the amine groups of gelatin molecules
Modified gelatin with the above substitutions can be preferably used. Hereinafter, this may also be referred to as a G agent. Examples of substituents for amino groups in gelatin include U.S. Pat.
, No. 582, No. 2,614,928, No. 2.525,
It is described in No. 753.

Useful substituents include (1) anlu groups such as alkylthiol, arylanru, acetyl, substituted and unsubstituted benzoyl, (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl, (3) alkylsulfonyl, arylsulfonyl, etc. sulfonyl group, (4) thiocarbamoyl group such as alkylthiocarbamoyl, arylthiocarbamoyl, (5) carbon number 1-18
(6) Aryl groups such as substituted or unsubstituted phenyl, naphthyl, and aromatic heterocycles such as pyridyl and furyl.

Among them, preferred modified gelatin has an allyl group (-COR
, ) or a carbamoyl group (-C0NR,).

The above R1 is a substituted or unsubstituted aliphatic group (for example, a group having 1 to 1 carbon atoms)
18 alkyl groups, allyl groups), aryl groups, or aralkyl groups (for example, phenethyl groups), and R2 is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.

Particularly preferred is the case where R1 is an aryl group and R2 is a hydrogen atom.

Specific examples of the G agent that can be used as a polymer flocculant in the present invention are illustrated below using amino group substituents, but the present invention is not limited thereto.

Exemplary G agent (amine group substituent): G-I G-2 C〇-C(CHs) s C0C
H3CHl -g G G -11G -12 When using a G agent during treatment with a dispersion medium that is difficult to remove,
The amount added is not particularly limited, but 0.00% of the substance (preferably gelatin) contained as a protective colloid during removal.
Generally, continuous light is 1 to 5 times the amount (by weight), and particularly preferably 0.3 to 2 times the amount (by weight).

In the present invention, in order to coagulate the silver halide emulsion, it is preferable to add an acid to lower the pH along with the addition of the polymer flocculant. 5.5 or less, particularly preferably 5.5 to 3.5. pH
The acid used for adjustment is not particularly limited, but organic acids such as acetic acid, citric acid, and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are preferably used. The polymer flocculant may be added as a solid to the silver halide emulsion and dissolved, or it is convenient to add it as an aqueous solution of 20% or less.

As a preferable polymer flocculant, JP-A-58-1403
The organic gelatin flocculant described in No. 22 and the polymer compound represented by the general formula [■] consisting of the following A chain and B chain (hereinafter sometimes referred to as P agent) can be mentioned.

General Formula [1] In the formula, R+ and R2 represent an aliphatic group, and may be different from each other or the same. R1 represents a hydrogen atom, an aliphatic group, an aryl group or an aralkyl group. X is 〇- or -N)
(-, MΦ represents a cation. n takes a numerical value of 10 to 10'. The two linking hands of chain B are R, , R2 of chain A.
may be bonded to either side of the tertiary carbon. Further, when X is -NH-, it may form a nitrogen-containing ring together with R1.

This polymer compound is preferably halo' in terms of molecular weight.
-10', more preferably 3 x 103 to 2 x lo5, and the amount added is preferably 1150-1 in weight ratio to the protective colloid (preferably gelatin) contained in the emulsion.
/4, more preferably L<Ha l/40-1/10.

The usage method is similar to the above-mentioned agent G.

Specific examples of the polymer compound represented by the general formula CI''J are listed below, but the invention is not limited thereto.

CH.

CH3 CH3 CI(.

CHl CH.

Go, H To CO2 CH3 CH.

CH3 02NB4 CH3 U2Na In the present invention, a polymer flocculant (for example, G agent, P agent)
and heavy metal ions may be used together. The heavy metal ion used is preferably one that binds to the carboxylic acid in the protective colloid gelatin brought in from the polymer flocculant and/or the physical ripening process of the silver halide emulsion, such as magnonium ion, Examples include cadmium ions, lead ions, zinc ions, zirconium ions, etc., and magnesium ions are particularly preferably used.

These heavy metal ions are usually added in the form of inorganic salts, and may remain solid, but are preferably added in a state dissolved in water.

The amount of these heavy metal ions added is preferably 1 to 0.2 mol/Q when added to the silver halide emulsion.

Can the polymer flocculants (e.g., G agent, P agent) and heavy metal ions mentioned above be added at any step in the silver halide emulsion manufacturing process? It is most convenient to add. As for the order of addition to the silver halide emulsion, the polymer flocculant, heavy metal ion, and acid may be added in any order, that is, any of the arithmetically possible combinations (6 ways) may be used. The following two types are most preferred.

■ Polymer flocculant - Heavy metal ion - Acid ■ Heavy metal ion - Polymer flocculant - Acid These flocculants can be added to the silver halide emulsion immediately or over time. good. The addition temperature is preferably used in the range of room temperature to 60'C, but the temperature of the silver halide emulsion from the time of starting to add these aggregates until the end of addition is 70 to 40'C.
It is preferable to keep it at a temperature to allow coagulation to occur.

The treatment with a non-gelling dispersion medium may be repeated once or several times. If the removal is repeated several times, the polymer flocculant and/or heavy metal ion may be added each time the removal is performed, or the flocculant polymer agent and heavy metal ion may only be added first.

In the present invention, a polymer flocculant and a heavy metal ion may be added, but it is also possible to use a polymer flocculant and a heavy metal ion together at the time of initial removal of dissolved substances (desalting and removal-resistant dispersion medium). preferable.

It is more preferable to use a coagulation method as the treatment with a dispersion medium that is difficult to remove and gel, and it is more preferable to use a G agent as the polymer flocculant (G agent, P agent).

After the treatment with a dispersion medium that is difficult to remove and gel, the silver halide emulsion may be redispersed by adding a dispersion medium having protective colloidal properties such as gelatin. In that case, it is preferable to use a dispersion medium other than a dispersion medium that is difficult to remove and gel, and it is particularly preferable to use general photographic gelatin (molecular weight of 70,000 or more).

The silver halide emulsion of the present invention is one in which part or all of the nucleation and/or crystal growth process of silver halide grains is carried out in the presence of at least one type of gelling-resistant dispersion medium for various purposes. There is no restriction on the preparation method other than that, but in particular, when it is prepared by the following method, the effect of the present invention is to reduce the nucleation and/or crystal growth of photosensitive silver halide grains in the silver halide emulsion. Part or all of the process is carried out by supplying a silver halide emulsion containing minute silver halide grains prepared in the presence of a gelling-resistant dispersion medium having protective colloidal properties.

The grain size of the fine silver halide grains (sometimes referred to as silver halide fine grains) added during the nucleation and/or crystal growth process of the photosensitive silver halide 5 grains is preferably 0.1 μm or less, and more preferably Preferably it is 0.05 μm or less, more preferably 0.03 μm or less.

The particle size is determined, for example, by actually measuring the particle diameter in an electron micrograph at a magnification of 30,000 to 60,000 times or the projected area.

The silver halide grains may be (a) prepared prior to the nucleation and/or crystal growth of the photosensitive silver halide grains; or (b) prepared and added in parallel. You can.

In the case of (b), since the stagnation time from the generation of the nucleus of the silver halide grains to the addition thereof is short, it is possible to suppress the increase in the size of the fine grains due to Ostwald ripening between the fine grains. In particular, adding the silver halide grains continuously while preparing them is effective in shortening the stagnation time.

When the photosensitive silver halide grains have at least one layer consisting of a mixed crystal of two or more types of /X silver halide, and the core layer is formed by supplying fine silver halide grains, (1) the objective It may be carried out using silver halide fine particles having a silver halide composition corresponding to the halide composition of the silver halide grains, or (2) two or more types of silver halide fine particles having different silver halide compositions. Using,
They may be supplied simultaneously or individually at a mixing ratio depending on the desired halide composition of the silver halide grains.

There are no particular restrictions on the method of adding (supplying) fine grains, the silver halide composition and number of types of fine grains to be added, and whether or not the fine grains to be added are treated with a dispersion medium that is difficult to gel. They may be combined in any way during the preparation of the silveride emulsion.

However, in the case where the photosensitive silver halide grains have at least two layers with different silver halide compositions and at least two of the core layers are formed by supplying silver halide grains, the fine grain addition (supply) method is In accordance with (a):
Combining (2) is preferable in terms of production efficiency.

The silver halide composition of the emulsion according to the present invention is arbitrary. For example, silver halides that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, Any silver halides such as silver chloroiodobromide and mixtures thereof are included, and silver iodobromide is particularly preferably used. When using silver iodobromide, those having a high silver iodide content layer inside the grains are particularly preferred.

The silver iodide content of the high silver iodide content layer is 15 to 45 mol%.
is preferable, more preferably 20 to 42 mol%, particularly preferably 25 to 40 mol%.

When a silver halide grain has a structure having a high silver iodide content layer inside the grain, the high silver iodide content layer is replaced with a low silver iodide content layer having a lower silver iodide content, or a salt layer. It is coated with a silver bromide layer.

In this case, the low silver iodide content layer can be configured to form the outermost layer of the grains in the following sense.

That is, when forming the outermost layer, the average silver iodide content of the silver iodide content layer, which has a lower content than the high silver iodide content layer, is preferably less than 5 mol%, particularly preferably. is 0 to 4 mol%. Further, another silver iodide-containing layer (intermediate layer) may be present between the outermost layer and the high silver iodide content layer.

The silver iodide content of the intermediate layer is preferably 8 to 22 mol%, particularly preferably 10 to 20 mol%.

It is preferable that the difference in silver iodide content between the outermost layer and the intermediate layer, and between the intermediate layer and the inner high silver iodide content layer is 6 mol% or more, and particularly preferably, there is a difference of 10 mol% or more in either of them. There is a difference of more than mol%.

In the above embodiment, the central part of the internal high silver iodide content layer,
Further silver halide layers may be present between the inner high silver iodide content layer and the intermediate layer, and between the intermediate layer and the outermost layer.

In addition, the volume of the outermost layer is preferably 3 to 70 mol% of the entire particle,
More preferably 5 to 50 mol%. The volume of the high silver iodide content layer is desirably 10 to 80% of the entire grain;
5 to 50%, more preferably 15 to 45%.

The volume of the intermediate layer is 5 to 70% of the entire particle, and even 10%.
~65% is good.

These layers may be a single layer with a uniform composition, a group of layers with a stepwise change in composition consisting of multiple layers with a uniform composition, or continuous layers within any layer. It may be a continuous layer whose composition changes over time, or it may be a combination of these layers.

In another embodiment of the silver halide emulsion of the present invention, silver iodide localized within the grains does not form a substantially uniform layer, but the silver iodide content is continuous from the center of the grains toward the outside. Examples include aspects that change depending on the situation.

In this case, it is preferable to have a silver iodide composition structure shown in JP-A-1-341582 and JP-A-2-943.

Also in this case, the silver iodide content in the outermost layer of the grain is 5.
It is preferably less than mol%, particularly preferably 0 to
It is 4 mol% silver iodobromide.

The silver halide emulsion of the present invention has an average silver iodide content of 4 to 2.
Preferably, the silver iodobromide content is 0 mol %, and particularly preferably, the average silver iodide content is 5 to 15 mol %.

Further, the silver halide grains according to the present invention have a structure in which the surface layer of the silver halide grain has a higher silver iodide content than the layer adjacent to the surface layer, as shown in Japanese Patent Application No. 2-34186 filed by the present applicant. It may have.

The silver halide emulsion of the present invention preferably satisfies at least one of the following conditions (1) to (4).

■ Average silver iodide content determined by X-ray fluorescence analysis (
Jl) and the silver iodide content on the grain surface determined by the xPS method (A
When comparing 2), the relationship J+>Jz must be satisfied.

Here, the xPS method will be explained as follows.

Prior to measurement by the xPS method, the emulsion is pretreated as follows. First, add pronase solution to the emulsion and
The gelatin was decomposed by stirring at C for 1 hour.

Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the above conditions. The sample is centrifuged again, the supernatant liquid is removed, and then distilled water is added to redisperse the emulsion particles in the distilled water, centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. This is applied thinly onto a mirror-polished silicon wafer to provide a measurement sample.

For measurements using the xPS method, for example, the equipment used is E manufactured by P.
Using SCA/SAM560 type, Mg is used for excitation X-rays.
-Ka line, X-ray source voltage 15KV, X-ray source current 40mA
, under the condition of a pass energy of 50 eV.

A43d, Br5d to determine the surface halide composition
.

Detects 13d3/2 electrons. The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak.

By using 5.10.0.81.4.592 as the relative sensitivity coefficient for Ag5d, Br5d, +3d3/2, respectively, the composition ratio is given in atomic percent.

■ Average silver iodide content determined by X-ray fluorescence analysis (
J,) and the average value of the silver iodide content measured on silver halide crystals that are 80% or more away from the center in the grain diameter direction of the silver halide grains using the XMA method (J,) When comparing, the relationship J+>Js must be satisfied.

XMA method (X-ray Micro Analysis
) is explained as follows. Silver halide particles were dispersed in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer in an electron microscope, the magnification was set so that one particle entered the field of view of the CRT with liquid nitrogen cooling, and AgLα, AgLα, Integrate the intensity of the ILa line. I
The silver iodide content can be calculated by preparing an intensity ratio of Lσ/AgLa in advance and using a calibration curve.

(4) Using CuK a-ray as a radiation source (420) At the highest peak height XO, 13 of the X-ray diffraction signal, a signal exists continuously over a diffraction angle of 1.5 degrees or more. More preferably, the highest peak height of the signal Xo,
In No. 15, the gnal exists continuously over a diffraction angle of 1.5 degrees or more. Further, the diffraction angle at which the signal exists is preferably 1.8 degrees or more, and particularly preferably 2.0 degrees or more.

The presence of a signal means that the signal intensity is greater than or equal to the highest peak height x 0.13 or X 0-15.

(4) The above (420) X-ray diffraction signal using CuKC rays as a radiation source has two or three peaks. Particularly preferred is one having three peaks.

The X-ray diffraction method, which is known as a method for investigating the structure of silver halide crystals, will be described as follows.

Various characteristic X-rays can be used as the X-ray source. Among them, CuKa ray targeting Cu is the most widely used.

Silver iodobromide has a rock salt structure and has a (420)
The diffraction lines are observed at 71 to 74 degrees 2θ, where the gnal strength is relatively strong and the angle is high, so the resolution is good and it is optimal for studying the crystal structure.

When measuring the X-ray diffraction of a photographic emulsion, it is necessary to remove gelatin, mix a standard sample such as silicon, and perform the measurement using a powder method.

Regarding the measurement method, reference can be made to Basic Analytical Chemistry Course 24 "X-ray Analysis" (Kyoritsu Publishing).

In the emulsion of the present invention, it is preferable that the silver iodide content among the grains is more uniform. When the average silver iodide content of individual silver halide grains is measured by the XMA method, it is preferable that the relative standard deviation of the measured values is 20% or less. More preferably it is 15% or less, particularly preferably 12% or less.

The relative standard deviation here is, for example, the value obtained by dividing the standard deviation of the silver iodide content when measuring the silver iodide content of at least 100 emulsions by the average silver iodide content at that time x 100
It is.

The crystal habit of the silver halide grains of the present invention is not particularly limited.

The silver halide grains of the present invention may be normal crystals such as cubes, octahedrons, dodecahedrons, tetradecahedrons, and icosahedrons, tabular or thin twin crystals, and irregularly shaped grains such as potato-shaped grains. It may be. It may also be a mixture of these.

In the case of tabular twin crystals, the ratio of the equivalent circular diameter to the grain thickness is 1 to 2o, which accounts for 60% of the projected area.
It is preferably 1.2 or more and less than 8.0, particularly preferably 1.5 or more and less than 5.0.

The silver halide emulsion of the present invention is preferably a monodisperse silver halide emulsion.

In the present invention, a monodisperse silver halide emulsion is one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size d is 70% or more of the total weight of silver halide. preferably 80% or more, more preferably 90%
% or more.

Here, the average particle size d is the frequency n1 of particles having particle size d.
It is defined as the grain size d1 when the product n, X d and s of x and d13 becomes maximum. (3 significant figures, minimum 4 digits)
The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times using an electron microscope, projecting the particles, and actually measuring the particle diameter or area at the time of projection on the print. (The number of particles to be measured is assumed to be 1000 or more indiscriminately.

Particularly preferred highly monodispersed emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less.

Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is the arithmetic mean.

The average grain size of the silver halide emulsion of the present invention is 0.1 am to 1
It is preferable that it is 000 μm, more preferably 0.00 μm.
2 μm to 5-0 μm, particularly preferably 0.3 μm to 3.0 μm.
It is 0 μm.

Monodisperse normal crystal emulsions are disclosed, for example, in JP-A-59-177.
No. 535, No. 60-138538, No. 59-5223
No. 8, No. 60-143331, No. 60-35726, No. 60-258536, No. 61-14636, etc.

Monodisperse twin emulsions are disclosed, for example, in JP-A-61-1463.
It can be obtained by referring to the method for growing a spherical seed emulsion disclosed in Japanese Patent No. 6.

Preparation of the emulsion of the present invention or other emulsions used in combination as necessary when constituting the light-sensitive material obtained using the emulsion of the present invention (hereinafter sometimes referred to as the light-sensitive material of the present invention) A substance other than gelatin that has adsorption properties to silver halide grains may be added at any time (including at the time of preparing the seed emulsion). Such adsorbing substances are useful, for example, compounds used in the art as sensitizing dyes, antifoggants or stabilizers, or heavy metal ions. Specific examples of the above-mentioned adsorptive substances are described in JP-A-62-7040.

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

Among the antifoggants and stabilizers, heterocyclic mercapto compounds and/or azaindene compounds are particularly preferred. Specific examples of more preferred heterocyclic mercapto compounds and azaindene compounds are described in detail in JP-A-6341848.

The amount of the above-mentioned heterocyclic mercapto compound and azaindene compound added is not limited, but preferably 1 x to-' to 3 x to-' mol per 1 mol of silver halide.
More preferably, it is 5 X 10-' to 3 X 10-' moles. This amount is appropriately selected depending on the manufacturing conditions of the silver halide grains, the average grain size of the silver halide grains, and the type of the above-mentioned compound.

In the light-sensitive material of the present invention, in addition to the silver halide grains of the present invention, other /% silver halide grains may be used in combination.

The silver halide grains used in combination may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or a monodisperse emulsion with a narrow grain size distribution may be used.

The light-sensitive material of the present invention is formed by containing the silver halide grains of the present invention in at least one of the silver halide emulsion layers constituting it, but other than the silver halide grains of the present invention are contained in the same layer. silver halide grains may be contained.

In this case, it is preferable that the emulsion containing the silver halide grains of the present invention accounts for 20% by weight or more, more preferably 40% by weight or more.

Further, when the light-sensitive material of the present invention has two or more silver halide emulsion layers, there may be an emulsion layer consisting only of silver halide grains other than the silver halide grains of the present invention.

In this case, the emulsion of the present invention preferably accounts for 10% by weight or more, more preferably 20% by weight or more of the silver halide emulsion used in all the photosensitive layers constituting the light-sensitive material.

The silver halide grains of the present invention are disclosed in Research Disclosure+-(Research Disclosure,
Spectral sensitization can be carried out using the spectral sensitizers described in the following volumes and pages of RD (hereinafter abbreviated as RD), or spectral sensitization can be carried out in combination with other sensitizers.

No, 17643 (P, 23-24) No, 1871
6 (P, 648-649) No. 308119 (P,
996. IV-A, B, C, D: H.

Items I and J) The effects obtained in the present invention become remarkable by spectrally sensitizing the silver halide grains of the present invention. In particular, the effects of the present invention become more pronounced when trimethine and/or monomethine cyanine dyes are used alone or in combination with other spectral sensitizers. Further, silver halide grains other than the silver halide grains of the present invention used in the light-sensitive material of the present invention, if necessary, can be optically sensitized to a desired wavelength range. In that case, there are no particular restrictions on the optical sensitization method, and for example, cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, cyanine dyes such as merocyanine dyes, or optical sensitizers such as merocyanine dyes are used alone. Alternatively, they can be used together to optically sensitize.

Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself has no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. These techniques are described in U.S. Patent No. 2,688,545;
, No. 912,329, No. 3,397.060, No. 3,
No. 615,635, No. 3,628.964, British Patent I.

195.302, 1,242.588, 1,2
No. 93,862, West German Patent (OLS) 2,030,3
No. 26, No. 2,121,780, Special Publication No. 43-140
No. 30, RD Vol. 176, 17643 C, December 1978 issue), page 23, Section 1, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

In the present invention, various commonly used chemical sensitization treatments can be performed. Chalcogen sensitizers used in chemical sensitization include sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred for use in photography. As the sulfur sensitizer, known ones can be used. For example, thiosulfate, allylthiocarbamide, thiourea, allylisothionoanate, cystine,
Examples include p-toluenethiosulfonate and rhodanine. In addition, U.S. Patent No. 1,574,944, U.S. Patent No. 2.
No. 410.689, No. 2,278,947, No. 2,7
No. 28.668, No. 3501.313, No. 3,656
, No. 955, West German Application Publication (0LS) 1.422, 86
No. 9, JP-A-56-24937, JP-A No. 55-45016
Sulfur sensitizers described in No. 1, etc. can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This appropriate amount varies over a considerable range under various conditions such as pH temperature and silver halide grain size, but as a guide, it is about 10-7 mol - about 1O-1 mol per mol of silver halide. is preferred.

Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethylselenide, and diethylselenide. Selenides such as
, No. 944, No. 1,602,592, No. 1,623.
No. 499.

As with the sulfur sensitizer, the amount added varies over a wide range, but as a guide, approximately 1 O-
A low 7-10-' molar degree is preferred.

In the present invention, the gold sensitizer may have a valence of +1 or +3, and various types of gold compounds may be used. Typical examples include chloroauric acids, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is approximately 10-' mol to 1 O per mol of silver halide.
A range of up to -1 mole is preferred.

The gold sensitizer may be added at the same time as the sulfur or selenium sensitizer, during or after the sulfur or selenium sensitization step.

The pAg of the emulsion subjected to sulfur sensitization, selenium sensitization, and gold sensitization in the present invention is 5.0 to 10.0, and the pn is 5.0 to 5.0.
A range of 9.0 is preferred.

The chemical sensitization method in the present invention can also be combined with a sensitization method using other noble metals, such as metal salts such as platinum, palladium, iridium, and rhodium, or complex salts thereof.

Furthermore, complexes of Rh, Pd, Ir, PL and the like are effective as compounds that release gold ions from gold-gelatinate and promote adsorption of gold ions onto silver halide grains.

A specific compound is (NH4)! [PtCl2a
], (NH4)! [PdCL], K3 [[rBrs
Ammonium tetrachloropalladate (n) (NH4) 2 [PdCl24
]. The amount added is preferably 10 to 100 times the stoichiometric ratio (mole ratio) to the gold sensitizer.

The addition time may be at the start of, during, or after the chemical sensitization process, but preferably during the chemical sensitization process, and particularly preferably at the same time as or after the addition of the gold sensitizer. Before and after.

In the present invention, reduction sensitization can also be used in combination. The reducing agent is not particularly limited, but includes known stannous chloride, thiourea dioxide, hydrazine derivatives, polyamines, and the like.

Although reduction sensitization is performed during the growth of silver halide grains, it is preferably performed after completion of chalcogen sensitization, gold sensitization, and noble metal sensitization.

Furthermore, in the chemical sensitization treatment, a compound having a nitrogen-containing heterocycle, particularly preferably an azaindene ring, may be allowed to coexist.

The amount of the nitrogen-containing heterocyclic compound added varies over a wide range depending on the emulsion grain size, composition, chemical sensitization conditions, etc., but preferably it forms a monomolecular layer to a IO molecular layer on the surface of the silver halide grains. It is best to add the amount to the extent that The amount added can also be adjusted by controlling the adsorption equilibrium state by changing pu and/or temperature during sensitization.

Alternatively, two or more of the above compounds may be added to the emulsion so that the total amount falls within the above range.

The compound may be added to the emulsion using a suitable solvent (such as water or an aqueous alkaline solution) that does not have a harmful effect on the photographic emulsion.
It can be added as a solution. The timing of addition is preferably before or at the same time as adding a sulfur sensitizer or a selenium sensitizer for chemical sensitization. The gold sensitizer may be added during or at the end of sulfur or selenium sensitization.

Further, the silver halide grains can be optically sensitized to a desired wavelength range using a sensitizing dye.

Various additives can be used in the photosensitive material when carrying out the present invention. For example, known photographic additives that can be used are exemplified in RD. Undercolor clouding prevention agent Pigment image stabilizer Brightening agent Ultraviolet absorber Light absorber Light scattering agent Filter dye Binder Static inhibitor Hardener Plasticizer Lubricant Activator/coating aid Matting agent Developer (Contained in photosensitive material) 25-26 25-26 Various couplers can be used in the present invention, and specific examples thereof are illustrated in the above RD. The relevant entries are shown in the table below.

[Item] (RD 308119 page) (RD 17643) Yellow coupler 10
01 ■-ri term ■ C-G term magenta kagura-1
001 ■-ri term ■ C-G term uncoupler-100
1■-ri term ■C-G term colored force graph-1002■-
Section G ■ Section G DIR coupler 1001 ■ Section F ■ Section F BAR coupler 1002 ■ Section F Alkali-soluble coupler 1001 Section E - Section E This section 4 Additives used in the invention are dispersion method described in RD308119X N It can be added by etc.

In the present invention, the aforementioned RD1764328 page, RD1
87, pages 6647-8 and R[1308119, X■] can be used.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119--.

The photosensitive material of the present invention can have various layer structures such as normal layer, reverse layer, and unit structure as described in the above-mentioned RD308119--.

The present invention covers color negative films for general use or movies, color reversal films for slides or televisions,
Color paper It can be preferably applied to various color photosensitive materials, typified by color positive film and color reversal paper.

Furthermore, it can be used for various purposes such as black and white general use, X-ray use, infrared use, micro use, silver dye bleaching method, diffusion transfer method, and reversal use.

The photosensitive material of the present invention can be developed by commonly used known methods. For example RD1764328
~29 pages, RD18716615 pages and I? D3081
It can be developed by the usual method described in 19X ff.

[Example 3] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example-1 (Preparation of silver bromide fine grain emulsion MC-1) A 9.6-wt.
gelatin (COL l: average molecular weight = 8000)
To 5000 mQ of the solution, 3500 mff each of aqueous solutions containing 10.6 moles of silver nitrate and potassium bromide were added at an accelerated flow rate (the flow rate at the end was 5 times the initial flow rate) over a period of 28 minutes. The temperature during microparticle preparation was kept at 15°C.

When the obtained silver bromide fine particles were confirmed by an electron micrograph at a magnification of 60,000 times, the average particle size was 0.028 μm.

(Preparation of silver iodide fine grain emulsion MC-2) 1.06% by weight of gelatin (COL-1) solution containing 0.004 mol of potassium iodide was added to 10100O of gelatin (COL-1) containing 0.004 mol of potassium iodide.
250 m each of an aqueous solution containing moles of silver nitrate and potassium iodide
(l is the accelerated flow rate (the flow rate at the end is 4 of the initial flow rate)
(times) was added over a period of 33.6 minutes. The temperature during microparticle preparation was kept at 15°C.

The obtained iodide l! When the fine particles were confirmed using an electron micrograph at a magnification of 60,000 times, the average particle size was 0.022 μm.

(Preparation of octahedral silver iodobromide emulsion EM-1) Average grain size 0.3
3 μm monodisperse silver iodobromide grains (silver iodide content 2 mo+
2%) as a seed crystal, an octahedral silver iodobromide emulsion was prepared.

Solution <G-1> at temperature 75°C, pAg 7.8, pH
7, Qi: : 144.4 mm of seed emulsion equivalent to 0.34 mol was added while stirring well. Thereafter, silver bromide fine grain emulsion (MC-1) silver iodide fine grain emulsion (AIG-2)
) was added over a period of 86 minutes at an accelerated flow rate (ending flow rate was 3.6 times the initial flow rate) while maintaining a flow rate ratio of 7:3. The fine particles consumed during this period are (MC-1) and (
MC-2) was equivalent to 1.82 mol in total.

Then pAglO,1, pH6,0i: N? l
ft. Silver bromide fine grain emulsion (MC-1) was added at an accelerated flow rate (the final flow rate was 5.2 times the initial flow rate) over a period of 65 minutes. Fine particles (MC-
1) was equivalent to 6.67 mol.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 1.15 μm, a distribution width of 10.7%, and a silver iodide content of 6 to 26 mof1%. This emulsion is
Let it be M-1.

(Preparation of octahedral silver iodobromide emulsion EM-2) An octahedral silver iodobromide emulsion was prepared in the same manner as emulsion EM-1.

However, for the first 86 minutes, <H-1> and <S-1> were used at a flow rate ratio of 1:1 instead of silver bromide fine grain emulsion (MC-1) and silver iodide fine grain emulsion (MC-2). , for the latter 65 minutes, H-2> and <S> were used instead of silver bromide fine grain emulsion (MC-1).
-2> were added by double jet method at a flow rate ratio of 11, respectively.

The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains with an average grain size of 1.15 μm and a width of 12.4% in 1 distribution and a silver iodide content of 6.26 mo (2%). This emulsion is
Let it be M-2.

The gelatin and solution composition used are as follows.

COL-0 2 General photographic gelatin average molecular weight - 100000 COL ]: Low molecular weight gelatin produced by enzymatically decomposing C0L-0 Average molecular weight - 8000 <G-1><H2>(S-2> Compound ■ = 10% ethanol aqueous solution of polyisopropylene polyethyleneoxy disuccinate sodium salt <H ■ ><S-1> (Preparation of EM-3 to E-8) For EM-1 and EM-2 , as shown in Table 1.At this time, the above-mentioned exemplified compound G-8 was used as the G agent, and JP-A-58-14 was used as the P agent.
Exemplary compound 11-1 of No. 0322 was used.

Each emulsion after processing was prepared to have the same dispersion medium content and volume as before processing. Adjustment of the dispersion medium content was performed using gelatin (COL-0). Further, the pH and I)Ag were adjusted to 5.8 and 8.06, respectively, at 40°C.

The amount of gelling-resistant dispersion medium contained in the emulsion was determined by gel filtration chromatography. At that time, a calibration curve prepared in advance was used.

(Preparation of silver halide photographic light-sensitive material samples) EM-1 to E
Each emulsion of M-18 was optimally subjected to gold/sulfur sensitization and spectral sensitization, and using these emulsions, each layer having the composition shown below was sequentially coated on a triacetyl cellulose film support on the support side. A sample of a multilayer color photographic material was prepared by forming the following steps.

In all the examples below, the amount added in the silver halide photographic material is expressed in grams per l+n2, unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye is expressed in moles per mole of silver in the same layer.

The composition of multilayer color photographic material Sample-1 is as follows.

Sample-1 (comparison) 1st layer; antihalation layer (HC-1) black colloidal silver 0.2 UV absorber (UV-1
) 0.23 High boiling point solvent (○112-1
) 0.18 gelatin
1.4 Second layer; First intermediate layer (IL-1) Gelatin 1.3 Third layer;
Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (EM-L) 1.0 sensitizing dye (S
D-1) 1.8X 10-' sensitizing dye (SD-2)
2.8X 10-' sensitizing dye (SD-3)3. OX
to-' Cyan coupler (C-1) 0
．． 70 colored cyan coupler (CC-1) 0.066
DIR compound (D-1) 0.03 DIR compound (D-3) 0.01 High-boiling point solvent (OIQ-1) 0.64 Gelatin 1.2 4th layer; medium-sensitivity red-sensitive emulsion layer (RM) Iridescent odor Silveride emulsion (EM-M) 0.8 sensitizing dye (S
D-1) 2.1X 10-' sensitizing dye (S D-2) 1.9X 10-' Sensitizing dye (S D-3) 1.9X 10
-'Cyan coupler (C-1) 0.28
Colored cyan coupler (CC-1) 0.027D
IR compound (D-1) 0.01 High boiling point solvent (O1ff-1) 0.26 Gelatin 0.6 5th layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (EM-1) 1. 70 sensitizing dye (SD-1) 1.9X 10-'
Sensitizing dye (SD-2) 1.7x 1
0-' Sensitizing dye (SD-3) 1.7
X 10-'Cyan coupler (C-1)
0.05 cyan coupler (C-2) 0.
10 colored cyan coupler (c c-1) 0.0
2DIR compound (D-1) 0.025
High boiling point solvent (01Q -1) 0.17
Gelatin 1.2 6th layer: 2nd intermediate layer (IL-2) Gelatin 0.8 7th layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (EM-L) 1.1 Sensitized Dye (S
D-4) 6.8X 10-' Sensitizing Dye (SD-5) 6.2X 10-' Magenta Coupler (M-1) 0.54 Magenta Power Puller C
M-2) 0.19 colored macenta coupler (CM-1) 0.06DIR compound (D-2
) 0.017DIR compound (D-3)
0.01 high boiling point solvent (Oi(1-2
) 0.81 gelatin
1.8 8th layer; Medium green-sensitive emulsion layer (GM) Silver iodobromide emulsion (EM-M) 0.7 Sensitizing dye (SD-6) 1.9X 10-' Sensitizing dye (SD- 7), 1.2XlO-'
Sensitizing dye (SD-8) 1.5X 1
0-5 magenta coupler (M-1) 0.0
7 Magenta coupler (M-2) 0.03
Colored magenta coupler (c M-1) 0.04D
IR compound (D-2) 0.018 high boiling point solvent
(Oi12-2) 0.30 gelatin
0.8 9th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (EM-1)
1.7 Sensitizing dye (SD-4) Sensitizing dye (SD-6) Sensitizing dye (SD-7) Sensitizing dye (SD-8) Magenta coupler (M-1) Magenta coupler (M-3) Colored magenta coupler (CM High point solvent (○112-2) Gelatin 10th layer; Yellow filter layer (Y C) Yellow colloidal silver 0.05 Color stain inhibitor (SC
-1) 0.1 high boiling point solvent (01Q -2
) 0.13 gelatin
0.7 Formalin scavenger (H5-1) 0.
09 Formalin Scavenger (H5-2) 0.07 1st
1st layer: Low-speed blue-sensitive emulsion layer (BL) silver iodobromide emulsion (E
M-L) 0.5 silver iodobromide emulsion (EM
-M) 0.5 sensitizing dye (SD-9
) 5.2X 10-'2, lX 10-
' 1.2X 10-' 1, OX 10-' 3.4X 10-' 0.09 0.04 1) 0.04 0.31 1.2 Sensitizing dye (SD-10) 1.9X
10 bow yellow coupler (Y-1) 0.6
5 yellow coupler (Y-2) 0.24DI
R compound (D-1) 0.03 High boiling point solvent (Oi(2-2) 0.18 Gelatin
1.3 Formalin scavenger (HS-1) 0.08 12th layer; High sensitivity blue-sensitive emulsion layer (B H) Silver iodobromide emulsion (EM-1) 1
．． 0 Sensitizing dye (SD-9) 1.8X
10 Sensitizing dye (SD-10) 7
．． 9x 10 bow yellow coupler (Y-1)
0.15 Yellow coupler (Y-2) 0.
05 High boiling point solvent (○i+2 2) 0.0
74 Gelatin 1.3 Formalin scavenger (HS-1) 0.05 Formalin scavenger (HS-2) 0.12 13th layer; 1st
Protective layer (Pro-1) Fine grain silver iodobromide emulsion 0.4 (average grain size 0.08 μm Agl 1 mol%) Ultraviolet absorber (UV
-1) 0.07 ultraviolet absorber (UV-2)
0.10 High boiling point solvent (○IQ-1) 0.
07 High boiling point solvent (O112-3) 0.07 Formalin scavenger (H3-1) 0.13 Formalin scavenger (HS-2) 0.37 Gelatin 1.3 14th layer: 2nd protective layer (Pro-2 ) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (W
AX-1) 0.04 gelatin
0.6 In addition to the above composition, coating aid 5u-1, dispersion aid 5u-2, viscosity modifier, hardening agent H-
ISH-2, stabilizer 5T-1, antifoggant AF-1,
Mw: 10,000 and Mw: 1,100,00
Two types of AF-2, 0 and 0, were added.

Emulsions EM-L and EM-M used in the above samples are as shown below.

Each emulsion was optimally gold-sulfur sensitized.

Q. Instead of EM-1, as shown in Table 2, emulsions EM-2 to EM-18 were used to prepare samples-2 to EM-1.
Sample-18 was created.

Each sample thus prepared was exposed to a wedge using white light, and then subjected to the following development treatment.

1. Color development...3 minutes 15 seconds 38.0±0,
1℃2, bleaching...6 minutes 30 seconds 38.0±
3.0°C3, water washing...3 minutes 15 seconds 24
~41°C4, fixation...6 minutes 30 seconds 38
．． 0±3.0°C5, washing with water...3 minutes 15 seconds 24-41°C6, stable...3 minutes 15 seconds 38.0±360°C7, drying...・50
The composition of the treatment liquid used in each step is shown below.

<Color developer> 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate 4, 75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (l hydrate) 2.5g Potassium hydroxide 1.0g Add water to adjust to IQ (pH = 10.1) <Bleach solution > Ethylenediaminetetraacetic acid iron(III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make lI2, and adjust to pu6.0 using ammonia water do.

<Fixer> Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 112, and adjust to pH 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5m12
Konidax (manufactured by Konica Corporation) 7.5 m12 Add water to make 112.

Relative fog and relative sensitivity were measured for each sample using red light, green light, and blue light immediately after sample preparation. Table 2 shows the measurement results for green light I.

Relative fog is the relative value of the minimum density (Dmin),
For Samples-3 to Sample-11, the Dmin value of Sample-1 is 100, and for Samples-12 to Sample-18, the Dmin value of Sample-2 is 100. .

Relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of Dmin + 0.15, and for samples -3 to -11, the sensitivity of sample -1 is taken as 100, and for samples = 12 to
For Sample-18, the sensitivity of Sample-2 is expressed as 100.

Note that the values shown in parentheses for Sample-2 are relative values when the value of Sample-1 is set to 100.

Furthermore, results similar to those shown in Table 2 were obtained in measurements using red light and blue light.

Example-2 (Preparation of hexagonal tabular silver iodobromide emulsion EM-A) Average grain size 0
．． 83 μm monodispersed tabular silver iodobromide grains (aspect ratio 4
, a silver iodide content of 2 moQ%) was used as a seed crystal to prepare a hexagonal tabular silver iodobromide emulsion.

The solution <G-2> in the reaction container was heated to a temperature of 75°C and a pAg of 8.
．． 4. After adding the seed emulsion equivalent to 1.10 mol while keeping the pH at 6.5 and stirring well, fine particles are prepared and continuously fed from a mixer for preparing fine particles installed near the reaction vessel. Crystal growth was performed by doing this. <H-3>, (S-3>, and <(, -3>) were added under pressure into a mixing container by a triple jet method at an accelerated flow rate over a period of 63 minutes.

The microparticles prepared in the mixer were added to the reaction vessel with an average residence time in the mixer of 30 seconds.

During this time, the rotation speed of the stirring blade of the mixer was 4000 r, p, m.
, the temperature was maintained at 15°C.

Subsequently, (H-4>, <S-4>, and (G-4>) were added in the same manner over a period of 48 minutes. During this time, the rotation speed of the stirring blade of the mixer was 3500 r, p, m, The microparticles prepared in the mixer were added to the reaction vessel with an average residence time of 20 seconds. Furthermore, <H-5>, S-5> and (G
-5> was added in the same manner over a period of 30 minutes. During this time,
The microparticles prepared in the mixer were added to the reaction vessel with an average residence time of 19 seconds.

When the particle size of the fine particles formed in the mixer was confirmed using an electron microscope photograph with a magnification of 60,000 times, the average particle size was 0.014.
It was μm.

The emulsion thus obtained had an average grain size of 1.51 μm.
The emulsion was a monodisperse emulsion containing hexagonal tabular silver iodobromide grains with an aspect ratio of 3, a distribution width of 11.2%, and a silver iodide content of 8.63 mof2%. This emulsion was designated as EM-A (G-
2><G3><H3><S-3>(G-4><H-4><S-4><G5><H5><S5> (EM-B -EM-D Preparation) Synthetic polymer compounds (COL-2 to COL-4) were used in place of the low molecular weight gelatin (COL-1) used in <G-3>, <G-4>, and <G-5>. Other than that, EM-
EM-B-EM-D were prepared in the same manner as A.

COL-2: Polyvinyl alcohol average molecular weight = 60,000 COL-3: Polyvinylpyrrolidone average molecular weight - 50,000 COL-4: Vinyl polymer having a quinoline group Average molecular weight = 60,000 (Preparation of EM-A' to EM-D') EM-A -For EM-D, as shown in Table 3,
EM-A' to EM-D' were prepared by treating the exemplified compound G-8 with a dispersion medium that is difficult to remove and gel.

Each of the emulsions EM-A' to EM-D' was prepared to have the same dispersion medium content and volume as before treatment.

Adjustment of the dispersion medium content was performed using gelatin (COL-0). Further, the pH and l) Ag were adjusted to 5, 8, and 8.06, respectively, at 40°C.

(Preparation of silver halide photographic material sample) EM-A, E
For each emulsion of M- to EM-D and EM-D
Optimal sulfur sensitization and spectral sensitization were carried out in the same manner as in Example-1, Sample-A1 Sample-A' to Sample-D, Sample = D'
was created.

For each sample, exposure, development, and fog/sensitivity measurements were performed in the same manner as in Example-1.

Table 4 shows the measurement results for green light.

Note that the relative fog is expressed as a value with the Dmin value of Sample-A being 100, and the relative sensitivity is expressed as a value with the sensitivity of Sample-A being 100.

Also, results similar to those shown in Table 4 were obtained in measurements using red light and blue light.

Table 1 As is clear from Tables 1 to 4, the silver halide emulsion of the present invention that has been treated with a gelling-resistant dispersion medium has a lower sensitivity than the comparative emulsion that is not subjected to this treatment. high and low fog.

Furthermore, the effects of the present invention are more pronounced when a coagulation method is used as the treatment with a dispersion medium that is difficult to remove and gel, and when a G agent is used as the treatment agent.

Furthermore, this is more noticeable in emulsions in which crystal growth is performed by supplying fine silver halide grains.

[Effects of the Invention] As described above, according to the silver halide emulsion of the present invention and the method for producing the same, it is possible to sufficiently reduce fog and increase sensitivity.

Claims (4)

[Claims] (1) In a silver halide emulsion consisting of a dispersion medium and photosensitive silver halide grains, gelation resistance in which part or all of the silver halide grains have protective colloidal properties during the nucleation and/or crystal growth process 1. A silver halide emulsion, which is treated in the presence of a dispersion medium and subjected to a gelling-resistant dispersion medium treatment after completion of crystal growth of the silver halide grains. (2) Part or all of the nucleation and/or crystal growth process of photosensitive silver halide grains in the silver halide emulsion is carried out in microscopic particles prepared in the presence of a gelling-resistant dispersion medium having protective colloidal properties. 2. The silver halide photographic emulsion according to claim 1, wherein the silver halide emulsion is produced by supplying a silver halide emulsion containing silver halide grains. (3) In a method for producing a photographic silver halide emulsion comprising a dispersion medium and photosensitive silver halide grains, a part or all of the nucleation and/or crystal growth process of the silver halide grains has protective colloidal properties. 1. A method for producing a silver halide photographic emulsion, which is carried out in the presence of a gelling-resistant dispersion medium, and is treated with a gelling-resistant dispersing medium after the crystal growth of the silver halide grains is completed. (4) Part or all of the nucleation and/or crystal growth process of photosensitive silver halide grains in a silver halide emulsion is carried out using microscopic particles prepared in the presence of a gelling-resistant dispersion medium having protective colloidal properties. 4. The method for producing a silver halide emulsion according to claim 3, wherein the method is carried out by supplying a silver halide emulsion containing silver halide grains.