JP2000241922A - Silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion having high sensitivity, high contrast and improved development stability and a silver halide photographic sensitive material using the silver halide emulsion. SOLUTION: In the silver halide emulsion, normal silver halide grains having >=10 dislocation lines 1 and <=30% coefficient of variation in the number of dislocation lines among the grains occupy >=50% of the number of all grains. In the silver halide emulsion, normal silver halide grains having >=10 dislocation lines 1 and the relation of I1<I2 between the average silver iodide content (I1) of the inside and the average silver iodide content (I2) of the outside including the dislocation line region preferably occupy >=50% of the number of all grains. The silver halide photographic sensitive material has at least one layer containing the photosensitive silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive silver halide emulsion containing normal crystal grains and a silver halide photographic light-sensitive material containing the emulsion. And a silver halide photographic light-sensitive material having improved gradation and development processing stability.

[0002]

2. Description of the Related Art In recent years, demands for silver halide emulsions for photography have become more and more intense.

US Pat. No. 4,434,226 discloses the use of tabular silver halide grains as a method for increasing the sensitivity of a silver halide emulsion, particularly as a method for increasing its quantum sensitivity.
Nos. 4,439,520 and 4,414,310
Nos. 4,433,048 and 4,414,306
No. 4,459,353, JP-A-58-11193.
No. 5, No. 58-111936, No. 58-111937
Nos. 58-113927 and 59-99433. As a method for further improving the sensitivity and granularity of a silver halide emulsion, a technique of introducing dislocation lines is generally known, and a technique of introducing dislocation lines into tabular silver halide grains is disclosed in US Pat. No. 4,956. , 269.

Although the above-described tabular grain technique is useful in achieving high sensitivity of silver halide grains, dislocation to silver halide grains having a high aspect ratio is required to take advantage of the properties of tabular grains. It has become clear that the introduction of a line may cause adverse effects such as deteriorating rather than deteriorating other photographic performance, for example, gradation and development processing stability.

On the other hand, JP-A-5-107670 and 4-
No. 31050, No. 5-53232, No. 4-3729
No. 43, No. 4-362628, and the like disclose a dislocation line introduction technique for normal crystal grains.

[0006] However, in the conventional normal crystal grain emulsion simply introducing dislocation lines, although the sensitivity is improved to some extent,
The stability of development processing, such as fluctuation of photographic performance with respect to gradation and development processing, cannot be said to be sufficient, and further improvement of these performances is desired.

The present inventors have conducted studies to further improve the photographic performance of the normal crystal grain emulsion into which dislocation lines have been introduced. Caused by uneven distribution among grains, high average silver iodide content in the portion inside dislocation lines in grains, and insufficient uniformity of crystal habit on the outer surface of grains. It was found that.

As a result of further intensive studies, it has been found that the sensitivity and gradation are improved by setting the intergranular variation coefficient of the number of dislocation lines to 30% or less, and the average silver iodide content in the grains is reduced inside the dislocation line region. The stability of development processing can be improved by lowering or making the inter-particle variation coefficient of (100) plane ratio of the outer surface of the particles 20% or less, and further, by combining these, sensitivity, gradation and development can be improved. It has been found that all of the processing stability can be improved, and the present invention has been accomplished.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion having high sensitivity and improved gradation or stability in development processing, and a photographic material using the same.

[0010]

The above object of the present invention is attained by the following constitutions.

(1) Normal crystal silver halide grains having 10 or more dislocation lines, and the coefficient of variation of the number of dislocation lines between normal crystal silver halide grains having 10 or more dislocation lines is 3
0% or less of silver halide grains is 50% of the total number of grains.
% Of a photosensitive silver halide emulsion.

(2) A normal-crystal silver halide grain having 10 or more dislocation lines, and the average silver iodide content inside the dislocation line region of the normal-crystal silver halide grain having 10 or more dislocation lines. Grains whose relationship between the ratio (I ₁ ) and the average silver iodide content (I ₂ ) on the outer side including the dislocation line region is I ₁ <I ₂ ;
A photosensitive silver halide emulsion having 50% or more of the total number of grains.

(3) It has 10 or more dislocation lines, and (10)
0) Normal-crystal silver halide grains having a plane ratio of 50% or more, having 10 or more dislocation lines, and (100) between normal-crystal silver halide grains having a (100) plane ratio of 50% or more. 1
00) A photosensitive silver halide emulsion in which silver halide grains having a coefficient of variation of the surface ratio of 20% or less are 50% or more of the total number of silver halide grains.

(4) It has 10 or more dislocation lines, and (1)
00) The coefficient of variation of the number of dislocation lines between normal crystal silver halide grains having an area ratio of 50% or more is 30% or less (3).
2. The photosensitive silver halide emulsion according to item 1.

(5) It has 10 or more dislocation lines, and (10)
0) A normal crystal silver halide grain having a face ratio of 50% or more, having 10 or more dislocation lines, and a dislocation line of a normal crystal silver halide grain having a (100) face ratio of 50% or more. The relationship between the average silver iodide content (I ₁ ) inside the region and the average silver iodide content (I ₂ ) outside the region including the dislocation line region is I ₁
<I ₂ and the coefficient of variation of the (100) plane ratio is 20
% Or less of the silver halide grains accounts for 50% of the total number of grains.
A photosensitive silver halide emulsion characterized by the above.

(6) At least one layer on the support,
A silver halide photographic material comprising the photosensitive silver halide emulsion according to any one of (1) to (5).

(7) At least one layer on the support,
A color-reversed silver halide photographic material containing the photosensitive silver halide emulsion according to any one of (1) to (5).

Hereinafter, this will be described in more detail.

The dislocation lines of the silver halide grains of the present invention are described, for example, in J. Am. F. Hamilton: Photo. Sc
i. Eng. 11 (1967), p. 57; Shio
Zawa: J.M. Soc. Photo. Sci. Japan
n 35 (1972), p. 213, that is, by a method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough.
The use of an electron microscope (200 kV) for a thickness of 25 μm allows more clear observation.

In the case of normal crystal grains, it is often difficult to observe the transmission of an electron beam due to the grain thickness. In such a case, as shown in FIG. With great care not to apply pressure, (100)
By cutting out a slice having a size of 0.25 μm or less in parallel with the plane and observing the slice, the presence or absence of dislocation lines can be confirmed.

The number of dislocation lines per normal crystal grain of the present invention is preferably 20 or more, and more preferably 30 or more. The number of dislocation lines per normal crystal grain referred to herein means that a flake having a thickness of 0.2 ± 0.05 μm including one (100) surface per cubic particle is cut out as described above. Is defined as the number of dislocation lines when observed from the (100) direction.

The standard deviation of the number of dislocation lines is σ, and the average value is α.
In this case, the interparticle variation coefficient K (%) is represented by the following equation.

K (%) = (σ / α) × 100 The silver halide grains of the present invention having a coefficient of variation of the number of dislocation lines are preferably achieved by the following method, but are not necessarily limited to them. is not.

The time required for introducing dislocation lines for preparing the normal crystal grains of the present invention depends on the uniformity of the number of dislocation lines.
The time from the start of iodide addition to the start of crystal growth of an external layer adjacent to the dislocation line is preferably within 10 minutes, more preferably within 5 minutes.

The pAg at the time of introducing dislocation lines is preferably less than 7.8 from the viewpoint of uniformity of the number of dislocation lines. In order to introduce dislocation lines uniformly, it is preferable that the crystal habit of the grains is uniform, and the coefficient of variation of the (100) plane ratio is preferably 20% or less.

The start of the introduction of dislocation lines is preferably 30 to 90%, more preferably 40 to 70% in terms of the amount of silver consumed for grain growth before the introduction of dislocation lines. .

There is no particular limitation on the method of introducing dislocation lines. However, at the start of dislocation line introduction, a layer containing high silver iodide is formed on the host grains, and further outside the layer, the iodide content is relatively high. A method of forming a silver halide layer having a low silver content, that is, a method of introducing dislocations using a gap of a silver halide lattice constant caused by a so-called steep halogen composition difference is preferable. As a method of forming a high silver iodide-containing layer,
A method of adding an aqueous iodide ion solution such as a potassium iodide aqueous solution and a water-soluble silver salt solution by double jet, a method of adding silver iodide fine particles, a method of adding only an iodide ion aqueous solution,
Although there is a method using an iodide ion releasing agent and the like, a method of adding fine silver iodide particles is most preferable.

When dislocation lines are introduced, the average silver iodide content (I ₂ ) outside the region including the dislocation line region is preferably 10 mol% or less, more preferably 5 mol% or less.

The outside including the dislocation line region in the present invention is a region defined as follows. That is, as described above, when a slice having a thickness of 0.25 μm or less is cut from a normal crystal grain, the silver halide grain of the present invention has a dislocation line normal to the surface from the grain center to the surface. Although observed, it refers to a region on the particle surface side from a boundary line formed by connecting the starting point of the group of dislocation lines on the particle center side between adjacent dislocation lines.

In a grain containing a dislocation line, a high iodine-containing phase having a different halide composition is clearly in contact with the starting point of the dislocation line on the grain center side, and is clearly different from the inner region by a transmission electron microscope. As observed in the image, the existence of the region is associated with the dislocation line forming operation, and is defined as included in the region “outside the dislocation line region” in the present invention.

The value of I ₂ -I ₁ is preferably at least 2 mol%, more preferably at least 3 mol%. The average silver iodide content of each silver halide grain is described in JP-A-60-25403.
It can be measured by a method using an X-ray microanalyzer as described in No. 2.

The silver halide emulsion of the present invention preferably has a silver chloride content of 5 mol% or less, and a silver iodide content of 0.5 mol% or more. More preferably, the silver iodide content is 1 to 5
Mol%.

The particle size of the silver halide grains is preferably from 0.1 to 1.2 μm, more preferably from 0.15 to 0.7 μm, based on the length of one side of a cube having the same volume.
The size distribution of the silver halide grains is the same volume of cube 1
The variation coefficient of the side length is preferably 15% or less, but is not necessarily a so-called monodispersed emulsion.

The intergranular distribution of the silver iodide content of the tabular grains of the present invention is obtained by dividing the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution by the average silver iodide content). Is preferably 20% or less, more preferably 10% or less.

The silver iodide content on the surface of the silver halide grains is 0.
To 15 mol%, more preferably 0.1 to 10 mol%.
Mol%. The silver iodide content on the grain surface in the present invention is a value measured by the XPS method described in JP-A-8-171157.

The "coefficient of intergranular variation in (100) plane ratio" of silver halide grains is determined by the following method.

The (100) plane ratio of each silver halide grain can be determined by depositing a metal from a diagonal direction of the grain (shadowing treatment), and then performing SEM (scanning electrification).
on Microscope (scanning electron microscope), and is obtained by image processing the observed image.

The present inventors have performed a shadowing treatment on the particles, and when the particles are observed from above by SEM using the shadow caused by the difference in the amount of adhering metal, the (100) plane and the non- (100) plane of the particles are obtained. Succeeded in distinguishing. The shadowing process is described in “Electron Microscope Sample Techniques”, Seibundo Shinkosha, 12
3, (1970), a method which has been conventionally used for shading silver halide grains in replica observation of the grains.

The procedure for measuring the (100) plane ratio is specifically as follows.

In order to extract silver halide grains from the silver halide emulsion used for the measurement, gelatin as a dispersion medium is decomposed with a protease under safelight, and the supernatant is removed by centrifugation and washed with distilled water. A method is generally used. When silver halide particles are present in a coating film containing gelatin as a main binder, gelatin may be similarly decomposed by a protease and the particles may be taken out, and when a polymer other than gelatin is contained. The polymer may be dissolved and removed using an appropriate organic solvent. When dyes, sensitizing dyes, and the like are adsorbed on the surface of the grains, they can be removed by appropriately using an alkaline aqueous solution, alcohol, or the like to obtain a clean silver halide grain surface. Particles dispersed in water are
It is used for measurement by coating and drying on a conductive substrate, but it is preferable to arrange the particles on the substrate without agglomeration. Observe the sample obtained by a series of procedures using an optical microscope or SEM. It is preferable to confirm. A dispersing aid may be used to prevent aggregation of the particles. Alternatively, a dispersion diluted with distilled water after being decomposed by a protease may be coated on a conductive substrate. Further, in order to arrange the particles on the substrate without agglomeration, a spin coater, a vacuum freeze dryer, or the like may be appropriately used. The conductive substrate is smooth,
It is preferable that a mirror-polished low-resistance silicon single crystal wafer having a resistivity of 1.0 Ω · cm or less be sufficiently washed and used. Further, a thin polyethylene terephthalate base obtained by thinly depositing carbon to impart conductivity may be used.

On the silver halide particles thus dispersed on the substrate, a metal is deposited from a direction of 45 ° with respect to the substrate. The metal to be deposited is generally Cr, Pt-Pd, or the like, but platinum carbon is preferred because of the granularity of the deposited film and the straightness in the deposition direction. If the metal deposition thickness is small, the contrast difference required for distinguishing the (100) plane and the non- (100) plane of the particles cannot be obtained in SEM observation. On the other hand, when the thickness is large, the measurement error increases, so that about 20 nm is preferable. The SEM used for observation increases the measurement accuracy.
Devices using as high a resolution as possible are preferred. The accelerating voltage of the electron beam is pointing upward in later image processing (100)
Observation was performed at 1.8 kV, at which a contrast difference that allows easy identification of the surface, the outer shape of the particles, and the substrate was obtained. In the observation, the particles were observed from just above without tilting the sample.

After the observation image is taken on a polaroid or negative film, it may be taken into a computer for image processing by a scanner. However, in order to suppress image deterioration at the time of taking the image, the SEM is connected to the computer for image processing, and online. Preferably, it is stored as a digital image. Impulse noise of the captured image was removed by a median filter using image processing software. afterwards,
The (100) plane facing upward and the contour of the particle were binarized using a “threshold” that allows image extraction, and a number was assigned to each particle, and the area of each was measured. The measured area of the (100) plane and the area within the contour of the particle are AS
Input to spreadsheet software in CII format, and (10
0) The area ratio was calculated.

The intergranular variation coefficient of the (100) plane ratio of the silver halide grains of the present invention is preferably 15% or less, more preferably 10% or less.

The standard deviation of the (100) plane ratio is given by σ
Assuming that the average value of the ₍₁₀₀₎ % and the (100) plane ratio is α ₍₁₀₀₎ %, the interparticle variation coefficient K (%) is expressed by the following equation.

K (%) = [σ ₍₁₀₀₎ / α ₍₁₀₀₎ ] × 100 Particularly, in a cubic silver halide grain containing dislocation lines, the variation coefficient of the (100) plane occupancy should be reduced. Is more preferred.

The (100) plane occupancy is preferably 50% or more, and more preferably 60 to 95% or less in terms of production stability.

As the method for producing the halogenated particles, methods known in the art can be appropriately combined. For example, JP-A Nos. 61-6643, 61-146305, 62-157024, 62-18556, and 63
-92942, 63-151618, 63-1
No. 63451, No. 63-220238, No. 63-31
For example, a known method such as that described in US Pat. For example, a double jet method, a double jet method, a so-called controlled double jet method for maintaining a constant pAg in a liquid phase in which silver halide is produced, which is one type of the double jet method, a soluble silver halide having a different composition, A triple jet method in which each is independently added can also be used.
A forward mixing method can be used, and a so-called reverse mixing method in which grains are formed in excess of silver ions can also be used. To control pAg (the logarithm of the reciprocal of silver ion concentration) in the liquid phase in which silver halide grains are formed in accordance with the growth rate of silver halide grains, it is necessary to obtain highly monodisperse grains. preferable. In determining the addition rate, JP-A-54-48521 and JP-A-58-4993 can be used.
The technology described in No. 8 can be referred to.

Further, a silver halide solvent can be used if necessary. Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. Nos. 3,271,157, 3,790,387, and 3,574,628 can be referred to.
The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used. However, in order to reduce fog of silver halide grains, a pH (hydrogen ion concentration Logarithmic value of the reciprocal of
Or less, more preferably 4.5 or less.

The silver halide grains having a variation coefficient of the (100) plane ratio of the present invention are preferably achieved by the following method, but are not necessarily limited thereto. The pAg for preparing the cubic particles of the present invention is preferably from 6.8 to 7.8 in view of the stability of the area ratio. In addition, a method of supplying iodine to a mixed solution for growing silver halide is important, and a method using silver iodide fine particles,
And a method using the above-mentioned iodide ion releasing agent (10
0) It is effective in reducing the variation coefficient of the surface ratio. This is considered to be an effect obtained by making the distribution of iodine ions in the mixing vessel uniform. In particular, this is important in preparing silver halide grains containing dislocation lines. Furthermore, in order to make the environment in the mixing vessel uniform, there are measures such as increasing the linear speed of stirring the solution in the mixing vessel or diluting the silver halide concentration of the solution in the mixing vessel. However, if the linear velocity of the stirring is too high, bubbles are generated and the production stability is deteriorated. Further, when the silver halide concentration of the solution is excessively diluted, the dislocation linear density is reduced. It is preferable that the stirring speed (the number of rotations) is so high that the liquid surface is observed and bubbles are not generated. The silver halide concentration is preferably 0 to 2 mol per 1 liter of solution immediately before the start of crystal growth, and 0.1 mol immediately after the completion of crystal growth.
1 to 5 mol is preferable, and 0 to 5 mol during crystal growth.
Molar or less is preferred.

Further, the silver halide grains of the present invention have a (10)
0) To reduce the coefficient of variation of the distribution of the surface ratio between particles,
The iodide ion is preferably supplied to the mixed solution using silver iodide fine particles or using an iodide ion releasing agent.

Examples of the iodide ion-releasing agent which can be used for preparing silver halide grains are shown below, but are not limited thereto.

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The silver halide grains are produced in the presence of a dispersion medium. Here, the term "in the presence of the dispersion medium" refers to a state in which the protective colloid is formed in a mixed solution in which the protective colloid grows with gelatin or another substance capable of forming a hydrophilic colloid, and preferably the presence of the colloidal protective gelatin. Do it below.

When gelatin is used as the protective colloid, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As hydrophilic colloids other than gelatin,
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. There are various kinds of synthetic hydrophilic polymer substances such as single or copolymer. In the case of gelatin, jelly strength 2
It is preferable to use one having a value of 00 or more.

The silver halide grains preferably contain a metal ion salt during grain formation, in a desalting step, during chemical sensitization, and before coating. For example, Mg, Ca, Sr, Ba, A
1, Sc, Y, La, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b, Bi, etc. can be used. These metals can be added in the form of ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, six-coordinate complex salts, four-coordinate complex salts, and the like. For example, Pb (NO ₃ ) ₂ , K ₂ Fe (CN) ₆ , K ₃ I
rCl ₆ , K ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like.

A chalcogen compound as described in US Pat. No. 3,772,031 can be added during the preparation of the emulsion.

The silver halide grains may be those obtained by removing unnecessary soluble salts after grain growth, or may be those containing them. Also, JP-A-60-13
As in the method described in No. 8538, desalting can be carried out at any point during silver halide growth. When removing the salts, use Research Disclosure (Rese
arch Disclosure (hereinafter abbreviated as RD)
No. 17643, page 23, section II. Specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method may be used in which gelatin is gelled, and inorganic salts, anionic surfactants, anionic surfactants Water-soluble polymer (polystyrenesulfonic acid, etc.) or gelatin derivative (acylated gelatin, carbamoylated gelatin, etc.)
May be used. Also, JP-A-8-22
Salt removal using an ultrafiltration membrane as described in No. 8468 can also be performed.

The silver halide emulsion may be subjected to reduction sensitization. Reduction sensitization is performed by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth.
Alternatively, it is carried out by ripening or growing a silver halide emulsion or a mixed solution for grain growth under a low pAg of 7 or less or a high pH condition of 7 or more. Further, these methods may be combined.

Also, JP-A-7-219093, 7-2
As shown in Japanese Patent No. 25438, reduction sensitization may be performed before or after the chemical sensitization step.

Further, reduction sensitization may be performed in the presence of the following oxidizing agents. In particular, it is preferable to perform reduction sensitization in the presence of the compounds represented by the following formulas (1) to (3).

Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salts. Other suitable reducing agents include borane compounds,
Examples include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 ^-2 per mol of silver halide.
Preferred is from 10 to 10 ^-8 mol.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3.

High pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

The method of adding the silver salt and the alkaline compound for reduction sensitization may be rush addition or addition over a certain period of time. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Also, the required amount may be added in several portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

In the silver halide emulsion of the present invention, an oxidizing agent for silver may be added during the production process. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts silver atoms by-produced in the process of forming silver halide grains into silver ions is effective. Here, the generated silver ion is
A water-soluble silver salt such as silver halide, silver sulfide or silver selenide may be formed, or a water-soluble silver salt such as silver nitrate may be formed.

The oxidizing agent for silver may be an inorganic substance or an organic substance. As inorganic oxidants, ozone,
Hydrogen peroxide and its adduct (NaBO ₂ .H ₂ O ₂ .3H _{2
O, 2NaCO 3 · 3H 2 O} 2, Na 4 P 2 O 7 · 2H 2 O 2,
_{2Na 2 SO 4 · H 2 O} 2 · H 2 O , etc.), peroxy acid salt _{(K 2 S 2 O 8,} K 2 C 2 O 6, K 4 P 2 O 8 , etc.), peroxy complex compound (K ₂ [ Ti (O ₂ ) OOCCOO] .3H ₂
O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O,
Na ₃ [VO (O ₂ ) (OOCCOO) ₂ .6H ₂ O]),
Permanganate (KMnO ₄ ), chromate (eg K ₂
Oxyacids such as Cr ₂ O ₇ , halogen elements such as iodine and bromine, perhalates (such as potassium periodate), salts of high-valent metals (such as potassium hexacyanoferric acid) and And thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (N-bromosuccinimide, chloramine T, chloramine B, etc.).
And the like.

Preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates and quinones, particularly preferably thiosulfonic acids represented by the following formulas (1) to (3): Most preferred are compounds of formula (1).

Formula (1) R ¹ -SO ₂ SM Formula (2) R ¹ -SO ₂ SR ² Formula (3) R ¹ SO ₂ SL _n SSO ₂ -R ^{3 In the} formula, R ¹ , R ² and R ³ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, and n represents 0 or 1. is there.

The amount of the oxidizing agent added is 10 ^-7 per mol of silver.
It is about 10 ^-1 mol, preferably 10 ^-6 to 10 ^-2 mol, more preferably 10 ^-5 to 10 ^-3 mol. The oxidizing agent is preferably added during grain formation, or before or during formation of a structure due to a difference in halogen composition. As the addition method, a usual method for adding an additive to a photographic emulsion, for example, a water-soluble compound is made into an aqueous solution of an appropriate concentration,
Compounds that are insoluble or poorly soluble in water are dissolved in water-miscible organic solvents (alcohols, glycols, ketones, esters, amides, etc.) that do not adversely affect photographic properties. Then, a method of adding as a solution or the like can be adopted.

The silver halide grains of the present invention can be subjected to chemical sensitization by a conventional method. That is, a chalcogen sensitization method using a compound having a chalcogen such as sulfur, selenium, tellurium, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination. The tabular grains of the present invention are preferably subjected to selenium sensitization. Preferred selenium sensitizers are described in JP-A-9-2.
No. 65145 or the like can be used.

The addition amount of the selenium compound is not uniform depending on the compound to be used, the type of silver halide emulsion, the conditions of chemical ripening, and the like.
In the range of 0 ^-8 to 10 ^-3 mol, 5 × 10 ^-8 to 1 × 10
A range of ^-4 moles is preferred.

Depending on the properties of the selenium compound to be used, the method of addition may be a method of dissolving in water or an organic solvent such as methanol, ethanol, ethyl acetate or the like alone or in a mixed solvent, a method of adding it by premixing with a gelatin solution, Alternatively, it is added at the time of chemical sensitization in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer as disclosed in JP-A-4-14039.

The pAg (logarithm of the reciprocal of silver ion concentration) during selenium sensitization is preferably 6.0 to 10.0, more preferably 6.5 to 9.5. The pH is preferably between 4 and 9, more preferably between 4.0 and 6.5.
It is. The temperature is preferably between 40 and 90C, more preferably between 45 and 85C.

For selenium sensitization, a sulfur sensitizer, a gold sensitizer, or both may be used in combination.

As the sulfur sensitizer, US Pat. No. 1,57
4,944, 2,410,689, 2,27
8,947, 2,728,668, 3,50
Nos. 1,313 and 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-55-450.
No. 16, 56-24937, JP-A-5-16513
No. 5, thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea; rhodanine Derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone are preferred. The addition amount of the sulfur sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but 1 × 1 per mol of silver halide.
It is preferably from 0 ^-4 to 1 × 10 ^-9 mol, more preferably from 1 × 10 ^-5 to 1 × 10 ^-8 mol.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate and the like, as well as thioureas, rhodanines, and gold complexes of other various compounds. The addition amount of the gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is from 1 × 10 ^-4 to 1 × 10 ^-9 mol per mol of silver halide. And more preferably 1 × 10 ⁻⁵ to 1 × 10
^-8 mol.

Other chemical sensitizers that can be used in combination include:
For example, US Patents 2,448,060 and 2,566
No. 245, No. 2,566,263, and the like, and salts of noble metals such as platinum, palladium, and rhodium.

These sensitizations can also be carried out in the presence of a silver halide solvent such as thiocyanate (such as ammonium thiocyanate or potassium thiocyanate) or tetrasubstituted thiourea (such as tetramethylthiourea).

The silver halide grains of the present invention may be of the surface latent image type or of the internal latent image type. JP 9
The particles may be shallow internal latent image type particles as described in JP-A-222684.

The silver halide used in the present invention is not particularly limited, and for example, RD30811
Those described in pages 9,993, section IA to page 995, section II can be used.

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization can be used. The additive used in such a process is RD17643,
Page 23, III to 24, VI-M, RD18716, 64
Pages 8 to 649 and RD308119, page 996 III-A
From page VI-M to page 1000.

Known photographic additives usable in the present invention are also described in RD17643, page 25, VIII-A to page 27.
Section XIII, RD18716, pages 650 to 651, RD30
8119, page 998, pages V to 1012, pages XXI-E, can be used.

Various couplers can be used in the present invention, and specific examples thereof are described in RD17643, page 25, VII-
Sections C to G, RD308119, page 1001 VII-C to G
It is described in the section.

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

In the present invention, the aforementioned RD 17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, 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 light-sensitive material is the same as that of 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 present invention can be applied to various color photographic materials represented 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. .

The light-sensitive material of the present invention can be obtained by using the above-mentioned RD 1764
3, 28-29, RD 18716, 647 and RD
By the usual method described in XIX at 308119,
It can be developed.

The silver halide emulsion of the present invention contains
It preferably contains a compound of the general formula [I], [II] or [III] described in JP-A-171157.

The light-sensitive material of the present invention includes, for example, the type / serial number, manufacturer name, emulsion No. Various information on photosensitive materials such as shooting date / time, aperture, exposure time, lighting conditions, filters used, weather, size of shooting frame, camera model, use of anamorphic lens, etc. Various information at the time; for example, the number of prints,
Various information required for printing, such as selection of a filter, preference of a customer's color, size of a trimming frame, etc .; similar various information obtained at the time of printing, and a magnetic recording layer for inputting customer information, etc. It may be provided.

This magnetic recording layer is preferably coated on the side opposite to the photographic component layer with respect to the support. The undercoat layer, the antistatic layer (conductive layer), and the magnetic recording layer are arranged in this order from the support side. Preferably, a sliding layer is formed.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . Methods for producing these magnetic powders are known, and they can be produced according to known methods.

The optical density of the magnetic recording layer is preferably small considering the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Corporation: Sakura densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

It is preferable that the amount of magnetization of the magnetic recording layer per 1 m ² of the photosensitive material be 3 × 10 ^-2 emu or more. The magnetization amount is measured by a sample vibration type magnetometer (VSM-
3) using an external magnetic field 10
After saturation once with 00 Oe, the external magnetic field is reduced to 0
Can be obtained by measuring the magnetic flux density (residual magnetic flux density) at the time of (1) and converting it to the volume of the transparent magnetic layer contained per 1 m ² of the photosensitive material. If the amount of magnetization per unit area of the transparent magnetic layer is less than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is preferably from 0.01 to 20 μm, more preferably from 0.05 to 15 μm, even more preferably from 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form a binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Further, it is necessary to adjust physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate-type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add nonmagnetic metal oxide particles, particularly alumina fine particles.

As the support of the photosensitive material, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film (TAC), cellulose diacetate film (DAC), polycarbonate film, polystyrene film, polyolefin Films and the like can be mentioned. In particular, JP-A Nos. 1-244446, 1-291248, 1-298350 and 2-8
No. 9045, No. 2-93641, No. 2-181749
No. 2-214852, 2-291135 and the like, using a high moisture content polyester as shown in,
Even if the support is thinned, the curl recovery property after the development processing is excellent.

The support preferably used in the present invention is PE
T and PEN. When these are used, the thickness is 50
It is preferably from 100 to 100 μm, particularly preferably from 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer or the undercoat layer, the same binder as that for the magnetic recording layer can be used.

It is preferable to coat a higher fatty acid ester, a higher fatty acid amide, a polyorganosiloxane, a liquid paraffin, a wax or the like as a sliding layer on the magnetic recording layer.

When the light-sensitive material of the present invention is a roll-shaped color light-sensitive material for photographing, not only the size of the camera and the patrone can be reduced, but also the resources can be saved, and the storage space for the developed negative film can be saved. , The film width is about 20 to 35 mm, preferably 20 to 35 mm.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² and preferably in the range of 400 to 600 mm ^2, the small format can be realized without deteriorating the image quality of the final photographic print, and the size of the patrone and the size of the camera can be reduced more than before. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 size 1: 1, half size 1: 1.4,135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the photosensitive material is used in the form of a roll, it is preferable that the photosensitive material be housed in a cartridge. The most common cartridge is the current one
This is a 35 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634, U.S. Pat. No. 4,221,479, and JP-A-1-231045.
Nos. 2-170156, 2-199451, 2-124564, 2-201441, and 2-2
No. 08584, No. 2-210346, No. 2-2114
No. 43, No. 2-214853, No. 2-264248
Nos. 3-37645, 3-37646, U.S. Pat. Nos. 4,846,418, 4,848,693, and 4,832,275 can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

The silver halide emulsion of the present invention is particularly effective in the development processing for reversal films.

[0115]

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 N-1 >> 250 ml of a 4N silver nitrate aqueous solution and potassium bromide-iodide were added to 500 ml of a 2.0% aqueous gelatin solution at 40 ° C. according to the method described in JP-A-50-45437. 250 ml of a potassium (KBr: KI molar ratio = 98: 2) aqueous solution was added to a solution of 35 by controlling the pAg to 9.0 and the pH to 2.0 by a controlled double jet method.
Minutes.

The pH of the resulting aqueous gelatin solution containing silver halide particles was adjusted to 5.5 with an aqueous calcium carbonate solution, and 364 ml of a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. as a precipitant, and magnesium sulfate as a polyvalent ion. 2
244 ml of 0% aqueous solution was added to cause coagulation, sedimentation by standing, and the supernatant was decanted.
0 ml was added and dispersed again. Magnesium sulfate 20
% Of an aqueous solution containing 28 g of ossein gelatin, and the mixture was dispersed at 40 ° C. for 40 minutes to obtain a seed emulsion N-1. .

As a result of observation with an electron microscope, this seed emulsion was a monodisperse emulsion having an average particle size of 0.093 μm.

<< Preparation of Silver Iodide Fine Particle Emulsion N-2 >> 0.0
To 5000 ml of a 6.0% by weight gelatin solution containing 6 mol of potassium iodide, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the fine particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

As a result of observation with an electron microscope, the average particle size of the silver iodide fine particles was about 0.05 μm.

<< Preparation of Emulsion Em-1 >> Emulsion Em-1 was prepared using the following solution.

(Solution Gr-1) 161.1 g of ossein gelatin 10% by weight methanol solution of surfactant (EO-1) 3.0 ml Seed emulsion N-1 97.7 ml Finished to 4.2 liters with distilled water EO -1: 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) (B-1) 3524.9 g of silver nitrate Finish up to 5.928 liters with distilled water (B-2) 2798.9 g of potassium bromide Potassium iodide 162.7 g Finished to 7.0 liter with distilled water (B-3) Potassium bromide 2915.5 g Finished to 7.0 liter with distilled water (B-4) Fine grain silver iodide emulsion N-2 376.1 g In a solution (Gr-1) stirred at 70 ° C., the solutions (B-1) and (B-2) were subjected to a controlled double jet method to obtain a pAg of 7.9 with a 1.75N potassium bromide solution. While maintaining the pH at 4.0 with an aqueous acetic acid solution, the mixture was supplied at an addition rate at which no new small particles were generated in the mixed solution. When 3.869 liters of the solution (B-1) was added, the addition of the solutions (B-1) and (B-2) was interrupted, and after stirring for 1 minute, the solution (B-4) was added for 2 minutes. The whole amount was added by rapid addition. Then, after stirring for 15 minutes, the solution (B-
1) Addition of (B-3) was started. PA with 1.75N potassium bromide solution until the addition of solution (B-1) is completed.
g of 7.7, and the pH was maintained at 4.0 with an acetic acid aqueous solution, while supplying the mixed solution at an addition rate at which no new small particles were generated. After the addition of the solution (B-1) was completed, a 3.5N potassium bromide solution was added, the pAg was adjusted to 9.1, and the mixture was stirred for 2 minutes. And then dispersed by adding gelatin,
At 40 ° C., the pH was adjusted to 5.80 and the pAg to 8.06. The emulsion thus obtained is designated as Em-1.

From the electron micrograph of the obtained silver halide grains, Em-1 was found to have an average cubic side length of 0.42 μm,
The cubic particles were shifted to a slightly tetrahedral shape with a variation coefficient of one side length of the cube of 16%.

<< Preparation of Emulsion Em-2 >> In the preparation of Emulsion Em-1, after adding the solution (B-4), the solution (B-
Emulsion Em-2 was prepared in the same manner as Em-1, except that the stirring time until the addition of 1) and (B-3) was started was 2 minutes.

Em-2 is an average value of the cubic side length of 0.42.
The particles were cubic particles having a μm size and a coefficient of variation of 15% of the length of one side of the cube shifted to a slightly tetrahedral shape.

<< Preparation of Emulsion Em-3 >> In the preparation of Emulsion Em-1, the pAg in the grain growth until the addition of the solution (B-4) was changed to 7.3, and the solution (B-4) was added. After that, the stirring time until the addition of the solutions (B-1) and (B-3) was started was set to 2 minutes, and p
Same as Em-1, except that Ag was changed to 7.9,
Emulsion Em-3 was prepared.

Em-3 is a mean value of a cubic side length of 0.42.
The particles were cubic particles having a μm of 13% and a variation coefficient of one side of the cube of 13%.

<< Preparation of Emulsion Em-4 >> In the preparation of Emulsion Em-3, the solution (B-5) was used in place of the solution (B-2) added before the addition of the solution (B-4). In the same manner as in Em-3 except that solution (B-2) was used instead of solution (B-3) added after addition of solution (B-4),
Emulsion Em-4 was prepared.

Em-4 is a cubic average value of one side length of 0.42.
It was a cubic particle having a μm of 1% length variation of a cube and a coefficient of variation of 15%.

(B-5) Potassium bromide 2857.2 g Potassium iodide 81.3 g Finish up to 7.0 liters with distilled water According to the method described in the present specification, 10 dislocation lines were obtained for emulsions Em-1 to Em-4. The number ratio of the normal crystal grains having the above (the number ratio of particles on 10 dislocation lines in Table 3), the coefficient of inter-particle variation of the number of dislocation lines (the coefficient of variation of the number of dislocation lines in Table 3),
Table 3 shows the results of measuring the intergranular variation coefficient of the (100) plane ratio of normal crystal grains having 10 or more dislocation lines and having a (100) plane ratio of 50% or more, together with the emulsions of Examples described later. Show.

In each of the emulsions, the normal crystal grains having 10 or more dislocation lines have a (100) plane ratio of 50%.
That was all. In Em-1 to 3, normal crystal grains having 10 or more dislocation lines satisfy I ₁ > I ₂ , and in Em-4, I ₁ <I ₂ and I ₂ −I ₁ Was in the range of 4.2 to 5.6 mol%.

Next, the following sensitizing dyes (S-1, S-2), potassium thiocyanate, chloroauric acid, sodium thiosulfate and triphenylphosphine selenide were added to the emulsions Em-1 to Em-4. According to the method, chemical sensitization was performed so that the fog-sensitivity relationship was optimized. Subsequently, the following stabilizer (ST-1) and antifoggant (AF-1,
AF-2) was added in an amount of 1 mol / mol silver halide.
g, 2 mg and 10 mg were added.

The following couplers (C-1) were added to the obtained emulsions.
And a general photographic additive such as a spreading agent and a hardening agent is added to prepare a coating solution. The solution is coated and dried on a cellulose triacetate support prepared in a conventional manner. Photosensitive material samples 101 to 104 were produced.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: 1- (4-carboxyphenyl) -5-mercaptotetrazole

[0135]

Embedded image

Each sample was passed through a Toshiba glass filter O-56 using a light source at 5400 ° K according to a conventional method to make 1/1.
Wedge exposure was performed for an exposure time of 00 seconds, and development processing was performed according to the following processing steps, and sensitivity, gradation, and development processing stability were evaluated.

<Sensitivity> The color density of the developed sample is 1.0
The sample 101 is obtained from the reciprocal of the exposure amount that gives the density
Is a relative value with the sensitivity of 100 as 100.

<Gradation (G)> This is a value obtained by subtracting 0.5 from the color density at 1/10 of the exposure amount at which the color density of the developed sample gives 0.5. This is a relative value set to 1. The larger the G, the harder the emulsion.

<Development Characteristics> The first of the following development processes
In the developing solution, to gradation G ₁ when 0.1% potassium iodide solution was added 2 ml, variation ratio of gray level G ₂ in the case of 10ml added _{ΔG (= G 2 / G 1} ) with a characteristic value Means that the closer the ΔG is to 1, the smaller the processing fluctuation and the more stable the processing.

<< Development Processing Step >> Processing Step Processing Time Processing Temperature First Development 4 minutes 38 ° C. Rinse 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color Development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleaching 6 minutes 38 C. Fixing 4 minutes 38.degree. C. Washing with water 4 minutes 38.degree. C. Stabilizing 1 minute Room temperature Drying The treatment liquid composition used in the above treatment step is as follows.

First developer solution Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to make up to 1000 ml. (PH 9.60) Reversal solution Nitrilotrimethylene phosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to make up to 1000 ml. (PH 5.75) Color developing solution Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Water was added to make up to 1000 cc. (PH 11.70) Conditioner Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added to complete 1000 ml. (PH 6.15) Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to make up to 1000 ml. (PH 5.56) Fixing solution 80 g of ammonium thiosulfate 5 g of sodium sulfite 5 g 5 g of sodium bisulfite Water was added to make up to 1000 ml. (PH 6.60) Stabilizing solution Formalin (37% by weight) 5 ml Konidax (manufactured by Konica Corporation) 5 ml Water was added to make up to 1000 ml. (PH 7.00) The results are shown in Table 1.

[0142]

[Table 1]

It is shown that the emulsion of the present invention can provide high sensitivity performance without impairing gradation. By making the silver iodide content outside the silver halide grains including the dislocation line region higher than that inside, the sensitivity and development processing stability are remarkably improved.

Example 2 << Preparation of Emulsion Em-5 >> In a solution (Gr-1) stirred at 70 ° C., solutions (B-1) and (B-6) were prepared by a controlled double jet method. While maintaining the pAg at 7.3 with a 1.75N potassium bromide solution and the pH at 4.0 with an aqueous acetic acid solution, the mixture was fed at an addition rate at which no new small particles were generated in the mixed solution. 3.86 of solution (B-1)
When 9 liters were added, the solutions (B-1) and (B-6)
Was stopped, and after stirring for 1 minute, the solution (B-4) was added at a constant rate over 2 minutes. Then, after stirring for 20 minutes, addition of the solutions (B-1) and (B-3) was started. Until the addition of the solution (B-1) is completed, new small particles are generated in the mixed solution while maintaining the pAg at 7.3 with a 1.75N potassium bromide solution and the pH at 4.0 with an acetic acid aqueous solution. Feed at no addition rate. After the addition of the solution (B-1) was completed, a 3.5N potassium bromide solution was added, and the pAg was changed to 9.1.
And stirred for 2 minutes.
Desalting is performed according to the method described in No. 58, and then gelatin is added to disperse the mixture.
g was adjusted to 8.06. The emulsion thus obtained was Em
-5.

From the electron micrograph of the obtained silver halide grains, Em-5 was found to have an average cubic side length of 0.42 μm,
Cubic particles having a coefficient of variation of one side length of a cube of 16% were obtained.

(B-6) Potassium bromide 2828.0 g Potassium iodide 122.0 g Make up to 7.0 liters with distilled water.

<< Preparation of Emulsion Em-6 >> In the preparation of Emulsion Em-5, the solution (B-4) was added after adding the solution (B-4).
Emulsion Em-6 was prepared in the same manner as Em-5, except that the stirring time until the addition of 1) and (B-3) was started was 2 minutes.

From the electron micrograph of the obtained silver halide grains, Em-6 was found to have an average cubic side length of 0.42 μm,
The particles were cubic shaped particles having a variation coefficient of one side of the cube of 13%.

<< Preparation of Emulsion Em-7 >> In the solution (Gr-1) stirred at 70 ° C., the solutions (B-7) and (B
-3) and silver iodide fine grain emulsion N-2 were newly formed in the mixed solution while maintaining the pAg at 7.3 with a 1.75N potassium bromide solution and the pH at 4.0 with an acetic acid aqueous solution. Feed was at an addition rate that did not occur. At this time, the amount of addition was adjusted such that the molar ratio of Br ions supplied from the solution (B-3) to iodine ions supplied from the emulsion N-2 was always 97: 3. When 3.756 liters of the solution (B-7) was added, the addition of the solutions (B-7) and (B-6) and the emulsion N-2 was stopped. After stirring for 1 minute, the solution (B-4) Was added at a constant speed for 2 minutes. Then, after stirring for 2 minutes, addition of the solutions (B-7) and (B-3) was started. At this time, the emulsion N-2 was not added. PA with 1.75N potassium bromide solution until addition of solution (B-7) is complete
g of 7.3, and the pH was maintained at 4.0 with an acetic acid aqueous solution, while supplying the mixed solution at an addition rate at which no new small particles were generated. After the addition of the solution (B-7) was completed, a 3.5N potassium bromide solution was added, the pAg was adjusted to 9.1, and the mixture was stirred for 2 minutes, and then desalted according to the method described in JP-A-5-72658. And then dispersed by adding gelatin,
At 40 ° C., the pH was adjusted to 5.80 and the pAg to 8.06. The emulsion thus obtained is designated as Em-7.

From the electron micrograph of the obtained silver halide grains, Em-7 was found to have an average cubic side length of 0.42 μm,
The particles were cubic shaped particles having a variation coefficient of one side of the cube of 11%.

(B-7) Silver nitrate 3455.9 g Finish up to 5.812 liters with distilled water.

<< Preparation of Emulsion Em-8 >> In the solution (Gr-1) stirred at 70 ° C., the solutions (B-8) and (B
-3) and silver iodide fine grain emulsion N-2 were newly formed in the mixed solution while maintaining the pAg at 7.3 with a 1.75N potassium bromide solution and the pH at 4.0 with an acetic acid aqueous solution. Feed was at an addition rate that did not occur. At this time, the addition amount was adjusted such that the molar ratio of Br ions supplied from the solution (B-3) to iodine ions supplied from the emulsion N-2 was always 98: 2. When 3.794 liters of the solution (B-8) was added, the addition of the solutions (B-8) and (B-3) and the emulsion N-2 was interrupted, and the mixture was stirred for 1 minute. Was added at a constant speed for 2 minutes. Then, after stirring for 2 minutes, addition of the solutions (B-8) and (B-3) and the emulsion N-2 was started. At this time, Br supplied from the solution (B-3)
The addition amount was adjusted such that the molar ratio of ions to iodine ions supplied from the emulsion N-2 was always 98: 2. Until the addition of the solution (B-8) is completed, new small particles are generated in the mixed solution while maintaining the pAg at 7.3 with a 1.75N potassium bromide solution and the pH at 4.0 with an acetic acid aqueous solution. Feed at no addition rate. 3.5 after the completion of the addition of the solution (B-8)
An N potassium bromide solution was added, the pAg was adjusted to 9.1, and the mixture was stirred for 2 minutes, then subjected to a desalting treatment according to the method described in JP-A-5-72658, and then dispersed by adding gelatin. At 40 ° C., the pH is 5.80 and the pAg is 8.
06. The emulsion thus obtained is named Em-8.

From the electron micrograph of the obtained silver halide grains, Em-8 was found to have an average cubic side length of 0.42 μm,
Cubic particles having a coefficient of variation of 9% for one side length of the cube.

(B-8) 3454.4 g of silver nitrate Finished up to 5.809 liters with distilled water.

Emulsions Em-5 to 8-8 were also prepared in
Each characteristic was measured in the same manner as described above. The results are shown in Table 3.

In each emulsion, all the normal crystal grains having 10 or more dislocation lines have a (100) plane ratio of 50%.
That was all. Further, in Em-5 to 8, the normal crystal grains having 10 or more dislocation lines satisfy I ₁ > I ₂ , and in Em-8, I ₁ <I ₂ and I ₂ −I ₁ Was in the range of 2.2 to 3.6 mol%.

Next, sensitizing dyes (S-3, S-4), potassium thiocyanate, chloroauric acid, sodium thiosulfate, and triphenylphosphine selenide were added to emulsions Em-1 and Em-5 to 8-8. And fog according to a conventional method.
Chemical sensitization was performed to optimize the sensitivity relationship. Subsequently, a stabilizer (ST-1) and an antifoggant (A
F-1, AF-2) were added in an amount of 1 g, 2 mg, and 10 mg, respectively, per mol of silver halide. A dispersion of the coupler (M-1) was added to each of the obtained emulsions, and a general photographic additive such as a spreading agent and a hardener was further added to prepare a coating solution.
Samples 201 to 205 were prepared by applying and drying each coating solution on a subbed cellulose triacetate support by a conventional method.

[0158]

Embedded image

These samples were subjected to 5400 ° K
Wedge exposure was performed with a light source of No. 1 through a Toshiba glass filter Y-48 for an exposure time of 1/100 second, and development processing was performed in the same manner as in Example 1 to evaluate sensitivity, gradation, and development processing stability. However, the processing time of the first developer is 5
Minutes. The sensitivity of the sample 201 is represented by a relative value where the sensitivity is 100 and the gradation is 1.

The results are shown in Table 2.

[0161]

[Table 2]

All of the emulsions of the present invention have little gradation fluctuation during processing fluctuation. In addition, by improving the dislocation line variation coefficient, sensitivity,
By improving the gradation and further increasing the silver iodide content on the outer side, the development processing stability is improved.

In addition to the results of Example 1, the emulsion of the present invention
It can be seen that the effect is particularly large when the variation coefficient of the number of dislocation lines and the variation coefficient between grains of the (100) plane ratio are small, that is, when the monodispersity of each is improved.

Emulsions Em-1 to E prepared in Examples 1 and 2
Table 3 summarizes characteristic values relating to the dislocation line of m-8 and the (100) plane ratio.

[0165]

[Table 3]

Example 3 In the preparation of Em-6 of Example 2, instead of the solution (B-4), the iodide ion releasing compound (5
A silver halide emulsion was prepared using 8) to obtain Em-9.

From the electron micrograph of the silver halide grains,
Em-9: Cube 1 side length average value 0.42 μm, Cube 1
The coefficient of variation of the side length is 13%, the number ratio of normal crystal grains having 10 or more dislocation lines is 79%, the variation coefficient of the number of dislocation lines between grains is 17%, and the ratio of (100) plane having 10 or more dislocation lines is Cubic particles having a coefficient of inter-particle variation of 20% of the (100) plane ratio of normal crystal particles of 50% or more.

The normal crystal grains having 10 or more dislocation lines have a (100) plane ratio of 50% or more, and the normal crystal grains having 10 or more dislocation lines have I ₁ > I _2. Met.

When the performance of Em-9 was evaluated in the same manner as in Example 2, the performance was as high as that of Em-6.

[0170]

The silver halide emulsion according to the present invention and the silver halide photographic light-sensitive material using the same have high sensitivity, high contrast, and excellent stability against fluctuations in development processing.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing the direction in which a normal crystal silver halide grain of the present invention is cut into thin slices for observing the number of dislocation lines in the electron microscope.

FIG. 2 is a schematic diagram showing a dislocation line image when the cubic silver halide grains of the present invention are observed with an electron microscope. (A) shows the case where the dislocation line exists on the entire surface, and (b) shows the case where the dislocation line exists only on a part of the surface. The area covered by the hatch,
The term “inside the dislocation line region” as used in the present invention, and the other region indicates “outside including the dislocation line region”.

[Explanation of symbols]

 1 Dislocation line image 2 Boundary line connecting the origins of dislocation lines on the particle center side

Claims (7)

[Claims] 1. A normal-crystal silver halide grain having 10 or more dislocation lines, wherein the coefficient of variation of the number of dislocation lines between normal-crystal silver halide grains having 10 or more dislocation lines is 30%.
A photosensitive silver halide emulsion, wherein the following silver halide grains account for 50% or more of the total number of grains. 2. An average silver iodide content of a normal crystal silver halide grain having 10 or more dislocation lines, wherein the average silver iodide content is inside a dislocation line region of the normal crystal silver halide grain having 10 or more dislocation lines. The grain whose relation between (I ₁ ) and the average silver iodide content (I ₂ ) including the dislocation line region is I ₁ <I ₂ is 50% or more of the total number of grains. Photosensitive silver halide emulsion. 3. Normal grain silver halide grains having 10 or more dislocation lines and a (100) plane ratio of 50% or more, and having 10 or more dislocation lines and a (100) plane ratio. Is 5
0% or more between normal crystal silver halide grains (100)
A light-sensitive silver halide emulsion, wherein silver halide grains having an area ratio variation coefficient of 20% or less are 50% or more of the total number of silver halide grains. 4. The method according to claim 1, wherein the dislocation lines have 10 or more
0) The photosensitive silver halide emulsion according to claim 3, wherein the coefficient of variation of the number of dislocation lines between normal crystal silver halide grains having an area ratio of 50% or more is 30% or less. 5. A normal crystal silver halide grain having 10 or more dislocation lines and a (100) plane ratio of 50% or more, and having 10 or more dislocation lines and a (100) plane ratio Is 5
Relationship between average silver iodide content (I ₁ ) inside the dislocation line region of normal crystal silver halide grains of 0% or more and average silver iodide content (I ₂ ) outside the region including the dislocation line region Is I ₁ <I ₂
And silver halide grains having a coefficient of variation of the (100) plane ratio of not more than 20% are not less than 50% of the total number of grains. 6. The method according to claim 1, wherein at least one layer on the support is provided.
A silver halide photographic material comprising the photosensitive silver halide emulsion of any one of claims 1 to 5. 7. The method according to claim 1, wherein at least one layer on the support comprises:
6. A color-reversed silver halide photographic material comprising the photosensitive silver halide emulsion according to any one of claims 1 to 5.