JPH03211543A - Silver halide photographic sensitive material improved in sensitivity and reciprocity law failure - Google Patents

Abstract

PURPOSE:To improve a reciprocity law failure without inducing desensitization by incorporating a specific emulsion which contains monodisperse emulsion particles having <5 ratio of diameter/thickness and has <1.5 deg. diffraction angle in diffraction ray width. CONSTITUTION:Over 50% of the total projection area of the monodisperse emulsion particles is occupied by the silver halide twin particles having <5 ratio of particle diameter/particle thickness. The (420) X-ray diffraction signal with a CuKa ray as a ray source has only the peak and the diffraction ray width at the max. peak height X 0.13 is <1.5 deg. at the diffraction angle (2theta). In addition, the silver halide photographic emulsion which mainly contains the silver iodobromide particles having a high silver iodide content in the particles and having a low silver iodide content phase on the particle surface and is further added with iodide ions at 10<-5> to 10<-1>mol per 1mol silver halide is incorporated into the above-mentioned photosensitive material. The reciprocity law failure relating to illuminance is improved without entailing the desensitization in this way.

Description

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

[Background of the invention]

Silver halide photographic materials are usually image-wise exposed and then developed to form a negative or positive image.

During image exposure of silver halide photographic materials, the aperture, exposure time, and filter of the camera are adjusted depending on the brightness of the subject or the purpose of image creation, and the illuminance and exposure time that the silver halide photographic material receives is adjusted accordingly. Generally, it is not constant.

For example, in the case of color negative film or color reversal film, which are commonly used for photography, the speed is around 1/60 seconds to 1/250 seconds for everyday snapshots, but 10 seconds for photographing high-speed objects or bright subjects. -" seconds to 101 seconds; conversely, when photographing a dark subject for a long time, such as in astrophotography, the exposure time ranges from several tens of minutes to several hours.

In general, silver halide photosensitive materials have different sensitivities depending on the illuminance and exposure time even if the amount of exposure is the same. This is what is called reciprocity failure, and it is common for sensitivity to decrease in the case of high-intensity short-time exposure or in the case of low-intensity long-time exposure.

Therefore, setting of photographing conditions becomes complicated and requires a long time, which reduces work efficiency, which is undesirable.

In order to improve this drawback, efforts have been made to dope silver halide grains with polyvalent metal ions, to select and combine the types of sensitizing dyes, and to adjust chemical sensitization.

In both cases, reciprocity failure related to illuminance is improved, but there is also desensitization, and further improvements are required.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide photographic material with improved reciprocity failure without causing desensitization.

[Structure and Effects of the Invention] The object of the present invention is to provide a silver halide photographic emulsion for use in a photographic light-sensitive material that: (1) 50% of the total projected area of the emulsion grains;
% or more is provided by silver halide twinned grains with a grain diameter/grain thickness ratio of less than 5, and (2) the emulsion grains are monodisperse, and (3) CuKa radiation is used as the radiation source (
420) The X-ray diffraction signal has only one peak and the highest peak height XQ.

(4) has a high silver iodide content phase inside the grain and a low silver iodide content phase on the grain surface; It mainly contains silver iodobromide grains, and furthermore (5) the emulsion having the above structure contains 1 rtro (lo- iodide ion per liter) of silver halide.
This is achieved by a silver halide photographic light-sensitive material characterized in that it contains a silver halide photographic emulsion to which 6 to 104 of 2 are added.

The present invention will be explained in more detail below.

The term "twin" refers to a silver halide crystal that has one or more twin planes within one grain, but the classification of twin crystal morphology is based on the paper by Klein and Moyser, Photographische Korres.
pondenz) Volume 99, page 99, Volume 100, 57
It is detailed on page. Two or more twin planes of a twin may or may not be parallel to each other. The twin plane is
Although it can be observed directly with an electron microscope, it is also possible to disperse silver halide grains in a resin and solidify it, and then observe it from the cross section as an ultrathin section sample.

The silver halide twin grains of the present invention preferably have two or more parallel twin planes, more preferably an even number of twin planes, particularly preferably two twin planes. .

In the present invention, "consisting mainly of twins having two or more parallel twin planes" means that the number of twin grains having two or more parallel twin planes is counted from large grains. 5
0% or more, preferably 60% or more, particularly preferably 70%
% or more.

The silver halide emulsion according to the present invention is composed of silver halide twin grains having a projected area of 50% or more or a grain diameter/grain thickness ratio of less than 5, preferably 7 of the projected area.
It is 0% or more, particularly preferably 90% or more. Further, the ratio of particle diameter/particle thickness is preferably 1.0 to 45, particularly preferably 1.1 to 4.0. The particle size here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The projected area of a particle can be determined from the sum of the particle areas. Both can be obtained by observing with an electron microscope a silver halide crystal sample distributed on a sample stage to such an extent that grains do not overlap. The thickness of the particles can be obtained by obliquely observing the sample using an electron microscope.

In the present invention, the particles consisting of twins have a ratio of twin particles to the whole particle of 60% or more, preferably 8% or more in terms of number.
It is 0% or more, particularly preferably 95 to 100%.

In the present invention, the silver iodobromide emulsion grain group consisting mainly of twins is monodisperse, but in the present invention, a monodisperse silver halide emulsion is defined as a grain size with a grain size of ±20% around the average grain size d. The silver halide weight within this range is 70% or more of the total silver halide weight, preferably 80% or more, and more preferably 90% or more.

Here, the average particle size d is the frequency n 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)
As mentioned above, the particle size referred to here is the diameter when the projected image of the particle is converted into a circular image of the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of particles to be measured is assumed to be 1000 or more indiscriminately.

) Preferred highly monodisperse emulsions of the present invention have a distribution breadth defined by 20% or less, more preferably 15% or less, particularly preferably 12% or less.

The grain size measurement method here follows the measurement method described above, but X-ray diffraction is known as a method for investigating the structure of silver halide crystals.

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

Silver iodobromide has a rock salt structure and has a (420)
Diffraction lines are observed at 2θ; 71 to 74 degrees. Since the signal intensity is relatively strong and the angle is wide, the resolution is good and it is ideal for investigating crystal structures.

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

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

The silver iodobromide emulsion mainly composed of twin crystals according to the present invention is composed of C
It is characterized in that the diffraction line width is less than 1.5 degrees at the diffraction angle (2θ) at the highest peak height Xo, 13 of the (420) . More preferably, the diffraction line width is less than 1.0 degrees, particularly preferably 0.90 degrees or less.

The presence of a signal means that the signal intensity is greater than or equal to the highest peak height x 0.13. The curved diffraction signal of the silver halide emulsion according to the present invention has only one peak. When counting the number of peaks, measurement noise and peaks less than 4% of the highest peak height shall not be counted.

The silver halide emulsion according to the present invention has the highest peak height x 0 of the (420) X-ray diffraction signal using the CuKc line as the radiation source.
．． 13, the line segment where the horizontally drawn line is cut by the signal is AA', and the intersection point with the line drawn vertically from the highest peak position is B, then the length of the line segment BA' is the length of the line segment AB. It is preferable that the ratio is 1.0 or less. Here, it is assumed that the line segment AA' is drawn from the narrow angle side of the diffraction angle to the li side. Further, the ratio of the length of line segment AB to the length of line segment BA' is more preferably 0.95 or less, particularly preferably 0.60 to 0.90.

The silver halide twin grains according to the present invention have (111) planes and (
100) It is preferable to have both planes, and 2 on the particle surface.
0% or more is (100) plane, more preferably 30%
Particularly preferably 40 to 70% of the above is (1,00) plane. It is preferable that the planes other than the (100) plane are mainly (111) planes.

The ratio of the (100) plane to the (111) plane is the signal intensity of the (200 plane, (222) plane, and (220) plane of a sample in which silver halide grains are distributed so as not to overlap on a flat sample stage. ratio and (200) plane in powder sample and (
It can be determined by comparing the ratio of one signal of the 222) plane and the (220) plane.

The silver halide emulsion of the present invention has an average silver iodide content of 6.
Preferably less than mol%, more preferably 0
~5 mol%, particularly preferably 1-4 mol%.

Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

The silver halide emulsion of the present invention can be obtained by localizing silver iodide within grains. A preferred embodiment is one in which silver iodobromide having a lower silver iodide content is deposited in a layered structure on an inner core having a higher silver iodide content.

The silver iodide content of the inner core is preferably 18 to 45 mol%. Particularly preferably 25 to 40 mol%.

It is preferable that the difference in silver iodide content between the outermost shell and the inner core is 10 mol% or more, and particularly preferably,
The difference is 20 mol% or more, particularly preferably 30 to 40 mol% or more.

In the above embodiment, another silver halide phase may be present at the center of the inner core or between the inner core and the outermost shell.

The volume of the outermost shell is preferably 10 to 90 mol%, more preferably 50 to 80 mol%, of the entire particle. The inner core, the outermost shell, and other silver halide phases may have a uniform composition, or may be a phase group consisting of multiple phases with a uniform composition and whose composition changes in a stepwise manner, Alternatively, it may be a continuous phase in which the composition changes continuously within the phase, or a combination thereof.

In the case of the continuously changing embodiment, it is preferable that the silver iodide content decreases monotonically from the point where the silver iodide content within the grain is maximum toward the outer side of the grain.

The silver iodide content at the point where the silver iodide content is maximum is preferably 15 to 45 mol%, more preferably 2
It is 5 to 40 mol%.

Further, the silver iodide content on the grain surface is preferably 3 mol% or less, more preferably 0 to 2 mol%, particularly preferably 0.1 to 1.0 mol% of silver iodobromide. .

The silver iodide content on the grain surface can be confirmed by X-ray photoelectron spectroscopy (so-called xPS method).

In the present invention, per mole of silver halide consisting of the surface-low silver iodide type twin grains, 10-5 to 10" moles, or 10-5 to 10" moles, particularly preferably 5X
10-5 to 5 X 10-' moles of iodide ions are added. When adding iodide ions, it is preferable to add them in the form of an aqueous solution of water-soluble iodide, such as potassium iodide or sodium iodide.

Addition of iodide ions a1: 35°C or higher, preferably 40°C or higher, particularly preferably 50°C or higher and 60°C
Added below.

Iodide ions may be added after the silver halide grains are formed and before being coated on the support, but preferably after the desalting step after grain formation, during chemical sensitization and spectroscopy. It is added until sensitization is completed.

As a method for obtaining the silver halide emulsion of the present invention, a method in which silver iodobromide or a silver bromide-containing phase is precipitated on monodisperse seed crystals is preferably used. Particularly preferred is the method described in JP-A No. 61-6643, which includes a growth step for enlarging a monodisperse spherical twin seed emulsion. Specifically, in a method for producing a silver halide photographic emulsion, which is carried out by supplying a water-soluble silver salt solution and a water-soluble halide solution in the presence of a protective colloid, (a) a silver iodide content of 0 to 5 mol%; For a period of at least 1/2 from the beginning of silver halogenide precipitate formation, the pBr of the mother liquor was reduced to 2.
A core particle generation step is provided in which the temperature is maintained at 0 to -0.7, and (b) the mother liquor I co-silver halide solvent is contained in the mother liquor I co-silver halide solvent at lo-5 to 2.0 moles per mole of silver halide. ,
A seed grain formation step is provided to form silver halide seed grains that are substantially monodisperse spherical twins; In addition, a method that includes a growth step for enlarging the seed particles is preferably used.

Here, the mother liquor is a liquid (also containing a silver halide emulsion) used for preparing a silver halide emulsion to produce a finished photographic emulsion.

The silver halide grains formed in the core grain generation step are twin grains made of silver iodobromide containing 0 to 5 mol % of silver iodide.

The term "twin" here refers to a silver halide crystal that has one or more twin planes within one grain, but two or more twin planes of a twin may or may not be parallel to each other. You can.

Also, the outer wall of the crystal consists of (Ill) planes, (100
) or both sides.

In the present invention, the twin core particles are produced by controlling the bromide ion concentration in the protective colloid aqueous solution from 0.01 to 5 mol/Q, that is, pBr=2.0 to
-0.7, preferably 0.03 to 5 mol/Q (p
B r = 1.5-0.7), and adding a water-soluble silver salt or a water-soluble silver salt and a water-soluble halide.

The nuclear particle generation step in the present invention refers not only to the period from the time when water-soluble silver salt is added to the protective colloid solution until substantially no new crystal nuclei are generated, but also the period after which the particles grow. It is defined as a step before the seed particle forming step.

In the present invention, the size distribution of the core particles is not limited and may be monodisperse or polydisperse. Polydispersity here refers to particles having a coefficient of variation (synonymous with the above-mentioned width of distribution) of 25% or more. The core particles of the present invention preferably contain at least 50% or more of twin grains, more preferably 70% or more, and most preferably 90% of the total number of core particles.

Next, a description will be given of a seed grain formation step in which the core grains obtained in the core grain generation step are ripened in the presence of a silver halide solvent to obtain seed grains consisting of monodisperse spherical grains.

Ripening in the presence of a silver halide solvent (hereinafter simply referred to as ripening) is thought to generally lead to a broader grain size distribution, with the small grains dissolving and the larger grains growing when large and small grains coexist. This seems to be different from the Ostwald ripening that has been described. The conditions for ripening the seed grains from the core grains obtained in the core grain generation step include the core grain generation step in which twin core grains are produced using silver halide with a silver iodide content of 0 to 5 mol%. Substantially monodisperse spherical seed grains are obtained by ripening the emulsion mother liquor that has undergone the process in the presence of a silver halide solvent of 10@-5 to 2.0 moles/silver mole. Substantially monodisperse means that the width of the distribution as defined above is less than 25%.

In addition, substantially spherical grains are defined as having a (l1l) plane or a (11
00) When a surface such as a surface is rounded to the extent that it cannot be clearly distinguished, and three-dimensional axes that are perpendicular to each other are set at one point near the center of gravity within the particle, the vertical, horizontal, and height of the plane image of the particle The maximum particle in the direction preferably refers to a particle in the range of 1.0 to 1.5.

In addition, in the present invention, the spherical particles account for 60? of the total number of seed particles. o
It is preferable that it accounts for at least 80%, more preferably, most of it.

The halogenated solvent used in the seed particle forming step of the present invention includes (a) U.S. Pat.
, 531,289, 3,574,628, JP-A-54-1019, JP-A-54-158917, and JP-B-Sho 58-30571;
(b) JP-A-53-82408'-]5. 55-29
Thiourea derivatives described in No. 829 and No. 55-77737, etc., (c) AgX solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A No. 53-144319. , (d) JP-A-54-1
Imidazoles, (e) sulfites, (f) thionanates, (g) ammonia, (
h) hydroxyalkyl-substituted ethylenediamines described in JP-A No. 57-196228, (i) substituted mercaptotetrazoles described in JP-A-57-202531, (j) water-soluble bromide, (k) Japanese Unexamined Patent Publication 1983
Examples include benzimidazole derivatives described in No.-54333.

Next, HO of these silver halide solvents (a) to (k)
CH, CHXSCH, CH, SCH□CH, 0HCHz
NHCOC1bCHxCOOH CB, SCH, C)1. SC, H5 CI(zNHcOcsHr CH25CI'l 2 CM 25C) 12 CH2C
00H (e') K2SOs, KalSOx (f) NH,SCN, KSCN (g) NH.

(h) (HOCH*GHz)zNcHzcHxNccHxcH
zOH)z(CzHs)zNcHtc)IJ(CHxC
)ItOH)x(j)NaBr, N)I4Br, KBr Two or more of these solvents can be used in combination.

Preferred solvents include thioethers, thionanates, thioureas, ammonia, and bromides, particularly preferably a combination of ammonia and bromide.

These solvents contain from 10-5 to 1 mole of silver halide.
It is used in a range of 2 moles.

Also, the pH is 3 to 13.8 degrees, which is 30 to 70 degrees.
C is preferred, particularly preferably pH 6 to 12, temperature 35
~50°C.

One example of a preferred embodiment of the present invention is pH 10,
8-11.2, ammonia 0.4 at a temperature of 35-45 °C
An emulsion containing suitable seed grains was obtained by using a combination of ~1.0 mol/12 and potassium bromide 0.03-0.5 mol/C and ripening for 30 seconds to IO minutes.

A water-soluble silver salt may be added for the purpose of adjusting ripening during the seed particle forming step of the present invention.

The seed grain growth process that enlarges the silver halide seed grains includes pAg during silver halide precipitation, Ostwald ripening,
pH 1 is achieved by controlling the temperature, the concentration and silver halide composition of the silver halide solvent, and the rate of addition of the silver salt and halide solution.

The conditions for enlarging the seed particles obtained in the present invention are as follows:
As seen in No. 49938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the addition rate is adjusted according to the enlargement of the particles so that new nucleation does not occur.
One method is to gradually change the temperature within a range that does not cause Ostwald ripening. As another condition for enlarging the seed grains, a method of enlarging the seed grains by adding silver halide fine grains, dissolving and recrystallizing can be used, as shown in the Proceedings of the 1988 Annual Conference of the Photographic Society of Japan, page 88, but the former The method is preferred.

In producing the silver halide emulsion according to the present invention, the growth conditions for silver halide grains are preferably pAg 5-11, temperature 40-85 DEG 0%, pH 1.5-5.8.

The pH is particularly preferably 1.8 to 3.5. l) Ag
The temperature is particularly preferably 6.0 to 9.5, and the temperature is 60 to 9.5.
Particularly preferred is 80°C.

During growth, it is preferable to add a silver nitrate aqueous solution and a halide aqueous solution by a double jet method. or,
It can also be supplied into the system as silver iodide. The addition rate is preferably such that new nuclei are not generated and the size distribution does not widen due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

The concentration of the silver nitrate aqueous solution used during the growth of the high silver iodide content phase (inner core) in the center of the silver halide emulsion according to the present invention is preferably IN or less, particularly preferably 0.3 to 0.8N.

In producing the silver halide emulsion of the present invention, stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which an additive liquid nozzle is installed in the liquid near the mother liquor inlet of the stirrer, is particularly preferably used. Also, at this time, the stirring rotation speed is 400 to 1
It is preferable to set it to 20 Orpm.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The present invention is preferably used for color photosensitive materials such as X-ray films, color negatives, and color reversals. In particular, it is preferably used in color reversal light-sensitive materials having at least one blue-sensitive layer, one green-sensitive layer, and one red-sensitive layer on a support.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

In addition, by coupling with a colored coupler having a correcting effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent can be obtained. , antifoggant ζ chemical sensitizer,
Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an anti-ration layer, and an anti-irradiation layer. These layers and/or emulsion layers may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Photosensitive materials include formalin scavengers, optical brighteners,
A matting agent, a lubricant, an image stabilizer, a surfactant, a color cast inhibitor, a development accelerator, a development retardant, and a bleach accelerator can be added.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

(Preparation of spherical seed emulsion N) A monodisperse spherical seed emulsion was prepared by the method disclosed in JP-A-61-6643.

Dl Ammonia water (28%) 705
Add B1 solution and C to solution A and solution stirred vigorously at 40°C.
1 liquid was added in 30 seconds using a double jet method to generate nuclei. The pBr at this time was 1,09 to 1.15.

After 1 minute and 30 seconds, liquid D1 was added for 20 seconds and aged for 5 minutes. The KBr concentration during aging was 0.071 mol/Q1 ammonia concentration was 0.63 mol/12.

Thereafter, the pH was adjusted to 6.0, and the solution was immediately desalted and washed with water. When this seed emulsion was observed under an electron microscope, the average grain size was 0.
．． It was a monodisperse spherical emulsion with a 36 μm distribution width of 18%.

Comparative Example 1 A tabular comparative emulsion Em-A having an average silver iodide content of 1.93 mol % was prepared using the seed emulsion N described above.

Two liquids B and C2 were added over 40.5 minutes to A2, which was vigorously stirred at 65°C, by a double jet method. During this time, the pH was maintained at 2.0 and the pAg at 9.0 with nitric acid throughout.

The addition rate of B2 solution and C2 solution was linearly increased so that it was 2.95 times the initial and final addition rates.

After the addition, in order to adjust the pH to 6.0 and remove excess salts, precipitation desalination was performed using an aqueous solution of Demol (manufactured by Kao Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate, and pAg
8.5. An emulsion with a pH of 5.85 was prepared at 40°C. Observation of the obtained emulsion using an electron microscope revealed that the average grain size was 0.92 μm, the width of the distribution was 14%, and the projected area was 88%.
The grains were tabular silver halide grains consisting of 100% (111) planes.

The average grain diameter 7/grain thickness ratio of the tabular silver halide grains was 3.6. The CuKα of this emulsion consisted of two sharp peaks with a peak interval of 0.27 degrees (2θ).

In addition, the measurement of the emulsion sample in this [Example] was carried out using JDX-11 model manufactured by JEOL Ltd. at +0 Ll.
, a graphite monochromator was used as a monochromator for diffraction lines, and the tube voltage was 40 kV as measurement conditions.

The test was carried out at a tube current of 50 mA and a step angle of 0.02 degrees (2θ).

Under these measurement conditions, the half-width of the (331) diffraction signal of the silicon powder used as a standard sample was 0.33 degrees (2θ
)Met.

Comparative Example 2 The above seed emulsion N was used, the average grain volume was the same as Em-A, the average silver iodide content was 8.0 mol%, and a high silver iodide content phase was formed inside the grains. Comparative emulsion Em-B, a monodisperse twin emulsion, was prepared.

Stir vigorously at 75°C. A. Liquid 83-1 and liquid C3-1 were added to liquid by double dient method. At this time, the pH was maintained at 2.0 with nitric acid, and I) Ag was maintained at 8.0. The addition time was 45 minutes, and the addition rate was increased linearly by a factor of 1.9 between the initial and final times. Next, liquid B, -6 and liquid C3-2 were added to the same liquid using the double jet method. At this time, the pH was maintained at 2.0 and the PAg at 8.0. The addition time was 28 minutes, and the addition rate was increased linearly by a factor of 1.75 between the initial and final times. After the addition, the pH was adjusted to 6.0, and in order to remove excess salts, precipitation desalination was performed using a Demol aqueous solution and a magnesium sulfate aqueous solution, and the pAg was
Emulsions g and s were obtained.

When the obtained emulsion was observed with an electron microscope, the average grain size was 0.75 μm, the distribution width was 15%, and the (100) plane and (
It was a monodisperse tabular silver halide emulsion having 111) planes.

The (420) diffraction line of this emulsion using the CuKa line as a radiation source was a wide signal consisting of two peaks with a peak interval of 1.32 degrees.

<Preparation of monodispersed twin emulsion Em-1 of the present invention> The above seed emulsion N was used and the average grain volume was Em-A.

E has the same volume as m-B and has an average silver iodide content of 2゜2
Emulsion Em-1 of the present invention was prepared with a concentration of 5 mol %.

Preparation of Em Liquid 84-1 and C*- were added by double jet method to liquid A4 which was vigorously stirred at 75°C. At this time, pi (was kept at 2.0 with nitric acid and pAg at 860. The addition time was 16
min, the addition rate was increased linearly by a factor of 1.27 between initial and final. Next, in the same solution, B4-2 solution and C4-
8 liquids were added by double jet method. At this time, the pH was adjusted to 2.
0 and PAg was kept at 8.0. The addition time was 38 minutes, and the addition rate was increased linearly by a factor of 1.80 between the initial and final times. After the addition was completed, desalting and precipitation were carried out in the same manner as in Comparative Examples 1 and 2 to obtain an emulsion with a PAg of 8.5 and a pH of 5.85 at 40°C.

When the obtained emulsion was observed under an electron microscope, it was found to be 100%
The silver halide emulsion consisted of twin grains, had an average grain size of 0.73 μm, and had a distribution width of 11%. Also, 1 of the projected area
00% had a particle diameter/particle thickness ratio of 1.0 to 1.5, had (100) planes and (111) planes, and the ratio was 64:36.

The (420) diffraction line using the CuKa line as the radiation source of this emulsion has only one peak, and the maximum peak height x 0.13
The diffraction width was 0.816 degrees (2θ).

Also, a line drawn perpendicularly from the highest peak and peak height x 0
．． Let B be the point where the lines drawn horizontally at 13 intersect, and let AA'' be the line segment where the lines drawn horizontally at 13 are cut by the signal, then AA' is AB by B: BA '=0.85:l.

<Preparation of monodisperse twin emulsion Em-2 of the present invention> B4 above
Emulsion Em-2 of the present invention having an average silver iodide content of 2.02 mol % was prepared in the same manner as Em-1 except that the solution in Example 1 was replaced with the solution shown below.

5 B.

i The same solution B as the solution A4, the same CS-Z as the solution C6-1, the same as -□ The same CS-Z as the solution C4-1 When the obtained emulsion was observed with an electron microscope, it was 100%.
It was a silver halide emulsion consisting of twin grains with an average grain size of 0.73 μm and a distribution width of 11%. Also, 1 of the projected area
00% had a particle diameter/particle thickness ratio of 1°0 to 1.5, had (100) planes and (ill) planes, and the ratio was 65:35.

The (420) diffraction line of this emulsion using the CuKa line as the radiation source had only one peak, and the diffraction width at the highest peak height XO,13 was 0.820 degrees (2θ). Also, a line drawn perpendicularly from the highest peak and peak height x 0°13
Let B be the point where the horizontal lines intersect, and let AA' be the line segment where the horizontal lines cut the signal at the peak height X O, 13. Then AA'' is AB by B:
BA' = 0.86:1.

<Sensitization treatment of each emulsion> The above silver halide emulsions E m, A SE m B
% Appropriate amounts of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate were added to each of Em-1 and Em-2, and chemical ripening was performed at 55°C. Next, add a sensitizing dye and 4-hydroxy-6-methyl-1,3,3a as a stabilizer.
.

7-chitrazaindene and l-phenyl-5-mercaptotetrazole were added.

On the other hand, in the same manner, the silver halide emulsion Em-A,
8X per mole of silver halide during chemical ripening for E m -B, E m -I SE m -2
The same sensitization treatment as above was carried out except that a 10-' mol potassium iodide aqueous solution was added, and Em-■, Em-■, Em
-■ and Em-■ emulsions were obtained. Using these emulsions, the following multilayer color photographic material was prepared.

[Example 1] Sample 1O1 was prepared as a comparative sample of a multilayer color reversal light-sensitive material by sequentially coating each layer having the following composition on a subbed triacetyl cellulose film support from the support side. The coating amount of each component is expressed in g/la2.

However, for silver halide, the coating amount is expressed in terms of silver.

■1 layer (Harane-Yon prevention layer) Ultraviolet absorber [J -10,3 Ultraviolet absorber U-20,4 High boiling point solvent o -11,0 Black colloidal silver 0.24 Gelatin 2.0 2nd layer (middle layer) 2.5-di-t-octylhydroquinone 0.
1 High boiling point solvent Q -10,2 Gelatin 1.0 Third layer (low sensitivity red sensitivity/10 Silver Genide emulsion layer) Red sensitizing dye (
AgBr1 (S-1,5-2) spectrally sensitized by
Agl 4.0 mol%, average grain size 0.25 μm) 0.5 Coupler C-10.3 High boiling point solvent 0-2 0.6 Gelatin 1.3 4th layer (high sensitivity red sensitivity) 10 Silver Genide Emulsion Layer) Red sensitizing dye (S-1
, 5-2) spectrally sensitized by AgBr1 (Agl
2.5 mol%, average particle size 0.6 μm) 0.8 Coupler C-11,Q High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer (intermediate layer) 2.5-di-t- Octylhydroquinone 0.
1 High boiling point solvent 0-1 0.2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) Green sensitizing dye (S-3
, 5-4) spectrally sensitized by AgBr1 (Agl
3.5 mol%, average particle size o, 25 μm) 0.6 Coupler M-10,15 Power puller M-20,04 Takasu point solvent'O-3Q,5 Gelatin 1°4vg7
layer (high sensitivity green-sensitive halogenated emulsion layer) green sensitizing dye (S
-3,5-4) and spectrally sensitized by I:AgBr1
(E m -A) 0.9 Coupler M-10,56 Power Blur M -20,12 High boiling point solvent 0-3 1.0 Gelatin l.5 8th layer (intermediate layer) 9th layer same as 5th layer (Yellow filter layer) Yellow colloidal silver 0.1 gelatin 0.92.5-di-
t-Octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 1st θ layer (low sensitivity blue-sensitive silver halide emulsion layer) AgBr1 spectrally sensitized with blue sensitizing dye (5-5) (Agl 2- 5 mol%, average particle size 0.35 μm) 0.6 coupler Y −
11,4 High boiling point solvent 0-3' 0.6
Gelatin l.3 No. 11
layer (high sensitivity blue-sensitive silver halide emulsion layer) blue sensitizing dye (
AgBr1 (Agl
2.5 mol%, average particle size 0.9 μm) '0.9 Coupler Y -13.5 High boiling point solvent 0-3 1.4 Gelatin 2.1 12th layer/1st protective layer UV absorber U -10 ,3 Ultraviolet absorber TJ-20,4 2,5-di-t-octylhydroquinone 0,
1 High boiling point solvent 0-3 0.6 Gelatin 1.2 13th layer:
Second protective layer average grain size (r) 0.08 μm, non-photosensitive fine-grain silver halide emulsion made of silver iodobromide containing 1 mol% of silver iodide
0.3 Polymethyl methacrylate particles (diameter 1.5 μm) 0.06 Surfactant SA-10,004 Gelatin 0.7 In addition to the above composition, each layer also contains gelatin hardener, ultraviolet absorber U, etc. Sensitizing dye S- 2 Sensitizing dye S- Sensitizing dye S- (CH,), so3" C, 11th sensitizing dye S Coupler C- ■ Coupler M~ ShiU Coupler M-2 Coupler Y Gelatin hardening agent H- 1 Surfactant SA- Na0sS-CHCOOCHz(CFzCFt)rHC
H, C00CH, (CF, CFt) IH〇 - -3 C, 11°C211°Next, the silver halide emulsion of the seventh layer of sample 101 is shown in Table-1.
Sample 1 was prepared in the same manner as sample 101 except that I was changed as follows.
02-108 were created.

Table - ■ Samples 101 to 108 were exposed to white light (5500°K) through a step wedge for 1/125 seconds, 10-
Exposure was carried out for 103 seconds. However, the exposure doses were all 10C, M, and S.

After exposure, the following development process was performed.

Processing process Processing time Processing temperature First development
6 minutes 38℃ water washing
2 〃 〃Reversal
2〃/l color development 61111 adjustment 2 //
! ! bleaching
5 // // Fixation 4 tt /
/Wash 4 tt
tt stable 1
// Constant tumble drying The composition of the processing solution used in the above processing step is as follows.First developer: Sodium detravoli phosphate 2g Sodium sulfite 20g Hydroquinone.
Monosulfonate 30g Sodium carbonate (monohydrate) 30g l-phenyl-4-methyl-4-hydroxymethyl-3
Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0,
1% solution) Add 2rxO water
100100O inversion liquid Nitrilotrimethylenephosphonic acid, hexasodium salt Stannous chloride (dihydrate) p-aminophenol Sodium hydroxide Add glacial acetic acid water Color developer Sodium tetrapolyphosphate Sodium tertiary phosphate Sodium bromide Potassium bromide Potassium (0.1% solution) Sodium hydroxide N-ethyl-N 3-methyl citrazate g g (dihydrate) 36 g g 0111a g 1.5 g β-methanesulfonamidoethyl 4-aminoaniline sulfate g g 0.1g g 15m (2 1000111Q 1g 2.2-ethylenedithiogetanol g Add water and adjust to 1000IIIQ Liquid sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) g Thioglycerin 0.4wrQ Ice vinegar i23 tn Q Add water to 1000+o1
2 Bleach Liquid Sodium ethylenediaminetetraacetate (dihydrate) g Iron tetraacetate (II ammonium 00g 1000 mff Ethylenediamine (dihydrate) Ammonium bromide Add water to fix Liquid Ammonium thiosulfate Monium sulfite Sodium bisulfite Sodium size: 0g g g 1000111Q Stable liquid formalin (37% by weight) 5m+1
2 Konidax (manufactured by Konica Corporation) 5m12
The density of the sample obtained by water processing and development was measured using a Status A filter with a densitometer model 310 manufactured by X-Rite. The relative sensitivity at a magenta density of 2.0 in the green sensitive layer was calculated and shown in Table 2.

(However, the sensitivity of sample 101 at 1/125 second exposure was assumed to be 100.) As is clear from Table 2, the configuration of the present invention has no reciprocity law failure at low and high illuminances without decreasing sensitivity. It can be seen that both have been improved.

Example-2 The emulsion of the fourth layer of sample 101 of Example-1 was 87 in Table-1.
Samples 201 to 208 were replaced to correspond to the emulsions in the layers.
was created. However, each emulsion used was red sensitizing dye S-1.
, S-2 was used. When the reciprocity law failure of the red-sensitive layer was evaluated in terms of relative sensitivity at a cyan density of 2.0 in the same manner as in Example-1, the same effect as in Example-1 was obtained.

Example 3 Samples 301 to 30 were prepared by replacing the 11th layer emulsion of sample 101 of Example 1 to correspond to the 7th layer emulsion in Table 1.
8 was produced. However, each emulsion used was blue sensitizing dye S-
5 was used. In the same manner as in Example 1, the reciprocity law failure of the blue sensitive layer was evaluated by the relative sensitivity at a yellow density of 2.0, and the same effect as in Example 2 was obtained.

Claims (1)

[Claims] The silver halide photographic emulsion used in photographic light-sensitive materials is (1)
50% or more of the total projected area of the emulsion grains is provided by silver halide twinned grains with a grain diameter/grain thickness ratio of less than 5, and (2) the emulsion grains are monodisperse; ) The (420) X-ray diffraction signal using CuKα radiation as the radiation source has a unique peak, and the maximum peak height x 0.13
(4) has a high silver iodide content phase inside the grain and a low silver iodide content phase on the grain surface; It mainly contains silver bromide grains, and (5) the emulsion having the above structure contains 10^-^5 to 10 iodide ions per 1 mol of silver halide.
A silver halide photographic light-sensitive material characterized by containing a silver halide photographic emulsion to which 1 mol of silver halide is added.