JPH03214154A - Silver halide color photographic sensitive material having improved color reproducibility - Google Patents

Abstract

PURPOSE:To improve color reproducibility by incorporating a specified silver halide photographic emulsion into at least one of photosensitive layers and a silver halide photographic emulsion contg. polydispersed silver halide twin particles into at least one of the remaining photosensitive layers. CONSTITUTION:A silver halide photographic emulsion contg. silver halide twin particles having <5 ratio of diameter to thickness by >=50% of the total projection area of all the silver halide particles is incorporated into at least one of photosensitive layers. The silver halide particles in the emulsion are singly dispersible, the (420) X-ray diffraction signal of the emulsion with Cukalpha-rays as a ray source has only one peak and the width of a diffracted ray at the height of the peakX0.13 is < 1.5 at the angle (2theta) of diffraction. A silver halide photographic emulsion contg. polydispersed silver halide twin particles is incorporated into at least one of the remaining photosensitive layers. Color reproducibility is improved.

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 color reproducibility and a halogen compound applied to the light-sensitive material. Concerning silver oxide photographic emulsions.

[Background of the invention]

In recent years, there has been an increasing demand for higher image quality for silver halide color photographic materials.

In order to improve color reproducibility, various improvement studies have been conducted regarding the development inhibiting effect (interimage effect; IIE) between layers having different color sensitivities.

In color reversal photosensitive materials, emphasis on IIE has been studied in each of the first development (monochrome development) and second development (color development).

Regarding the second development, a technique is known in which a compound that releases a development inhibitor during development, such as a DIR coupler, is included in the light-sensitive material, but this is not sufficient.

Regarding the first development, a technique is known in which a compound that releases a developer during development is contained in the photosensitive material. for example,
JP 49-129536, U.S. Patent No. 3379529
No. 3620746, No. 4332878, No. 43
Examples include old R-hydroquinones described in JP-A No. 77634, etc.; old R-aminophenols described in JP-A No. 52-57828, etc.; and p-2 benzyl derivatives described in EP 45129.

Further, JP-A No. 61-213847 discloses a type of compound as a redox compound that releases a photographically useful group while causing an oxidation-reduction reaction within the molecule.

However, these compounds also did not have sufficient improvement effects. Also, when these compounds are introduced into photosensitive materials,
There was also the problem of deterioration in storage stability over time.

Regarding the first development, it is known that IIE using iodide ions released during development is effective. For example, Japanese Patent Publication No. 59-35011 or Japanese Patent Publication No. 62-91
No. 946 discloses a technology using fogging emulsions and internal fogging. However, this technique has the disadvantage of requiring a significantly higher amount of silver. Similarly, IIE using iodide ions can also be obtained by controlling the silver halide composition and silver halide grain structure of the silver halide emulsion in each color-sensitive layer. JP-A-63-2
No. 85549 and No. 63-305355 attempted to apply tabular silver halide emulsions having a grain diameter/grain thickness (cross-sectional ratio) of 5 or more. However, even with these techniques, the improvement effect is not sufficient, and further improvements are desired.

C. Object of the Invention] In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide color photographic light-sensitive material with improved color reproducibility. Yet another object of the present invention is to provide a novel silver halide emulsion that meets the above objectives.

[Structure of the invention]

The object of the present invention is to provide a silver halide color photographic light-sensitive material having two or more types of photosensitive layers having different color sensitivities on a support, in which 50% or more of the projected area has a grain diameter/grain thickness ratio. A silver halide photographic emulsion consisting of silver halide twin grains having a particle diameter of less than 5, the silver halide emulsion being monodisperse and using CuKa radiation as a radiation source (420), which has a unique X-ray diffraction signal. Has a peak, maximum peak height x 0
．． At least one of the light-sensitive layers contains a silver halide photographic emulsion having a diffraction linewidth of less than 1.5 degrees at a diffraction angle (2θ) in No. 13, and is composed of polydisperse silver halide twin grains. This is achieved by a silver halide color photographic light-sensitive material characterized by containing a silver halide photographic emulsion in at least one of the remaining light-sensitive layers.

The present invention will be explained in more detail below.

Twin crystals refer to silver halide crystals that have one or more twin planes in one grain, but the classification of twin crystal morphology is based on Klein and Moyser's ``Photographishe Korresp'' correspondent.
ondenz) Volume 99, page 99, Volume 100, 57j
[Details are given in [].

In the present invention, two types of twinned grain emulsions are used. One of them is a silver halide photographic emulsion in which 50% or more of the projected area is composed of silver halide twin grains having a grain diameter/grain thickness ratio of less than 5, and the silver halide emulsion is It is monodisperse, and CuKa radiation was used as the radiation source (4
20) The X-ray diffraction signal has only one peak, and the diffraction line width at the highest peak height X O,13 is equal to the diffraction angle (
2θ) of less than 1.5 degrees, and hereinafter referred to as the monodisperse twinned emulsion of the present invention.

The other type is a twin emulsion having a wider grain size distribution than the monodisperse twin emulsion of the present invention, and is hereinafter referred to as a polydisperse twin emulsion.

(Monodisperse twin emulsion according to the present invention) The monodisperse twin emulsion according to the present invention preferably mainly consists of silver iodobromide.

The monodisperse twinned emulsion of the present invention preferably has two or more parallel twin planes, more preferably an even number of twin planes, and most preferably two twin planes. be.

Two or more twin planes of a twin may or may not be parallel to each other. Twin planes can be observed directly with an electron microscope, but silver halide grains can also be dispersed and hardened in a resin and observed from the cross section as an ultrathin section sample.

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 monodisperse twinned emulsion of the present invention is composed of silver halide twinned grains in which 50% or more of the projected area has a grain diameter/grain thickness ratio of less than 5, preferably 70% or more of the projected area, Particularly preferably, it is 90% or more. Also, particle diameter/
The particle thickness ratio is preferably 1.0 to 4.5,
Particularly preferably, it is 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, "consisting mainly of twin grains" means that the ratio of twin grains to the total number of grains is 60% or more, preferably 80% or more, particularly preferably 95 to 100%.

The silver halide emulsion mainly composed of twin crystals in the present invention is monodisperse.

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

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,' of x and d13 becomes maximum. (3 significant figures, minimum 4 digits)
The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The particle size can be obtained, for example, by 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 width defined by 20% or less, more preferably 15% or less, particularly preferably 12% or less.

Here, the particle size measurement method shall follow the measurement method described above,
The average particle size is a simple average.

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 CuKσ line 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 the gelatin, mix a standard sample such as silicon, and perform the measurement using a powder method.

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

The monodispersed silver iodobromide emulsion mainly composed of twin crystals according to the present invention has a diffraction line width at a maximum peak height Xo of 13 of a (420) X-ray diffraction signal using CuKa radiation as a radiation source, and a diffraction angle ( 2θ) is less than 1.5 degrees. 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 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 monodisperse twin emulsion of the present invention uses CuKa radiation as a radiation source (
420) Maximum peak height Xo of X-ray diffraction signal, 1
3, 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 line segment B is the length of line segment AB.
It is preferable that the division is performed such that the value of the length of A' is 1.0 or less.

Here, the line segment AA' is drawn from the narrow angle side of the diffraction angle to the wide angle 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 monodisperse twin emulsion of the present invention preferably has both (111) planes and (100) planes, with 20% or more of the grain surface being (100) planes, more preferably 30% or more, particularly preferably 40% planes. ~70% are (100) planes. (10
It is preferable that the planes other than the 0) 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 the signals of the 222) plane and the (220) plane.

The monodispersed twin emulsion of the present invention preferably has an average silver iodide content of less than 6 mol%, more preferably 0 to 6 mol%.
5 mol%, particularly preferably 1 to 4 mol%.

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

The monodisperse twin emulsion of the present invention can be obtained by localizing silver iodide within the 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%.

The silver iodide content of the outermost shell and inner core is 10 mol% each.
It is preferable that there is a difference of at least 20
The difference is 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 an insulated phase in which the composition changes continuously within the phase, or a combination thereof.

In the case of the above-mentioned embodiment in which the silver iodide content rate changes continuously, the silver iodide content rate decreases monotonically from the point where the silver iodide content rate within the grain is maximum toward the outer part of the grain. It is preferable that there be.

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. .

As a method for obtaining the monodisperse twin 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 preferably JP-A-6
The method described in No. 1-6643 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%; The pBr of the mother liquor was kept at 2.0 for at least 1/2 period from the beginning of silver halide precipitate formation.
(b) Following the core particle generation step, the mother liquor contains lo-6 to 2.0 moles of a silver halide solvent 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.

In the present invention, the twin core particles are produced by controlling the bromide ion concentration in the protective colloid aqueous solution to 0601 to 5 mol/a, that is, pBr-2,θ to
-0.7, preferably 0.03 to 5 mol/Q (p
It can be obtained by maintaining Br=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 21% 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 broadening of the grain size distribution, with the small grains dissolving and the large 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 twins are obtained by ripening the emulsion mother liquor that has gone through the process in the presence of a silver halide solvent of 1 O -5 to 2.0 mol/silver mol. Substantially monodisperse means that the width of the distribution as defined above is 20% or less.

In addition, substantially spherical grains are defined as (Ill) planes or (1
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.

Further, in the present invention, it is preferable that the spherical particles account for 60% or more, preferably 80% or more, and more preferably most of the total number of seed particles.

The silver halide solvent used in the seed grain forming step of the present invention includes (a) U.S. Pat. No. 3,271,157;
, 531,289, 3,574.628, JP-A-54-1019, JP-A-54-158917, and JP-A-58-30571;
(b) JP-A-53-82408, JP-A No. 55-29829
(c) an AgX solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, which is described in JP-A-53-144319; (d) Japanese Patent Publication No. 54-1007
Imidazole described in No. 17, (e) sulfite,
(f) Thiocyanates, (g) Ammonia, (h) Ethylenediamines substituted with hydroxyalkyl described in JP-A-57-196228, (i) JP-A-57-1962
Substituted mercaptotetrazoles described in No.-202531, (j) water-soluble bromide, (k) JP-A-58-54
Examples include benzimidazole derivatives described in No. 333.

Next, specific examples of these silver halide solvents (a) to (k) will be given.

FIOCHzCH2SCHzCH2SCHzCI(io
HCH,NHCOCH,CH,Cool(CHzSCH
xCHzSCJs CH, NHCαjH2 CH*5CHxCH*5CH-CH-COOH(e) KzSOs, KazSO.

( f) NH, SCN, KSCN (g) N.H.

(h) (HOCH2C)If)2NCR,CH2N(CH,C
H, OH).

(C2H,)zNCH2CH,N(CH,CH,OH)
! (j) NaBr, NH, Br, KBr Two or more of these solvents can be used in combination. Preferred solvents include thioethers, thiocyanates, thioureas, ammonia, and bromides, particularly preferably a combination of ammonia and bromide.

These solvents contain from IO-6 to IO-6 per mole of silver halide.
It is used in a range of 2 moles.

In addition, the pH is 3 to I3, and the temperature is 30 to 70°.
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℃
Bromination power is 1.0 mol/ff! J'ymu 0.03~0
．． 5 mol/ (I used all 11 together, 30 seconds ~ lO
An emulsion containing suitable seed particles was obtained by ripening for a minute.

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 involves pAgSP during silver halide precipitation and Ostwald ripening.
This is achieved by controlling H, temperature, concentration and silver halide composition of silver halide solvent, and rate of addition of silver salt and halide solution.

Conditions for enlarging the seed particles obtained in the present invention include JP-A Nos. 51-39027, 55-142329, 58-113928, 54-48521 and
As seen in No. 8-49938, 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 and Ostwald ripening does not occur. One possible method is to gradually change it within a range. As another condition for enlarging the seed grains, a method of enlarging the seed grains by adding l\ silver halide fine grains, dissolving and recrystallizing can also be used, as shown in the Abstracts of the 1981 Annual Conference of the Photographic Society of Japan, page 88. However, the former method is preferred.

In producing the silver halide emulsion according to the present invention, growth conditions for silver halide grains include pAg5 to IL temperature 4.
Preferably, the temperature is 0 to 85°C and the pH is 1.5 to 5.8.

The pH is particularly preferably 1.8 to 3.5. The pAg is particularly preferably 6.0 to 9.5, and the temperature is 60 to 8.
0°C is particularly preferred.

During growth, it is preferable to add a silver nitrate aqueous solution and a /10 genide aqueous solution by a double jet method. In addition, the modified state can also be supplied into the system as silver iodide. The addition rate should be such that new nuclei are not generated and the size distribution does not widen due to Ostwald ripening.
That is, it is preferable to add at a rate of 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 Japanese Patent Application Laid-Open No. 160128/1983, in which the additive liquid nostle is placed 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
200 rpm+rubbing is preferred.

(Polydisperse twin emulsion according to the present invention) In the present invention, polydispersity means 21% or more, preferably 21% or more and less than 40%, particularly preferably 22% or more and less than 35% in the definition of the width of the distribution. be.

Furthermore, two or more types of monodisperse twin emulsions having different average grain sizes may be mixed and used as a polydisperse twin emulsion.

The polydisperse twin emulsion used in the present invention may be any silver halogenide emulsion having one or more twin planes in one grain, and the grain diameter/grain thickness ratio, There are no restrictions on line diffraction signal characteristics, crystal phase planes, nitrogen composition, . . . rogen distribution, etc.

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.

In the present invention, two or more types of photosensitive layers having different color sensitivities are provided on a support, at least one of the photosensitive layers contains the monodisperse twin emulsion of the present invention, and the remaining photosensitive It is sufficient that at least one of the layers contains a polydisperse twin emulsion.

In a further preferred embodiment, at least one of the photosensitive layers of the silver decagenide color photographic light-sensitive material is composed of two or more layers having the same color sensitivity but different sensitivities, and at least one of the two or more layers is The monodisperse twin emulsion of the present invention can be contained in the monodisperse twin emulsion of the present invention, and at least one of the other layers can contain the polydisperse twin emulsion.

In a more preferred embodiment, the support has two or more types of photosensitive layers having different color sensitivities, and at least one of the photosensitive layers is composed of two or more layers having the same color sensitivity but different sensitivities; This is an embodiment in which at least one of the sensitive layers contains the monodisperse twin emulsion of the present invention, and at least one of the other highest sensitivity layers contains the polydisperse twin emulsion.

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

The present invention is preferably used for color photosensitive materials such as 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. , antifoggants, chemical sensitizers,
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 antihalation layer, and an antiirradiation layer.

These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material 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 by giving Examples.

(Preparation of spherical seed emulsion N) Monodisperse spherical seed emulsion N was prepared by the method disclosed in JP-A No. 61-6643.

Dl Aqueous ammonia (28%) 705 Seed Q To liquid A, which was vigorously stirred at 40°C, liquid B and liquid C1 were added in 30 seconds by 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 ripening was 0.071 mol/Q, and the ammonia concentration was 0.63 mol/Q.

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, it was found to be a monodisperse spherical emulsion with an average grain size of 0.36 .mu.m and a 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.

Add 40% of B2 solution and 02 solution to A and vigorously stirred at 65℃.
．． It was added by double jet method in 5 minutes. During this time, the pH was maintained at 2 and the (H: pAg) at 9.0 with nitric acid.

The addition rates of Solution B and Solution C were linearly increased to 2.95 times between 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 Kako Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate, and pAg
An emulsion having a pH of 5.85 at 40° C. was obtained.

When the obtained emulsion was observed under an electron microscope, it was found to be tabular silver halide grains having an average grain size of 0.92 μm, a width of 14% distribution, and 88% of the projected area consisting of 100% (l1l) planes.

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

In all measurements of emulsion samples in this [Example], a JDX-11 model manufactured by JEOL Ltd. was used as the device, and a graphite monochromator was used as a monochromator for diffraction lines.
The measurement conditions were a tube voltage of 40 kV.

The test was conducted with 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 (2e
)Met.

Comparative Example 2 The above seed emulsion N was used, the average grain volume was the same as EmA, the average silver iodide content was 8.0 mol%, and a monomer having a high silver iodide content phase inside the grains was used. Comparative emulsion Em-B, a dispersed twinned emulsion, was prepared.

Preparation of Em-H Stir vigorously at 75°C. Liquid B, -3 and liquid C1-1 were added to liquid A3 by a double jet method. At this time, the pH was maintained at 2.0 with nitric acid, and the [)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, -2 and liquid CI-2 were added to the same liquid by a double jet method. At this time, the pH
was maintained at 2.0 and pAg at 8.0. Addition time is 28
The addition rate was increased linearly so that the initial and final addition rates were 1.75 times. After the addition was completed, the pH was adjusted to 6.0, and in order to remove excess salts, precipitation desalination was performed using an aqueous solution of Demol and an aqueous solution of magnesium sulfate, and the pH was adjusted to 6.0 at 400C.
An emulsion of g8.5 was obtained.

When the obtained emulsion was observed under an electron microscope, it was found to be a monodisperse tabular/X silver halide emulsion with an average grain size of 0.75 μm and a distribution width of 15%, having (100) and (111) planes. there were.

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 the monodispersed twin emulsion Em-1 of the present invention> Using the above-mentioned seed emulsion N, the average grain volume was the same as that of Em-A%Em-B, and the average silver iodide content was 2°25. Emulsion Em-1 of the present invention was prepared in mol %.

8 by double jet method into A4 liquid stirred vigorously at 75℃.
Liquid 4-1 and liquid 04-1 were added. At this time, the pH was maintained at 2.0 and the pAg at 8.0 with nitric acid. Addition time was 16 minutes.
The addition rate was increased linearly between initial and final l, 27 times I:. Next, add 84- to the same solution and add 04-□
The liquid was added by double jet method. At this time, set J)H to 2.
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 Example 1.2 to obtain an emulsion with pAg 8.5 and pH 5.85 at 40°C.

When the obtained emulsion was observed with an electronic M microscope, it was found to be 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 (111) planes, and the ratio was 64:36.

The (420) diffraction line of this emulsion using the CuKa line as the radiation source has only one peak, and the maximum peak height is X O,13
The diffraction width was 0.816 degrees (2θ). Also, a line drawn perpendicularly from the highest peak and peak height x 0.1
Let B be the point where the lines drawn horizontally at 3 intersect, and let AA' be the line segment where the lines drawn horizontally at peak height XO, 13 are cut by the signal. It was divided into -0,85+1.

Preparation of monotwinned emulsion Em-2 of the present invention> B, -
Emulsion E of the present invention having an average silver iodide content of 2.02 mol % was prepared in the same manner as Em-1 above, except that solution 2 was replaced with the following solution.
m-2 was prepared.

A, #Same as solution A4 B, -1 Same as solution B4-1 C3-1 Same as solution C6-1 C6-8 Same as solution C, -2 When the obtained emulsion was observed with an electron microscope, it was 100%.
It is a silver halide emulsion consisting of twin grains with an average grain size of 0.73 μm and a distribution width of 11%. In addition, 100% of the projected area has a particle diameter/particle thickness ratio of 1.0 to 1.5.
It had a (100) plane and a (111) plane, and the ratio was 65:35.

The (420) diffraction line of this emulsion using the CuK a line as the radiation source has only one peak, and the highest peak height is X O,13
The diffraction width at 011t was 20 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 cross the peak height X O, and the line drawn horizontally at 8 is AA'. '-0,86:l.

<Preparation of polydisperse twin emulsion Em-3,4 of the present invention> The above E
In the preparation of m-A, except that the addition rate of B, liquid and 02 liquid was constant and pag was not controlled
Em-3 was prepared in the same manner as the preparation of -A.

Em-3 was a polydisperse twin emulsion with an average grain size of 0.70 μm and a distribution width of 33%.

On the other hand, in the preparation of Em-H, B5-7 solution and C3
Em-4 was prepared in the same manner as in the preparation of Em-B, except that the addition rate of the -2 solution was kept constant and pAg was not controlled.

Em-4 was a polydisperse twin emulsion with an average grain size of 0.68 μm and a distribution width of 26%.

<Sensitization treatment of each emulsion> The above silver halide emulsions Em-A and Em-B.

Appropriate amounts of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate were added to each of Em-1, Em-2, Em-3, and Em-4, and chemical ripening was performed at 50°C. After chemical ripening, 4-hydroquine-6-methyl-1,3,3a,7-chitrazaindene was added as a sensitizing dye and a stabilizer.
.

Using these emulsions, the multilayer color photosensitive material shown below was prepared.

[Example 1] Sample 101 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 shown in g/112. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Ultraviolet absorber U -10,3 Ultraviolet absorber U -20,4 High boiling point solvent 0-1 1.0 Black colloidal silver 0.24 Gelatin
2.0 Second layer (middle layer) 2.5-di-t-octylhydroquinone 0.
1 High boiling point solvent 0-1 0.2 Gelatin l・0 3rd layer (low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1
, 5-2) spectrally sensitized by AgBr1 (Ag1
4.0 mol%, average particle 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-sensitive silver halide emulsion layer) Red Sensitizing dye (S-1,
AgBr1 (Agl
2.5 mol%, average particle size 0.6 gm) Coupler C-1 High boiling point solvent 0-2 Gelatin 5th layer (middle layer) 2.5-di-t-octyl high high boiling point solvent 0-1 Droquinone 0. 8 1.0 1.2 1.8 (Ll 0.2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) Spectral enhancement by green sensitizing dye (S-3, 5-4) AgBr1 felt
(Agl 3.5 mol%, average particle size 0.25 μm) 0.
6 Coupler M-10,15 Coupler M-20,04 High boiling point solvent 0-3 0.5 Gelatin 1.4 7th layer (high sensitivity green-sensitive halogenated emulsion layer) Green sensitizing dye (S-3,5
-4) and was spectrally sensitized by 7':AgBr1 (E
m -A) Coupler M-1 Coupler M-2 High boiling point solvent 0-3 Gelatin 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer 0.9 0°56 0.12 1. 0 1.5 Yellow colloidal silver 0.1 Gelatin 0.92.5-di-octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 1st theta layer (low sensitivity sensitive silver halide emulsion layer) Blue enhancement AgBr1 spectrally sensitized with sensitive 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 1,3 11th layer (high sensitivity silver halide emulsion layer) Blue sensitizing dye (5-5
) spectrally sensitized by AgBr1 (E m −A
) Coupler Y-1 High boiling point solvent 0-3 Gelatin 12th layer: 1st protective layer UV absorber U-1 UV absorber U-2 0,9 3,5 1,4 2,1 0,3 0,4 2.5-di-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 grains made of silver iodobromide containing 1 mol% of silver iodide/Silver halide emulsion 0.3 polymethyl methacrylate grains (diameter 1.5μ111) 0.06 Surfactant SA-10,004 Gelatin 0.7 In addition to the above composition, gelatin hardening agent H-1 and a surfactant were added to each layer.

Ultraviolet absorber U-1 Ultraviolet absorber U Sensitizing dye S Sensitizing dye S Sensitizing dye S (CHzJ3SOs'7 (shiH2)3SiJ3Na Sensitizing dye S- Sensitizing dye S- Coupler-C-1 Coupler M ■ Coupler M- ShiQ Coupler Y- ■ Gelatin hardening agent H-1 Surfactant SA- ■ NaOs 5-CHCOOCH2 (CF ICF !
) s HCHzCOOCIh(CFzCFz)zH1 C2H.

C,H.

Next, Samples 102 to 108 were prepared by changing the silver halide emulsions in the seventh and eleventh layers of Sample 101 as shown in Table 1.

Table 1 Green light (
After wedge exposure, the following development process was performed using a Kodak CC90G filter.

Processing process Processing time Temperature first development
6 minutes 38°C water washing
2 〃 〃Reversal
2// tt color development 5 tt tt adjustment
2tt tt floating
white 5 tt
// established 4 〃
〃Washing with water
4 tt tt stable
1 tt Dry at room temperature
Drying The composition of the processing solution used in the above processing step is as follows: First developer: Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone.
Monosulfonate 30g Sodium carbonate (l aqueous salt) 30
g l-phenyl-4methyl-4-hydroquinemethyl-3pyrazolidone 2g potassium bromide 2.5g potassium diocyanate 1.2g potassium iodide (0,1
% solution) 2m (add 2 water
1000+m (1 inversion) Solution Nitrilotrimethylenephosphonic acid 6-sodium salt Stannous chloride (dihydrate) P-aminated/7-enol Sodium hydroxide Add glacial acetic acid water and color developer Sodium tetrapolyphosphate Sodium sulfite Sodium phosphate (dihydrate) Potassium bromide potassium iodide (0.1% solution) g g 0.1g g 15+++ (2 1000II14 g g 6g g 90v (7) Sodium hydroxide 3g Nthrazinate 1.5g N-ethyl -N-β-methanesulfonamidoethyl 3-methyl-4
-Aminoaniline sulfate 2.2-Ethylenedithiogetanol Adjust by adding water Liquid sodium sulfite Sodium ethylenediaminetetraacetate 1g g 1000m0゜2g (dihydrate) g Q, 4m (1 mff 000mC Thioglycerin glacial acetic acid water) Bleach by adding liquid sodium ethylenediaminetetraacetate (dihydrate) g iron ethylenediaminetetraacetate (I [[) ammonium (2
water salt) 120g ammonium bromide Add 100g water
1000tQ fixation liquid Ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Add water
1000a+4 Stable liquid formalin (37% by weight) 5+a(
2 Konidax (manufactured by Konica Corporation) 5o++
2 Add water to 1000 o 12
The concentration was measured using a Status A filter. Yellow when the magenta density of the green image is 1.0 According to Table 2, the composition of the present invention has high yellow and cyan density when the magenta density is 1.0, and has excellent green color reproducibility. I understand.

[Example-2] Sample 201 was prepared by changing the silver halide emulsion in the fourth layer of Sample 101 of Example-1 as shown in the 11th layer column of Table-1.
~20g was made. However, all the silver halide emulsions used in the fourth layer were red-sensitive emulsions by using a red-sensitive sensitizing dye. The green reproducibility was evaluated in the same manner as in Example 1, and it was found that the composition of the present invention had excellent green reproducibility.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having two or more types of photosensitive layers with different color sensitivities on a support, 50% or more of the projected area is made of halogen with a grain diameter/grain thickness ratio of less than 5. A silver halide photographic emulsion comprising silver twin grains, the silver halide emulsion being monodisperse, C
A halogen whose (420) X-ray diffraction signal using uKα radiation as a radiation source has a single peak, and whose diffraction line width at the maximum peak height x 0.13 is less than 1.5 degrees in terms of diffraction angle (2θ). A silver halide photographic emulsion is contained in at least one of the photosensitive layers, and a silver halide photographic emulsion comprising silver halide polydisperse twin grains is contained in at least one of the remaining photosensitive layers. A silver halide color photographic light-sensitive material characterized by: