JPH03214151A - Silver halide color photographic sensitive material having improved shelf stability - Google Patents

Abstract

PURPOSE:To improve shelf stability while maintaining high sensitivity by incorporating a specified silver halide photographic emulsion into at least one of photosensitive layers and a silver halide photographic emulsion contg. silver halide particles of normal crystals 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 projec tion 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 peak X 0.13 is <1.5 at the angle (2theta) of diffraction. A silver halide photographic emulsion contg. silver halide particles of normal crystals is incorporated into at least one of the remaining photosensitive layers. Shelf stability can be improved while maintaining high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved storage stability.

[Background of the invention]

After the silver halide grains used in silver halide color photographic light-sensitive materials are formed, they are usually chemically sensitized to increase their sensitivity, and spectral sensitizing dyes are used to increase their sensitivity to light in a specific range of wavelengths. It is felt.

The silver halide emulsion obtained as described above is layered and coated on a support together with photographic additives such as couplers and dyes, mainly using gelatin as a binder, and dried to produce a silver halide color photographic light-sensitive material. It is formed. The photosensitive material is then imagewise exposed and developed to obtain a desired image. However, after the photosensitive material is formed and before it is imagewise exposed, it may be left for a long time or placed in a high temperature and high humidity atmosphere. When exposed, fogging, desensitization, and gradation disturbances may occur.

This is due to changes in the adsorption state of various photographic additives such as sensitizing dyes, chemical sensitizers, antifoggants, development inhibitors, and latent image stabilizers adsorbed on the surface of silver halide grains. It is known that the main cause is attachment and detachment.

In the past, in order to improve storage stability, studies have been made to select the type of additive, improve the addition method, adjust the amount added, etc. However, if the type of silver halide grains differs, Adjustment is required, and the effect is not sufficient.

On the other hand, among silver halides, emulsions consisting of normal crystal grains have relatively good storage stability, but they are susceptible to the influence of other silver halide grains contained in adjacent layers, and It has been found that increasing the silver iodide content has the disadvantage of deteriorating storage stability.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that has improved storage stability while maintaining high sensitivity.

[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 light-sensitive 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)
A silver halide photographic emulsion in which the line diffraction signal has a unique peak and the diffraction line width at the maximum peak height X O,13 is less than 1.5 degrees in terms of the diffraction angle (2θ) is used in the photosensitive layer. A silver halide color photographic light-sensitive material characterized in that a silver halide photographic emulsion containing normal crystal grains of silver halide is added to at least one layer of the remaining light-sensitive layers. achieved.

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, Photography Korras.
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 linden fat and solidify it, and then observe it from the cross section as an ultra-thin 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 50 when counted from large grain size particles.
% or more, preferably 60% or more, particularly preferably 70%
This is the case above.

The silver halide emulsion according to the present invention is composed of silver halide twin grains in which 50% or more of the projected area has 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 4.5, 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 twinned grains according to the present invention, the ratio of twinned grains to the entire grain is 50% or more, preferably 70% or more, and particularly preferably 85 to 100% in terms of projected area.

In the present invention, the silver iodobromide emulsion mainly consisting of twin crystals is monodisperse, but in the present invention, the monodisperse silver halide emulsion is defined as having a grain size within ±20% of the average grain size d. The weight of silver halide contained in is 7 of the total weight of silver halide.
0% or more, preferably 80% or more, more preferably 90% or more.

Here, the average particle size d is the frequency n of particles having a particle size d8,
It is defined as the particle size d1 when the product n, X d, 3 of
people).

The particle size referred to here is the diameter when a projected image of the particle is converted into a circular image with the same area.

The particle size can be determined, 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, CuKa ray 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 the measurement method, reference can 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) X-ray diffraction signal using the uKc line as the radiation source. be. 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 Xo, 13. The diffraction signal of the silver halogenide 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 a maximum peak height Xo of a (420) X-ray diffraction signal using CuKa radiation as a radiation source.
, 13, the line segment where the line drawn horizontally 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 BA' with the length of line segment AB is It is preferable that the partitioning be performed such that the ratio to the length is 1.0 or less. Here, the ratio of the length of the line segment AA' on the low angle side of the diffraction angle to the length of the line segment BA' is more preferably 0.95 or less, particularly preferably 0.60 to 0.90. be.

The silver halide twin grains according to the present invention have (III) 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 (100) 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 halogenated rice particles are distributed so as not to overlap on a flat sample stage. The ratio and powder sample are 8 times (200) plane and (
It can be determined by comparing the ratio of the signals 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%.

May be included.

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 in the grain surface portion is preferably 3 mol% or less, more preferably 0 to 2 mol%, particularly preferably o, i - i, o mol% of silver iodobromide. .

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 degenide precipitate formation, the pBr of the mother liquor was reduced to 2.
(b) Following the core particle generation step, a /% silver halide solvent is added to the mother liquor at 1 O -6 to 2.0 mol per mol of silver halide. Contains
A seed grain formation step is provided to form silver halide seed grains that are substantially monodisperse spherical twins, and (c) a water-soluble silver salt solution and a water-soluble silver halide solution and/or silver halide are then added A method that includes a growth step of adding fine particles to enlarge the seed particles is preferably used.

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

The silver iogenide 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.

In addition, the outer wall of the crystal consists of (111) planes, (100
) or both sides.

In the present invention, the twin core particles reduce the bromide ion concentration in the protective colloid aqueous solution to 0.0 during the initial 1/2 or more period of the core particle generation process. O1~5 mol/Q or pBr-2, θ~
-0.7, preferably 0.03 to 5 mol/Q (p
B r -1,5 to -0,7), and adding a water-soluble silver salt or a water-soluble silver salt and a water-soluble chloride.

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 referred to as nest ripening) occurs when large grains and small grains coexist, the small grains dissolve and the large grains grow, and generally the grain size distribution becomes wider. This seems to be different from the Ostwald ripening that is thought of. 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 (1) a silver halide solvent of 0-5 to 2.0 mol/silver mol. 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 (111) plane or a (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. ．． Organic thioethers described in No. 157, No. 3,531.289, No. 3,574.628, JP-A-54-1019, JP-A-54-158917, and JP-B No. 58-30571, (b) JP-A-53-82408, JP-A No. 55-2982
Thiourea derivatives described in No. 9 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-53-144319; , (d) Japanese Patent Publication No. 54-100
Imidazoles described in No. 717, (e) sulfites, (f) thiocyanates, (g) ammonia, (h)
Ethylenediamines substituted with hydroxyalkyl described in JP-A-57-196228, (i) JP-A-57-196228;
Substituted mercaptotetrazoles described in No. 7-202531, (j) water-soluble bromide, (k) JP-A-58-5
Examples include benzimidazole derivatives described in No. 4333.

Next, HO of these silver halide solvents (a) to (k)
CH, CH, SCH, CH, SCH, CH, 0)ICH
2NHCOCH, CH2C00H CH, 5Ct1. CH, SC! Hs CHxlJHCOCxHt CHzSCHxCH2SCHtCH2COOH(e) K1SO3,KazSOs (f) NH,SCN, l[scN (g) NHl (h) (HOCHzCHz)zNcHzcHzN(CH2CF
IzOH)z(CzHi)zNcHzcHzN(CHz
CLOH)z(j) NaBr, NH4Br, 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 10-' to 1 mole of silver halide.
It is used in a range of 2 moles.

Moreover, the pH is 3 to 13. Temperature: 30-70℃
is preferable, particularly preferably pH 6-12 and temperature 35-12.
The temperature range is 50°C.

One example of a preferred embodiment of the present invention is pH 10,
8-11.2, ammonia 0.4- at temperature 35-45℃
1.0 mole/(l and potassium bromide 0.03-0.5 mo4
An emulsion containing seed particles suitable for ripening for 30 seconds to 10 minutes was obtained.

During the seed particle forming step of the present invention, a water-soluble silver salt may be added for the purpose of modulating the ripening.

The seed grain growth process for enlarging silver halide seed grains involves pAg, p 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.

The conditions for enlarging the seed particles obtained in the present invention are as follows:
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 method is to gradually change the amount within a range. 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 Proceedings of the 1981 Annual Conference of the Photographic Society of Japan, 88, but the former The method is preferred.

In the production of the silver halide emulsion of the present invention, the growth conditions for silver halide grains are pH 6 to 12. Preferably, the temperature is 40 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 halide aqueous solution by a double jet method. or,
The modified state 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 the speed to 200 rpm+m.

In the photosensitive material of the present invention, normal crystal grains are used together with the twin crystal grains.

The normal crystal particles include cubic, octahedral, tetradecahedral,
Alternatively, spherical particles are preferably used.

Among these, any ratio of the (100) plane to the (111) plane can be used in normal crystal grains other than spherical ones.

The surface ratio of the grains in the silver halide emulsion is as follows:
It can be measured by line diffraction method.

Using Cu as a target and the Ka line of Cu as a radiation source, the (100) plane of silver halide, with a tube current of 10lA,
When we measured the diffraction pattern of the (110) plane and then the (111) plane, the diffraction angle (2θ) was in the range of 29 to 33 degrees (
A diffraction peak (A) for the 100) plane appears, and the diffraction angle (
A diffraction peak (B) corresponding to the (110) plane appears in the range of 2θ) from 43 to 47 degrees.

Furthermore, the diffraction angle (2θ) is in the range of 53 to 57 degrees (11
1) A diffraction peak (C) corresponding to the surface appears. Based on the respective diffraction peak intensities, an arbitrary surface ratio can be determined by the following calculation formula.

(Example) Calculation of (100) surface ratio (%) 1; Silver bromide (
The probability of appearance of the (100) side of silver bromide is 0.55; the probability of the appearance of the (100) side of silver bromide is 0.16.
; The appearance probability of the (100) plane of silver bromide, the (110) plane ratio, and the (Ill) plane ratio can also be determined in the same manner.

In the normal crystal emulsion, the (111) plane ratio is 20%.
The above is preferred, and more preferably 70% or more is used.

In addition, spherical silver halide grains are disclosed in Japanese Patent Application Laid-open No. 57182.
No. 730, No. 59-179344, No. 59-1784
As disclosed in No. 47, etc., it can be obtained by ripening in the presence of a silver halide solvent after the formation of silver halide grains is completed.

In the present invention, being spherical means that when focusing on the surface having the largest area among the polygons forming the outer shape of the silver halide grain, the length a is 1 when the longest side of the polygon is assumed. It is defined as having a roundness with a radius of curvature corresponding to /6Q-1/212 in the ridge portion of the polygon before sphericalization.

The roundness of grains can be determined by observing silver halide grains using an electron microscope.

The normal crystal grains of the present invention are preferably core/shell type grains.

Core/shell type grains consist of silver halide grains with a shell layer structure composed of two or more phases with different silver iodide contents, and the silver iodide content is between the inner core (the core and the core). Silver iodobromide, which has fewer surface shells (referred to as shells) than silver (referred to as shells), is preferred.

The silver iodide content of the inner core is preferably 6 mol% or more, more preferably 8 mol% or more, particularly preferably 10 mol% or more. The silver iodide content of the surface shell is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.
It is.

The volume occupied by the shell portion of the core/shell type silver halide grains is preferably 10 to 80%, more preferably 15 to 7%.
It is 0%.

Further, the volume occupied by the core portion is preferably 10 to 80% of the entire particle, and more preferably 20 to 50%.

In the present invention, when the core/shell type grain is silver iodobromide, the difference in content between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grain has a sharp boundary. It is also possible to have a boundary that is not necessarily clear and that changes continuously, but it is more preferable to have a sharp boundary. A multi-shell structure is also useful, and a core/shell structure having an intermediate shell having a silver iodide content intermediate between that of the core part and the surface well part is also preferably used.

When consisting of core/shell type silver halide grains having the intermediate shell, the volume of the intermediate shell is 5 to 60% of the entire grain;
Furthermore, 20 to 55% is better.

The difference in silver iodide content between the surface shell and the intermediate shell, and between the intermediate shell and the core is preferably 3 mol% or more, and the difference in the silver iodide content between the surface shell and the core is preferably 6 mol% or more.

The average silver iodide content of the normal crystal core/shell type silver halide emulsion that can be used in the present invention is preferably 4 to 20 mol%, more preferably 5 to 15 mol%.

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

The core/shell type emulsion used in the present invention is JP-A-59-1
77535, No. 60-138538, No. 59-522
No. 38, No. 60143331, No. 60-35726, No. 60-258536, and the like. Japanese Unexamined Patent Publication 1986-1385
It is preferable to grow a core/shell type silver halide emulsion starting from seed grains as described in the Example No. 38; in this case, the center of the grains should have a halogen composition region different from that of the core. is possible. In such a case, the silver halide composition of the seed grains can have any composition such as silver bromide, silver iodobromide, silver chloroiobromide, silver chlorobromide, silver chloride, etc. Silver iodobromide or silver bromide having a content of 10 mol % or less is preferred.

The volume of the seed grains in the total silver halide is preferably 50% or less, particularly preferably 10% or less.

Also preferably used is a method in which halogen substitution using iodide is carried out at a position such as immediately before or after the formation of the core or intermediate shell during the formation of the core/shell type grains.

The distribution state of silver iodide in the above-mentioned core/fel type silver halide grains can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures or by X-ray diffraction.

A known silver halide solvent such as ammonia, thioether, thiourea, etc. may be present during the growth of the core/shell type silver halide grains.

The core/shell type silver halide grains are treated with cadmium salt, cadmium salt,
Zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts)
By adding metal ions using at least one selected from the following, these metal elements can be contained inside the particles and/or on the surface of the particles, and by placing them in an appropriate reducing atmosphere, the inside of the particles and the metal elements can be contained. /Or reduction sensitizing nuclei can be added to the particle surface.

Unnecessary soluble salts may be removed from the core/shell type silver halide emulsion after the growth of silver halide grains is completed, or they may be left in the core/shell type silver halide emulsion. When removing the salts, please refer to Research Disclosure ar-(Re
seacb Disclosure (hereinafter abbreviated as RD) 1
This can be carried out based on the method described in No. 7643, Item (3).

The core/shell type/S silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The core/shell type silver halide grains may have a size of 0.1 to 10 μm, preferably 0.2 to 5 μm, particularly preferably 0.3 to 2 μm.

The core/shell type silver halide emulsion may have any grain size distribution. A polydisperse emulsion with a wide grain size distribution may be used, or a monodisperse emulsion with a narrow grain size distribution may be used. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used, but it is preferable to use monodisperse emulsions alone or in combination of two or more. The term "monodisperse emulsion" in an emulsion consisting of normal crystal grains has the same meaning as described above.

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

Antifoggants, stabilizing cocoons, etc. can be added to silver halide emulsions. 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 an emulsion consisting of the twin crystal grains of the present invention, and the remaining photosensitive layers At least one layer thereof contains an emulsion consisting of normal crystal grains.

In a further preferred embodiment, at least one of the photosensitive layers of the silver halide 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 has the present invention. At least one of the other layers contains an emulsion consisting of normal crystal grains.

In a further preferred embodiment, two or more types of photosensitive layers having different color sensitivities are provided on the support, and at least one of the photosensitive layers is
consists of two or more layers with the same color sensitivity but different sensitivities, in which at least one layer of the highest sensitivity layer contains an emulsion consisting of twin crystal grains of the present invention, and at least one layer of the lowest sensitivity layer contains an emulsion consisting of normal crystal grains. added.

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 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 may be provided with auxiliary layers such as a filter layer, a halation R stop layer, and an irradiation prevention 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.

For photosensitive materials, formalin scavenger! photobrightener,
A capping 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) A monodisperse spherical seed emulsion; Em-7 was prepared by the method disclosed in JP-A-61-6643.

Preparation of seed emulsion, ammonia water (28%) 70
B8 liquid and C4 liquid were added in 30 seconds to A1 liquid that was vigorously stirred at 5 va (140°C) by a double jet method to generate nuclei. At this time, pBr was 1.09 to 1.15.
Met.

1 minute and 30 seconds vkD1 liquid was added for 20 seconds and aged for 5 minutes. KBr concentration during ripening is 0.071 mol/+2,
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 μl and a distribution width of 18%.

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

Liquid B2 and liquid C2 were added to A2 which was vigorously stirred at 65° C. over 40.5 minutes by a double jet method. During this time, the pH was maintained at 2.0 and the pAg at 940 with nitric acid. The addition rate of B2 solution and C8 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 obtained at 40°C.

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 distribution width of 14%, and 88% of the projected area consisting of 100% (111) planes.

The average grain diameter/grain thickness ratio of the tabular silver halide grains was 3.6. The CuKa 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 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 the standard sample was 0.33 degrees (2θ).

Comparative Example 2 Using the above seed emulsion Em-7, the average grain volume was E m
- Same as A, average silver iodide content 8°0 mol%
A comparative emulsion Em-B, which is a monografted twin emulsion having a high silver iodide content phase inside the grains, was prepared.

Stir vigorously at 75°C. Liquid 83-1 and liquid C3-1 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 pAg was maintained at 8.0. The addition time was 45 minutes, and the addition rate was linearly increased to 1.9@ between the initial and final amounts. Next, in the same liquid, B, -2 liquid and 0
3-! The liquid was added by 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 was completed, the pI (pI) 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 to give a pAg of 8 at 40°C.
．． Emulsion No. 5 was obtained.

When the obtained emulsion was observed under an electron microscope, it was found to be a monodisperse tabular silver halide emulsion with an average grain size Q of 75 μm, a distribution width of 15%, and (100) and (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 emulsion Em-1 of the present invention) Using the above seed emulsion, the average grain volumes were Em-A and Em-B.
An emulsion Em-1 of the present invention was prepared, having the same volume as the above emulsion and having an average silver iodide content of 2.25 mol %.

8 by double jet method into A4 liquid stirred vigorously at 75℃.
4-, liquid and C3-1 liquid were added. At this time, the pH was maintained at 2.0 and I) Ag at 840 with nitric acid. The addition time was 16 minutes, and the addition rate was increased linearly from initial to final to 1.27. Next, in the same liquid, 84-2 liquid and C1-2
The liquid was added by double jet method. At this time, adjust the pH to 2.0.
I) Ag 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 at 40°C to obtain an emulsion with a pAg of 8.5 and a pH of 5.85.

When the obtained emulsion was observed under an electron 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% has a particle diameter/particle thickness ratio of 1.0 to 1.5, has (100) planes and (111) planes, and the ratio is 64:36.

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

Also, a line drawn perpendicularly from the highest peak and the peak height
Let the point where the horizontal lines intersect at O, 13 be B,
If AA' is a line drawn horizontally at peak height X O, 13 and cut by a signal, then AA' is B
AB:BA'-0,85:l.

(Preparation of emulsion Em-2 of the present invention) The above Em
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.

A.

B, - C8- C White solution A, same solution B, -1 same solution C4-1 and same solution C4-! The same obtained emulsion as electronic 1B! When observed with a microscope, 10
The silver halide emulsion was composed of 0.09 mm twin grains, had an average grain size of 0.73 μm, and had 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 and had a (100) plane and a (111) plane, with a ratio of 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 maximum peak height x 0.13 was 0.820 degrees (2θ). Also, the point where the line drawn vertically from the highest peak intersects with the line drawn horizontally at peak height x 0.13 is designated as B, and the line segment where the line drawn horizontally at peak height x 0.13 cuts the signal is defined as B. When AA' is set, AA' becomes AB by B: B
It was divided into A'-0,86:l.

(Preparation of normal crystal emulsions Em-3, 4, 5 and 6) JP-A No. 5
Referring to the method of No. 9-1713447, the silver iodide content was 30 mol% in the core part, 0.1 mol% in the shell part, 5.0 mol% on average, and the average grain size was 0.27 μm1.The width of the distribution was 1
A monodisperse core/shell emulsion Em-3 consisting of 2% tetradecahedral grains was prepared.

Using the same method, the silver iodide content was determined to be 12 mol% in the core, 0.1 mol% in the shell, 2.5 mol% on average, and an average grain size of 0.27.
A monodisperse core/shell emulsion Em-4 consisting of tetradecahedral grains with a width of 12% and a distribution width of 12% was prepared.

Em using the same method except that the average particle size was 0.65μ
Em-5, which is the same as -3, was prepared. Furthermore, the silver iodide content was 40 mol% in the core part using the same method.

Shell part 0.5 mol% average 8.0 mol% average particle size 0.5 mol%
A monodisperse core/shell emulsion Em-6 consisting of 12% wide dodecahedral grains with a 65 μm 1 distribution was prepared.

<Sensitization treatment of each emulsion> Above silver halide emulsion E m A SE m B
%Em-1. Em2, Em-3, Em-4, Em
Appropriate amounts of sodium thiosulfur, chloroauric acid, and ammonium thiocyanate were added to each of Samples -5, Em-6, and Em-7, and chemical ripening was performed at 50°C. After chemical ripening, a sensitizing dye and a stabilizer, 4-=hydroxy-6-methyl-1.3.3a,7-chitrazaindeni/, were added.

Using these emulsions, the following multilayer color light-sensitive materials were 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 expressed in g/2.

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 1.0 Third layer (low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1,
AgBr1 (Agl
4. 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-1,5
-2) spectrally sensitized by AgBrI (Agl 2
．． 5 mol%, average particle size 0.6 μ+++) 0.8 Coupler C-11,0 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 (E m -
3) 0.6 force blur M-10
, 15 Coupler M -20,04 High boiling point solvent 0-3 0.5 Gelatin 1.4 No. 71 (high sensitivity green-sensitive halogenated emulsion layer) Green sensitizing dye (S-3,5
-4) is spectrally sensitized by t:AgBr1 (E
m-A)
0.9 force puller M-10,56 force blur M -20,12 high boiling point solvent 0-3 1.0 gelatin 1.5@8 layer (middle layer) 9th layer same as 5th layer (yellow filter layer) Yellow colloid ffi 0.
1 gelatin 0.9 2.5-di-t-octylhydroquinone 0.1
High boiling point solvent 0-1 0.2Lig
10 layers (low sensitivity)/silver halide emulsion layer) AgBr1 (A
gl 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 blue-sensitive silver halide emulsion layer) Blue sensitizing dye (5-5
) spectrally sensitized by AgBr1 (Agl 2.5
Mol%, average particle size 0.9 μ@) 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 light Absorbent U-20,4 2,5-di-t-octylhydroquinone 0.1
High boiling point solvent 0-3 0.6 Gelatin 1.2 13th layer: 2nd protective layer Average grain size (r) 0.08 μm 1 Non-photosensitive fine grain halide consisting of silver iodobromide containing 1 mol% of silver iodide silver emulsion
Silver amount 0.3 Polymethyl methacrylate particles (diameter 1.5 μm) 0.06 Surfactant S^ 0.004 Gelatin 0.7 In addition to the above composition, gelatin hardening agent (■) and surfactant are added to each layer. Added.

Ultraviolet absorber U ■ Ultraviolet absorber U Sensitizing dye S ■ Sensitizing dye S Sensitizing dye S Sensitizing dye S Sensitizing dye S 5 Coupler C Coupler M ■ Coupler M Coupler Y ■ Gelatin hardening agent H-1 Interface Activator SA- NaOs 5-C1ffC00CR! (CF!C
F! )! HCH, Cα)CHz(CFzCh),
H-1-3 C,H.

C2H* next, Table 1 shows the /% silver halide emulsion of the old 6th and 7th layers of sample l. ■Noyo Samples 102 to 110 were made by changing to sea urchin. accomplished.

After surface samples 101-110 were subjected to forced deterioration treatment at 40° C. and RH 80% for 7 days, they were subjected to the following development treatment after wedge exposure using white light at the same time as the untreated samples.

Processing process Processing time Processing temperature First development
6 minutes 38・C water washing
2〃〃Reversal
21/〃Color development 6〃
〃Adjustment 2〃l/Bleach [3tt
tt fixed 4 //
ttWash 4 〃
〃Stability l
〃 Room temperature drying The processing liquid composition used in the above processing step is as follows.First developer: Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate 30g Sodium carbonate (monohydrate) 1-phenyl-4-methyl-4-hivirazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and invert Liquid! -Trilotrimethylenephosphonic acid 6-sodium salt Stannous chloride (dihydrate) Sodium p-aminophenol hydroxide Add glacial acetic acid water to develop color developer Sodium tetrapolyphosphate 0g Droxymethyl-3-g 2.5g 1.2g 5f2 1O00IIQ g g O,1g g 15a 1000mff Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide Potassium iodide (0.1% solution) 90mQ
Sodium hydroxide 3g Nthradinic acid 1.5g N-ethyl-N
-β-methanesulfonamidoethyl-3-methyl-4-
Aminoaniline sulfate ug 2.2-ethylenedithiogetanol Add 1g water to 1000a + 72 Adjustment Liquid sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) g Thioglycerin 0.4m (2 glacial acetic acid 3-12 water In addition, l000++ff drift
White Liquid sodium ethylenediaminetetraacetate (dihydrate) g Iron ethylenediaminetetraacetate (I [[) Ammonium (2
water salt) 120g ammonium bromide Add 100g water
1000s12 Liquid ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Add water
1000m4 Constant liquid formalin (37% by weight) 5■a Konidax (manufactured by Konica Corporation) 5.12 Add water
The density of each sample subjected to the 1000 mff development process was measured using a densitometer model 310 manufactured by X-Rite and a Status A filter. The measurement results using green light show that fog increases due to forced deterioration treatment (this example is a reversal photosensitive material, so this appears as a decrease in maximum density)8
and sensitivity value (sensitivity of sample 101 without forced aging treatment is set to 1)
00) was calculated and shown in Table 2.

Note that the sensitivity value was calculated and obtained at a density of 1.8 determined by green light measurement.

Stability Table 2 This example shows that storage stability was improved when an emulsion consisting of twin crystal grains of the present invention was added to the high-speed layer and an emulsion consisting of normal crystal grains was used in the low-speed layer. . high sensitivity layer,
In the case of an emulsion consisting of normal crystal grains in both the low-speed layer, the storage stability is affected by the silver iodide content of the low-speed layer emulsion, and the sensitivity increases due to changes in the height of the high-speed layer emulsion. However, it can be seen that the storage stability deteriorates and is not preferable.

[Example-2] Em-A, B and Em-1~7 used in Example-1 were made into red-sensitive emulsions by using a red-sensitive sensitizing dye, and the third emulsion of sample 101 of Example-1 was prepared. Regarding the layer and the fourth layer, samples 201 to 210 were prepared in the same manner as in Example-1. Hereinafter, the same forced deterioration treatment and exposure as in Example-1 were performed, and the density of the obtained sample was measured and evaluated using red light, and the same effects as in Example-1 were observed.

[Example-3] Em-A, B, and Em-1 to Em-7 used in Example-1 were made into a blue-sensitive emulsion by using a blue-sensitive sensitizing dye, and the 1st θ of sample 101 of Example-1 was Sample 301 was prepared in the same manner as Table 1 of Example 1 for the layer and the 11th layer.
~310 were produced. Hereinafter, the same forced deterioration treatment and exposure as in Example-1 were performed, and the density of the obtained sample was measured and evaluated using blue light, and the same effects as in Example-1 were observed.

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 consisting of silver twin grains, the silver halide emulsion being monodisperse, Cu
The (420) X-ray diffraction signal using Kα radiation as the radiation source has a unique peak, and the maximum peak height is x 0.13.
A silver halide photographic emulsion in which a silver halide photographic emulsion having a diffraction line width of less than 1.5 degrees at a diffraction angle (2θ) is added to at least one of the light-sensitive layers, and the silver halide photographic emulsion is composed of silver halide normal crystal grains. A silver halide color photographic material, characterized in that the following is added to at least one of the remaining photosensitive layers.