JPH08171159A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material high in sensitivity and improved in pressure desensitization and superior in the high illuminance irregularity of reciprocity rule. CONSTITUTION: This silver halide color photographic sensitive material has at least one silver halide emulsion layer on a support, and at least one of the emulsion layers contains flat silver halide grains occupying >=50% of the projection areas of the total silver halide grains and having an even number of twin crystal faces parallel to principal crystal faces and an average aspect ratio of >=2, and >=10 dislocation lines per each one grain and containing at least one kind of multivalent metal compound near the dislocation line introduced part and having a silver iodide content of <=6mol% in the surface of each grain measured by the X-ray photoelectron spectrophotometry.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide emulsion useful in the field of photography and a silver halide color photographic light-sensitive material using the emulsion. More specifically, it relates to a silver halide color photographic light-sensitive material having high sensitivity, improved pressure desensitization, and excellent high illumination failure characteristics.

[0002]

2. Description of the Related Art In recent years, performance requirements for silver halide emulsions for photography have become more and more stringent, and high sensitivity, low fog,
There is a demand for higher standards for photographic characteristics such as high image quality.

In connection with the trend toward higher sensitivity and higher image quality, the demand for improving the pressure characteristics of silver halide color photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) is increasing more than ever before. . Although it has been studied to improve the pressure characteristics by various means, the technique of improving the stress resistance of the silver halide grains themselves is better than the technique of using an additive such as adding a plasticizer. The view that it is practically preferable and that the effect is large is influential.

In response to these demands, emulsions comprising core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied. In particular, a silver iodobromide emulsion containing a core / shell type grain having a high silver iodide content phase of 10 mol% or more inside the grain has attracted much attention as an emulsion for a color negative film, for example.

Techniques for improving pressure characteristics with core / shell type particles include, for example, JP-A-59-99433 and JP-A-60-357.
No. 26, JP-A-60-147727, the technology disclosed is known.

Further, JP-A-63-220238 and JP-A-1-201
No. 649 discloses a technique for improving graininess, pressure characteristics and exposure illuminance dependency with high sensitivity by introducing dislocations into silver halide grains.

Further, a metal doping technique is known as a technique for controlling charge carriers (carriers) such as free electrons and holes in silver halide grains. For example, it has been reported by Leubner that an electron-trapping property is exhibited when a silver halide is doped with an iridium complex. (The Journal of Photographic Science Vol.31,9
3 (1983)). Further, for example, JP-A-3-15040 discloses an iridium ion-containing emulsion in which iridium ions do not exist on the grain surface and a method for producing the same. Further, for example, in JP-A-6-175251, there is a technique that makes both sensitivity at 1/100 second exposure and reciprocity law failure characteristics compatible with in-plane epitaxy type grains to which an iridium compound is added during the silver halide grain manufacturing process. It is disclosed.

However, these conventional techniques have not been satisfactory as a silver halide color photographic light-sensitive material having high sensitivity, improved pressure desensitization, and excellent high illumination failure characteristics.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is improved in the above problems and has a high sensitivity, an improved pressure desensitization and a high illuminance failure characteristic. To do.

[0010]

The above object of the present invention can be achieved by the following constitutions.

In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains contained in at least one of the silver halide emulsion layers are At least 50% or more of the total projected area is composed of tabular silver halide grains having an average aspect ratio of 2 or more having an even number of twin planes parallel to the principal plane, and each grain has 10 dislocation lines. Or more, and the grains contain at least one polyvalent metal compound in the dislocation line introduction portion, and the silver iodide content on the grain surface measured by X-ray photoelectron spectroscopy is 6 mol% or less. A silver halide color photographic light-sensitive material characterized by being present.

The present invention will be described in detail below.

The silver halide grains according to the present invention have dislocation lines. Dislocation lines are, for example, JF Hamilton, Pho
t.Sci.Eng.vol11, 57 (1967) and T.Shiozawa J.Soc.Pho
It can be observed by a direct method using a transmission electron microscope at low temperature described in t.Sci.Japan vol.36 213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample is taken to prevent damage (printout etc.) due to electron beam. Observation is carried out by the transmission method in the state of being cooled. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-pressure electron microscope (200 KV or more for particles having a thickness of 0.25 μm).

From the photograph of the grains obtained by such a method, the position and the number of dislocations of each grain when seen from the direction perpendicular to the principal plane can be obtained.

In the present invention, the center of a silver halide grain means that silver halide microcrystals are dispersed in a methacrylic resin in the same manner as the method shown in the abstracts of Inoue et al. A circle when a solidified, ultrathin section with a microtome has the maximum cross-sectional area or a section sample with a cross-sectional area of 90% or more than that, and the minimum circumscribed circle is drawn for the cross-section Is the center of.

In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn from the center of the circle to the outside.

The dislocation line of the silver halide grain in the present invention is 0.58 L from the center of the silver halide grain toward the outer surface.
It occurs in the area of up to 1.0 L, but preferably 0.80
It occurs in the region of L to 1.0L. The direction of the dislocation line is approximately the direction from the center to the outer surface, but it often meanders.

Regarding the number of dislocation lines in the silver halide grains according to the present invention, 50% is the number of grains containing 10 or more dislocation lines.
It is preferable that the number (number) or more is present. More preferably
It is preferable that 80% (number) or more of particles containing 10 or more dislocation lines are present, and particularly preferably 80% (number) or more of particles containing 20 or more dislocation lines.

In the present invention, the silver iodide content and the average silver iodide content of individual silver halide grains are determined by the EPMA method (Electr.
on Probe Micro Analyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and elemental analysis of a minute portion can be performed as compared with X-ray analysis by electron beam excitation by irradiating an electron beam.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodine emitted from each grain. If the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

The silver halide grains according to the present invention preferably have a more uniform iodide content between grains.
When the iodide content distribution between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

The silver iodide content on the surface of the silver halide emulsion of the present invention can be measured by X-ray photoelectron spectroscopy.

In X-ray photoelectron spectroscopy, prior to the measurement, the emulsion is pretreated as follows. First, about 1 ml of emulsion
Then, 10 ml of 0.01 wt% pronase aqueous solution is added, and gelatin is decomposed by stirring at 40 ° C. for 1 hour. Next, the emulsion particles are settled by centrifugation to remove the supernatant, 10 ml of an aqueous solution of pronase is added, and gelatin is decomposed again under the above conditions. After centrifuging this sample again and removing the supernatant, 10 ml of distilled water is added to redisperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. This washing operation
After repeating three times, the emulsion grains are redispersed in ethanol (the work up to this point is performed in a dark room). This is thinly coated on a mirror-polished silicon wafer in a dimly lit room to obtain a measurement sample. The sample coated on the silicon wafer is measured by X-ray photoelectron spectroscopy within 24 hours.

For measurement by X-ray photoelectron spectroscopy, an ESCA / SAM560 type manufactured by PHI is used as an apparatus. The sample is fixed to a 60-degree tilt holder, evacuated for 10 minutes using a turbo molecular pump in the sample pre-evacuation chamber, and then introduced into the measurement chamber. Within 1 minute after sample introduction, excitation X-ray (Mg-K
Irradiation of (α-ray) is started, and measurement is started immediately. Measurement is X-ray source voltage 15kV, X-ray source current 40mA Pass energy 50
Perform under eV conditions.

Ag3d, Br for determining the surface halide composition
3d, I3d3 / 2 electrons are detected. To detect Ag3d electrons, scan the binding energy range from 381 eV to 361 eV.
2eV, 100msec for each step, and for detection of Br3d electrons, total energy 79eV to 59eV for scan step 0.2eV, 100msec for each step, 5 measurements, I3d3
To detect / 2 electrons, a total energy range of 644 eV to 624 eV is measured at 0.2 eV scan steps and 100 msec at each step 40 times. The data is obtained by repeating the above operation twice.

The integrated intensity of each peak is used to calculate the composition ratio. The integrated intensity of the Ag3d peak is 4e in the intensity of the energy value obtained by adding 4eV to the total energy at which the Ag3d3 / 2 peak shows the maximum value and the binding energy at which the Ag3d5 / 2 peak shows the maximum value.
The straight line connecting the intensities of the added V is taken as the baseline, and the integrated intensity of the Br3d peak is 4eV in the total energy at which the Br3d5 / 2 peak shows the maximum value.
The straight line connecting the intensity of the added energy value and the intensity of the energy value obtained by subtracting 3eV from the total energy at which the Br3d5 / 2 peak shows the maximum value is calculated with cps · eV as the base line, and the integrated intensity of the I3d3 / 2 peak is 4 from the intensity of the energy value obtained by adding 4 eV to the total energy at which the I3d3 / 2 peak shows the maximum value, and the total energy at which the I3d3 / 2 peak shows the maximum value.
The straight line connecting the intensities of the energy values reduced by eV is used as the baseline, and cps · eV is used as the unit.

When the composition ratio is calculated from the integrated intensity of each peak, the relative sensitivity coefficient method is used and Ag3d, Br3d, I3d3
By using 5.10, 0.81, and 4.592 as the relative powers of / 2, the composition ratio is given in atomic percent. I mole percent is determined by dividing the atomic percent value of I by the atomic percent value of Br and the atomic percent value of I.

The silver iodide content on the surface of the silver halide grains according to the present invention by the above-mentioned measuring method is 6 mol% or less, preferably 4 mol% or less.

The silver halide grains according to the present invention are tabular halogens in which at least 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion layer has an even number of twin planes parallel to the principal plane. The average aspect ratio of the tabular silver halide grains is 2 or more, preferably 2 to 20, and more preferably 4 to 16. The average aspect ratio is an average value of aspect ratios (average particle diameter / particle thickness ratio).

The silver halide grains according to the present invention may be any such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution. It may be a mixture of several emulsions. When a light-sensitive material is prepared using the silver halide grains of the present invention, it is preferably a monodisperse emulsion.

As the monodisperse silver halide emulsion, the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. A certain amount is preferable, more preferably 70% or more, further preferably 80% or more.

[0032] Here, the average particle diameter r is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, the minimum Digits are rounded to 4).

The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of a non-spherical grain whose projected image is converted into a circular image of the same area. Is.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (measurement). The number of particles shall be indiscriminately 1000 or more).

A particularly preferred highly monodisperse emulsion of the present invention is one having a distribution width of 20% or less when defined by (standard deviation / average grain size) × 100 = distribution width [%]. It is more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

As a method for obtaining a monodisperse emulsion, two or more reaction elements arbitrarily selected from a water-soluble silver salt solution, a water-soluble halide solution and silver halide fine particles in a gelatin solution containing seed particles. Can be obtained by adding under the control of pAg and pH. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of tetrazaindene disclosed in JP-A-60-122935 can be applied.

The silver halide grain of the present invention contains at least one polyvalent metal compound in the dislocation line introduction portion.

Here, the terms used in the present invention are defined, but "doping" or "doping" means containing a substance other than silver ions or halide ions in the silver halide grains.

The term "dopant" refers to compounds that dope silver halide grains. The term "metal dopant" refers to a polyvalent metal compound that is doped in silver halide grains.

The preferred content of metal dopant in the silver halide grains of the present invention is 10 ^-9 per mol of silver halide.
It is ^-10 to 10 ^-4 mol, more preferably 10 ^-8 to 10 ^-5 mol.

As the metal dopant, Mg, Al, Ca,
Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Sr, Y,
Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, Sn, Ba, Ce, Eu,
Metal compounds such as W, Re, Os, Ir, Pt, Hg, Tl, Pb, Bi and In can be preferably used.

The polyvalent metal compound to be doped is preferably selected from a single salt or a metal complex. When selected from a metal complex, a hexacoordinate, a pentacoordinate, a tetracoordinate, and a bicoordinate complex are preferable, and an octahedral hexacoordinate and a plane tetracoordinate complex are more preferable. The complex may be a mononuclear complex or a polynuclear complex. As the ligand that constitutes the complex, CN ^-, C
O, NO ₂ ^-, 1,10-phenanthroline, 2,2'-bipyridine,
SO ₃ ^-, ethylenediamine, NH _3, pyridine, H ₂ O, NCS ^-,
NCO ⁻ , O ₃ ⁻ , SO ₄ ⁻ , OH ⁻ , N ₃ ⁻ , S ₂ ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , I ^{− and the} like can be used.

As a particularly preferred metal dopant, K ₄
Fe (CN) ₆ , K ₃ Fe (CN) ₆ , Pb (NO ₃ ) ₂ , K ₂ IrCl ₆ , K ₃ IrCl ₆ , 2I
Examples include rBr ₆ and InCl ₃ . The distribution of silver halide grains of the metal dopant is obtained by gradually dissolving the grains from the surface to the inside and measuring the dopant content of each portion. The following method can be given as a specific example.

Prior to metal determination, the silver halide emulsion is pretreated as follows. First, 0.2% in about 30 ml of emulsion
Add 50 ml of aqueous actinase solution and stir at 40 ° C for 30 minutes to decompose gelatin. This operation is repeated 5 times. After centrifugation, washing with 50 ml of methanol 5 times, 50 ml of 1N nitric acid 2 times, and ultrapure water 5 times were repeated. After centrifugation, only silver halide was separated. The surface portion of the obtained silver halide grains is dissolved with an aqueous ammonia solution or with pH-adjusted ammonia (ammonia concentration and pH are changed according to the type and dissolution amount of silver halide). Of the silver halide, the method for dissolving the extreme surface of the silver bromide grain is 2 g
On the other hand, about 20% of 10% aqueous ammonia solution can be used to dissolve about 3% from the particle surface. At this time, the amount of silver halide dissolved is determined by centrifuging the aqueous solution of silver after dissolution of the silver halide and the silver halide, and measuring the amount of silver present in the resulting supernatant by a high frequency induction plasma mass spectrometer ( ICP-MS) High-frequency plasma emission spectrometer (I
CP-AES) or atomic absorption.

From the difference between the amount of metal contained in the silver halide after surface dissolution and the total amount of metal not dissolved, the amount of metal per mol of silver halide present at about 3% of the grain surface is determined. You can ask. Quantitative determination of metals was performed by dissolving in ammonium thiosulfate aqueous solution, sodium thiosulfate aqueous solution, or potassium cyanide aqueous solution, and matrix matching ICP-MS.
Method, ICP-AES method, or atomic absorption method. Of these, potassium cyanide as the solvent and IC as the analyzer
When P-MS (FISON Elemental Analysis) is used, about 40 mg of silver halide is dissolved in 5 ml of 0.2N potassium cyanide, and then the internal standard element Cs solution is added to 10 ppb, and the mixture is made up to 100 ml with ultrapure water. The sample with a fixed volume is used as the measurement sample. Then, the metal in the measurement sample is quantified by ICP-MS using a calibration curve in which the matrix is combined with metal-free silver halide. At this time, the accurate amount of silver in the measurement sample was diluted 100 times with ultrapure water and the measurement sample was diluted with ICP-AE
It can be quantified by S or atomic absorption. After such dissolution of the grain surface, the silver halide grain is washed with ultrapure water, and the dissolution of the grain surface is repeated in the same manner as described above to obtain a metal in the inner direction of the silver halide grain. Quantitation of quantity can be performed.

The polyvalent metal ion contained in the silver halide grain according to the present invention exists in a region of 0.80L to L from the center of the silver halide grain toward the outer surface. Preferably, it exists in the region of 0.9 to 0.99L.

A known silver halide solvent such as ammonia, thioether or thiourea may be present during the production of the silver halide grains according to the present invention, or the silver halide solvent may not be used.

The silver halide grains according to the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium.

Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed by gelatin or another substance that can form a hydrophilic colloid (a substance that can serve as a binder), and is preferably a colloid. An aqueous solution containing a protective gelatinous form.

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

Hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacryl Acid, polymethacrylic acid,
There are various types of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers.

In the case of gelatin, it is preferable to use one having a jelly strength of 200 or more in the Paggy method.

The silver halide grain according to the present invention is at least one selected from cadmium salt, zinc salt, lead salt, thallium salt and iridium salt (including complex salt) in the step of forming and / or growing the grain. A metal ion can be added by using a seed so that these metal elements can be contained inside and / or on the surface of the particle, and by placing in a suitable reducing atmosphere, reduction sensitization inside and / or on the surface of the particle can be carried out. Can give a nucleus.

The silver halide grain according to the present invention may be either a grain in which a latent image is mainly formed on the surface or a grain in which the latent image is mainly formed. The size of silver halide is 0.05 to 5.0. μm, preferably 0.1-
It is 3.0 μm.

The silver halide grains according to the present invention may be those in which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or they may be contained as they are.

Further, as in the method described in JP-A-60-138538, it is possible to carry out desalting at any point of silver halide growth. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II. More specifically, in order to remove the soluble salts from the emulsion after the formation of a precipitate or after the physical ripening, a Nudel water washing method performed by gelling gelatin may be used,
Alternatively, a precipitation method (flocculation) using an inorganic salt, an anionic surfactant, an anionic polymer (for example, polystyrene sulfonic acid), or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide grains according to the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization,
A selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a gold or other noble metal compound can be used alone or in combination.

The silver halide grain according to the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more kinds. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye is included in the emulsion. May be.

Antifoggants, stabilizers and the like can be added to the silver halide grains of the present invention. It is advantageous to use gelatin as the binder. The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

A coupler is used in the emulsion layer of the light-sensitive material. Further, by a coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during development processing may be contained.

Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, optical brighteners, surfactants, development accelerators and development retarders can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0066]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Preparation of Twin Crystal Emulsion T-1] By the following method.
A seed emulsion having two parallel twin planes was prepared.

Ocein gelatin 80.0 g Potassium bromide 47.4 g A HO (CH ₂ CH ₂ O) m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) 10 weight % Methanol solution 0.48 ml Finish with distilled water to 8000.0 ml B Silver nitrate 1200.0 g Finish with distilled water to 1600.0 ml Ocein gelatin 32.2 g C Potassium bromide 823.8 g Potassium iodide 23.45 g Finish with distilled water to 1600.0 ml D Ammonia water 470.0 The liquid B and the liquid C were added to the liquid A stirred vigorously at 40 ° C. for 7.7 minutes by the double jet method to generate nuclei. During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Furthermore, the D liquid was added in 1 minute, and the aging was continued for 5 minutes. The KBr concentration during aging was 0.03 mol / l, and the ammonia concentration was 0.66 mol / l.

After completion of the aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. A 10% by weight aqueous gelatin solution was added to the desalted emulsion, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and distilled water was added to the emulsion to give 5360 g of an emulsion.

When the seed emulsion grains were observed with an electron microscope, they were tabular grains having two twin planes parallel to each other.

The average grain size of the seed emulsion grains was 0.295 μm, the average aspect ratio was 5.0, and the number of grains having two parallel twin planes was 80% (number ratio) of all grains.

[Preparation of Emulsion EM-1 of the Present Invention] 8 shown below
The tabular emulsion EM-1 of the present invention was prepared using various kinds of solutions.

(Solution A) ossein gelatin 67.0 g distilled water 3176.0 ml HO (CH ₂ CH ₂ O) m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) 10% by weight methanol solution 2.50 ml Seed emulsion (T-1) 98.51 g Finish with distilled water to 3500 ml (Solution B) 3.5N silver nitrate aqueous solution 4606 ml (Solution C) Potassium bromide 1915.1 g Ocein gelatin 200 g Finish with distilled water to 4606 ml (Solution D) Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) (*) 2465.5 g * The preparation method is shown below.

6.0% by weight containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution of 10 ml over 10 minutes. The pH during fine particle formation is 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

(Solution E) 1.75N potassium bromide aqueous solution 500 ml (Solution F) Fine particles composed of silver bromide grains (average particle diameter 0.04 μm) prepared in the same manner as the silver iodide fine grain emulsion described in Solution D. Emulsion 1127.7 g (however, the temperature during the formation of fine particles was controlled at 30 ° C.) (Solution G) K ₂ IrCl ₆ 0.829 mg Nitric acid (specific gravity 1.38) 0.50 ml 25% by weight aqueous NaCl solution to make 50.0 ml (Solution H) Solution A was added to a 100 ml reaction vessel containing an aqueous solution containing 29.3 g of potassium iodide, and the solution B to
Solution D was added according to the combination shown below by the simultaneous mixing method to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, the addition rates of (1) solution B, solution C and solution D, and (2) addition rates of solution B and solution C are set so as to correspond to the critical growth rate of silver halide grains. However, the addition rate was controlled so as to prevent polydispersion due to generation of small particles and Ostwald ripening other than growing seed crystals.

When the growth grain size was 1.42 μm, the addition of the solutions B, C and D was stopped, and the solution H was added at a constant rate over 1 minute. Then, after aging for 5 minutes, the addition of solutions B, C and D was started again.

When the growth grain size is 1.585 μm, the solution G
Was rush added (at this time, solutions B and C were being added).

Further, the temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. pA
Solution E was added as needed for g control.

The grain size at that time with respect to the addition time of the reaction solution and the silver iodide content of the silver halide phase forming the surface are shown below.

When the growth grain size was 1.648 μm, the addition of solutions B and C was completed, desalting was carried out according to the method described in JP-A-5-72658, and then gelatin was added and redispersed at 50 ° C. for 20 minutes. Then, add solution F at a constant rate over 20 minutes, and add 50 more
Redispersion was continued for 30 minutes at ° C. Then, cool down to 40 ℃ and p
The H was adjusted to 5.80 and the pAg was adjusted to 8.06. From an electron micrograph of the obtained emulsion grains, it was confirmed that the grains were tabular grains having an average grain size of 1.668 μm, an average aspect ratio of 5.0 and a grain size distribution of 18.0%.

Addition solution Addition time Grain size Silver iodide content (min) (μm) (mol%) (1) B, C, D 0.00 0.295 2.0 0.01 0.296 10.0 43.28 0.556 10.0 76.85 0.677 10.0 83.00 0.787 10.0 100.90 1.058 10.0 110.10 1.134 10.0 125.00 1.300 10.0 133.80 1.420 10.0 (2) H 139.80 1.420 (3) B, C, D 139.81 1.420 10.0 149.10 1.536 10.0 167.20 1.551 10.0 (4) B, C 167.21 1.552 0.0 174.70 1.585 0.0 182.11 1.620 0.0 187.30 1.648 0.0 Further, in the method of preparing the emulsion EM-1, the growth grain size was 1.16.
At the time of 8 μm, Solution H was added, followed by ripening for 5 minutes, and thereafter, Emulsion EM-2 was prepared by the same preparation method as Emulsion EM-1.

Further, in the method for preparing the emulsion EM-1,
Emulsion EM-3 was prepared at the growth grain size of 1.450 μm by the same preparation method as emulsion EM-1, except that solution G was rushed.
It was created.

Furthermore, in the method of preparing the emulsion EM-1,
The amount of solution F added was reduced to 1/2, and thereafter the emulsion EM-
Emulsion EM-4 was prepared by the same preparation method as in 1.

Further, in the method of preparing the emulsion EM-1,
Solution H was added at the growth grain size of 0.751 μm, and then 5
After ripening for a minute, thereafter, Emulsion EM-5 was prepared by the same preparation method as Emulsion EM-1.

Furthermore, in the method of preparing the emulsion EM-1,
Emulsion EM-6 was prepared by the same preparation method as Emulsion EM-1 except that Solution G was rush added at the growth grain size of 1.00 μm.
It was created.

Furthermore, in the method of preparing the emulsion EM-1,
Desalting is not carried out at the growth particle size of 1.648 μm, and the solutions B and C are continuously added as they are, and after growing to 1.668 μm, desalting is carried out. Further, the solution F is not added during high temperature dispersion after desalting. Otherwise, the emulsion EM-1 was prepared in the same manner as the emulsion EM-1.
-7 was created. Furthermore, in the method for preparing the emulsion EM-7, the addition of the solutions G and H was not carried out, and otherwise the emulsion EM-
Emulsion EM-8 was prepared in the same manner as in 7.

The preparation conditions of the emulsions EM-1 to EM-8 and the obtained results are summarized in Table 1.

[0090]

[Table 1]

As can be seen from Table 1, the emulsions EM-1 to EM-7 to which the solution H was added during the growth of silver halide grains were
Occurrence of 10 or more dislocation lines was found.

Further, it can be seen that the surface silver iodide content of the grains changes depending on the addition amount of the solution F after desalting.

Example 2 (Preparation of Light-Sensitive Material Sample) Emulsions EM-1 to EM-8 were optimally subjected to gold-sulfur sensitization, and these emulsions were used to show the following on a triacetyl cellulose film support. Each layer having such a composition was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

In all the following descriptions, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide.

The constitution of the multilayer color photographic light-sensitive material sample-1 (using the emulsion EM-1 of the present invention) is as follows.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High Boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye ( SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) ) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer: medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C -1) 0.33 color Dosian coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: high sensitivity red sensitive layer Emulsion EM-1 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10
^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 6th layer: Intermediate compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-5) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye ( SD-7) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Color Doma Zenta coupler (CM-2) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: high sensitivity green sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^-5 Sensitizing dye (SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta Coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 12th layer : Low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point Medium (OIL-2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD -11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 DIR compound (D-6) 0.02 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average) Grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling solvent (OIL-1) 0.07 High boiling solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd Protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Agent Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and a preservative D
I-1 was added.

The emulsions used for the above samples are as follows. Each emulsion was optimally gold and sulfur sensitized.

[0098]

[Table 2]

The diameter and thickness in the table are the diameter and thickness of each silver halide grain.

[0100]

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[0101]

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[0102]

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[0103]

[Chemical 4]

[0104]

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[0105]

[Chemical 6]

[0106]

[Chemical 7]

[0107]

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[0108]

[Chemical 9]

[0109]

[Chemical 10]

[0110]

[Chemical 11]

As for the emulsions EM-2 to EM-8, as shown below, by using each of these emulsions in place of the emulsion EM-1 of the sample-1, the multilayer color photographic light-sensitive material samples 2 to 8 were similarly obtained. It was created.

Sample name 2 3 4 5 6 7 8 Emulsion used EM-2 EM-3 EM-4 EM-5 EM-6 EM-7 EM-8 Each of the obtained samples was given a usual wedge exposure,
Development processing was performed according to the following processing steps.

Processing Steps 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Settling 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Dryness 50 ° C or less The composition of the treatment liquid used in each treatment step is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid ammonium ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter and pH was adjusted with ammonia water.
Adjust to = 6.0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

Each of the obtained samples was subjected to the usual wedge exposure for sensitometry (1/100 second), and the relative sensitivity, pressure desensitization characteristic and high illuminance failure characteristic of the red-sensitive layer were evaluated.

The relative sensitivity was 23 ° C. after the preparation of the photosensitive material sample.
A sample stored at a relative humidity of 55% for 24 hours was exposed for 1/100 second, and color development processing was started to obtain the relative value of the reciprocal of the exposure amount giving a density of Dmin (minimum density) +0.15.
The value is shown with the sensitivity of 100 as 100 (the smaller the value, the lower the sensitivity).

High illuminance sensitivity is 23 after the preparation of the photosensitive material sample.
Samples stored for 24 hours at 55 ° C and 55% relative humidity were exposed for 1/10000 seconds, color development processing was started, and the relative sensitivity of Sample 101 was set to 1
The relative sensitivity of each sample was calculated for the value of 00.

The pressure desensitization was carried out under the conditions of 23 ° C. and 55% (relative humidity) by using a scratch strength tester (manufactured by Shinto Kagaku Co., Ltd.) and applying a load of 5 g to a needle having a tip radius of curvature of 0.025 mm. After scanning at a constant speed by applying, exposure and development processing is performed, and the density change (ΔDp) of the portion to which a load is applied at the density of Dmin + 0.4 is obtained,
The value is shown with the value of ΔDp of Sample 101 being 100 (the smaller the value with respect to 100, the better the improvement).

The results are shown below.

Sample Name Invention / Red Sensitive Layer Comparative Comparison Relative Sensitivity Pressure Sensitivity High Illuminance Sensitivity 101 Invention 100 100 100 102 Invention 101 115 103 103 Invention 99 99 91 104 Invention 92 100 98 105 Comparative 98 160 98 106 Comparative 99 98 75 107 Comparative 63 99 98 108 Comparative 65 211 58 As is apparent from the results shown above, Samples 101 to 104 of the present invention containing the emulsion of the present invention have high sensitivity and high sensitivity. Illumination failure and pressure desensitization are improved.

Among these, it is understood that the sample 101 using the emulsion EM-1 which satisfies the best combination of the present invention is particularly excellent.

On the other hand, the sample 105 using the emulsion EM-5 having the dislocation lines extremely introduced into the grains and the sample 108 using the emulsion EM-8 having no dislocation lines introduced had the pressure desensitization characteristics. It can be seen that it has deteriorated significantly. Further, the sample 106 using the emulsion EM-6 in which Ir ions were extremely introduced into the grains and the sample 108 using the emulsion EM-8 in which no Ir ions were added had the high illuminance failure characteristics significantly deteriorated. .
Furthermore, sample 107 and emulsion EM-8 using emulsion EM-7 to which solution F (silver bromide fine grain emulsion) after desalting was not added
It can be seen that the sample 108 using No. 1 has a large desensitization at 1/100 second exposure.

As described above, according to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material having high sensitivity, excellent illuminance failure and pressure desensitization characteristics.

[0127]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material according to the present invention has high sensitivity, improved pressure desensitization, and can produce an image excellent in high illuminance failure characteristic.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide contained in at least any one of the silver halide emulsion layers. At least 50% or more of the total projected area of the grains is composed of tabular silver halide grains having an average aspect ratio of 2 or more having an even number of twin planes parallel to the principal plane, and the number of dislocation lines per grain of the grains. Is 10
Or more, and the grains contain at least one polyvalent metal compound in the dislocation line introduction portion, and the silver iodide content on the grain surface measured by X-ray photoelectron spectroscopy is 6 mol% or less. A silver halide color photographic light-sensitive material characterized by being present.