JPH10123649A - Silver halide photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly sensitive emulsion with low level of fog and excellent granularity by containing a sliver chloride bromide or silver iodide bromide grain having a specified quantity of silver chloride area to the total silver quantity, and containing a metal ion. SOLUTION: This photographic emulsion contains a silver chloride bromide or silver iodide bromide chloride grain having a silver chloride area of 0.3 mole % or more and 50 mole % or lower to the total silver quantity and containing at least one ion of the group consisting of ions of Ga, In and metals of the eighth group to the tenth group. Namely, the emulsion grain is formed of silver chloride bromide or silver iodide bromide chloride containing the silver chloride area, preferably, formed of silver iodide bromide chloride. Since the fluctuation coefficient of distribution of grain size is preferably 20% or less in case of silver iodide bromide chloride, the silver iodide bromide content is preferably 7 mole % or less and 1 mole % or more. When not only the metal ions of the eighth group to the tenth groups but also ligand complexes of Ga<3+> and In<3+> are used as dopant, an effective shallow electron trap can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide emulsion, and more particularly, to a silver halide emulsion containing silver halide grains having a silver chloride region.

[0002]

2. Description of the Related Art In the field of color photographic light-sensitive materials, especially color reversal light-sensitive materials often used by professional photographers,
A color photosensitive material having high sensitivity is required for shooting a scene such as a sports photograph requiring a high shutter speed or a stage photograph where it is difficult to obtain a sufficient amount of light for exposure. However, since the current high-sensitivity color photographic light-sensitive materials have coarse grains, it has been desired to improve the relationship between the sensitivity and the graininess.

Various techniques can be used to increase the sensitivity of silver halide emulsions. As a metal doping technique, silver bromide grains and iodobromide are effective in increasing sensitivity by forming grains in the presence of various metals that become shallow electron traps (SET) in the grains and doping the grains. Silver particles are disclosed in U.S. Pat. No. 4,937,180 and the like, and a system having a composition of silver chloride of 50 mol% or more and silver iodide of 5 mol% or less is disclosed in U.S. Pat. No. 4,945,035. ing. In addition, by doping a metal complex having a shallow electron trap into ultra-thin silver iodobromide grains formed on the grain surface by epitaxial growth containing silver chloride,
No. 5,503,970 and US Pat.
No. 1.

[0004]

The present inventors have studied the halogen composition of silver halide and the technique of metal doping as disclosed in the above publications and confirmed the effects of increasing sensitivity and increasing contrast. However, further studies and improvements are needed to achieve the currently targeted high sensitivity level without deteriorating graininess.

Accordingly, it is an object of the present invention to provide a high-sensitivity silver halide photographic emulsion having a low level of fog and excellent graininess.

[0006]

Means for Solving the Problems The present inventor has found that sensitivity /
A study was conducted in search of a photographic emulsion having excellent fog ratio and sensitivity / granularity ratio. As a result, US Pat. No. 4,937,18
As disclosed in Nos. 0 and 4,945,035, a complex having a cyan ligand having a shallow electron trap is used as a metal compound to be contained in grains, and a silver halide region having a different halogen composition from a silver halide region is used. It has been found that the presence of this complex near the interface is most effective for the above purpose, and the present invention has been completed.

That is, the present invention provides the following silver halide photographic emulsion.

(1) 0.3 mol% or more of the total silver 5
Silver chlorobromide or iodine having a silver chloride region of 0 mol% or less and containing Ga, In, and at least one ion of a group 8, 9, and 10 metal ion; A silver halide photographic emulsion comprising silver bromochloride grains, (2) the emulsion according to (1), wherein the grains contain silver iodide in an amount of 1 mol% to 7 mol%.
(3) The emulsion is characterized in that the emulsion has a parallel (111) plane as a main plane and 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 3 or more. Or (2) the emulsion according to (2), wherein the particles are
Ga, In, and 8th are locally added to the interface of the silver chloride region.
The emulsion according to any one of (1) to (3), wherein the emulsion contains at least one ion from the group consisting of ions of metals belonging to Group 9, Group 9, and Group 10.
(5) The emulsion according to any one of (1) to (4), wherein the silver chloride region is present on the outermost surface of the grain, and (6) the ion of the metal is an eighth. (1) to (1) to (1) to (9), which are ions of a metal belonging to Group 9, 9 or 10 and which exist as a metal complex having 1 to 6 CN ^- ligands with the ion of the metal as a central metal. (5) The emulsion according to any one of (1) and (7), wherein the metal complex is a 6-cyano complex.
The emulsion according to any one of (1) to (6).

Hereinafter, the present invention will be described in detail.

The emulsion grains are made of silver chlorobromide or silver iodobromochloride containing a silver chloride region, preferably silver iodobromochloride. In the case of silver iodobromochloride, since the coefficient of variation of the grain size distribution is preferably 20% or less, the silver iodide content is preferably 7 mol% or less and 1 mol% or more. The silver iodide distribution of the emulsion grains may have a structure in the grains,
It may be uniformly distributed in the particles. By reducing the silver iodide content, it becomes easy to reduce the variation coefficient of the grain size distribution of the grain emulsion. The coefficient of variation of the distribution of the silver iodide content between grains is preferably 20% or less, more preferably 10% or less.
% Or less is preferable. Emulsion grains of the present invention may be regular grains such as cubic and octahedral or tabular grains,
Tabular grains are most preferred.

The tabular grain emulsion preferably occupies 50% or more of the total projected area by grains having an aspect ratio of 3 or more. Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference. Tabular grains are usually hexagonal, triangular or circular when viewed from above with respect to the main plane,
The value obtained by dividing the equivalent diameter of a circle having an area equal to the projection area by the thickness is the aspect ratio. The shape of the main plane of the tabular grains is 6
The higher the ratio of the polygons, the better, and the ratio of the lengths of the adjacent sides of the hexagon is preferably 1: 2 or less.

Since the effect of the present invention is more remarkable as the aspect ratio is higher, more preferably 50% or more of the total projected area of the tabular grain emulsion is occupied by grains having an aspect ratio of 5 or more. Most preferably, 50% or more of the total projected area has an aspect ratio of 8 or more. However, if the aspect ratio is too large, the coefficient of variation of the grain size distribution tends to increase. The following is preferred. In the emulsion grains of the present invention, the diameter of a circle having an area equal to the projected area is 0.15 μm to 1.80.
μm.

In the present invention, a preferred tabular grain emulsion comprises parallel (111) principal planes and side faces connecting the principal planes, and at least one twin plane exists between the principal planes. In the tabular grain emulsion of the present invention, two twin planes are usually observed. The distance between the two twin planes is described in U.S. Pat. No. 5,219,7 (hereinafter sometimes abbreviated as "US").
As described in No. 20, it can be smaller than 0.012 μm. Furthermore, as described in JP-A-5-249585, the value obtained by dividing the distance between the (111) main planes by the twin plane spacing can be 15 or more.

When a photon is absorbed by the silver halide grains, electrons (hereinafter referred to as "photoelectrons") are promoted from the valence band of the silver halide crystal lattice to its conduction band, and holes are formed in the valence band. (Hereinafter referred to as “photohole”). In order to create latent image sites within the grains, multiple photoelectrons generated in a single imagewise exposure must reduce some silver ions in the crystal lattice to form small clusters of Ag atoms. The photographic sensitivity of the silver halide grains is reduced to the extent that photoelectrons are dissipated by a competing mechanism before a latent image can be formed. For example, if the photoelectrons return to the photohole, their energy is dissipated without contributing to latent image formation.

It is conceivable to form a shallow electron trap inside the particle which contributes to more efficient use of photoelectrons for forming a latent image. This means that the face-centered cubic lattice is replaced by the ion (s) replaced in the crystal lattice.
Is achieved by introducing a dopant that exhibits a net valency that is more positive than the net valency of For example, in the simplest form possible, the dopant can be a polyvalent (+2 to +5) metal ion that replaces a silver ion (Ag ⁺ ) in the crystal lattice structure.

For example, when a monovalent Ag ⁺ cation is replaced by a divalent cation, a crystal lattice having a local net positive charge remains. This locally reduces the energy of the conduction band. The amount by which the local energy of the conduction band is reduced is described in J. Mol. F.
Hamilton, Advances in Phy
sics, 37 (1988), 395, and E
xcitonic Processes in Sol
ids, M.C. Ueta, H .; Kanazaki, K .; K
obayasi, Y .; Toyozawa and E.I. Han
amura, (1986), Spri, Berlin
It can be estimated by applying an effective mass approximation as described on page 359, published by Nger-Verlag.

If the silver chloride crystal lattice structure receives a net positive charge of +1 by doping, the energy of its conduction band is reduced by about 0.048 electron volts (eV) near the dopant. With a net positive charge of +2, the shift is about 0.192 eV. In the case of the silver bromide crystal lattice structure, the net positive charge +1 imparted by doping locally reduces the conduction band energy by about 0.026 eV. If the net positive charge is +2, the energy drop is
It is about 0.104 eV.

When the absorption of light produces photoelectrons, the photoelectrons are attracted by the net positive charge at the dopant site and are temporarily retained (ie, bound or trapped) at the dopant site with a binding energy equal to the local reduction in conduction band energy. Is done. Dopants that cause a local deflection of the conduction band to lower energies may have "binding energy" to hold (trap) photoelectrons at the dopant site that is insufficient to permanently store the electrons at the dopant site. It is called "shallow electron trap". Nevertheless, shallow electron trapping sites are useful. For example, a very large number of photoelectrons generated by high-illumination exposure can be temporarily held in a shallow electron trap so that they are not immediately dissipated, while taking a certain amount of time to efficiently place latent image formation sites. To be able to move to.

In order for the dopant to be useful in forming a shallow electron trap, it simply provides a net valence that is more positive than the net valency of the ion or ions being replaced in the crystal lattice. More than one further criterion must be met. When the dopant is incorporated into the silver halide crystal lattice, a new electron energy level (orbit) is formed near the dopant, in addition to the energy level or orbit consisting of the valence electrons and conduction band of the silver halide. For a dopant to be useful as a shallow electron trap, these additional criteria must be satisfied: (1) its highest energy electron occupied molecular orbitals;
orbital: HOMO; also commonly referred to as "frontier orbits"). For example, if a trajectory can hold two electrons (the highest possible number), it must contain two electrons instead of one. (2) The lowest energy unoccupied orbit (Lowest energy
Unoccupied molecularorbital (LUMO) must have an energy level higher than the lowest energy level conduction band of the silver halide crystal lattice. If conditions (1) and / or (2) are not satisfied, the crystal lattice (unfilled HOMO or LUM) may be at an energy lower than the local dopant induced conduction band minimum energy.
O) has a local dopant-derived orbit and preferentially retains the photoelectrons in this low-energy site, thereby preventing efficient movement of the photoelectrons to the latent image forming site.

The metal ion that most satisfies the criterion (1) is F
ions of metals belonging to Group 8 such as e, Ru and Os; Group 9 such as Co, Rh and Ir; and Group 10 metals such as Ni, Pd and Pt (hereinafter referred to as “Group 8 metal ions”). Name)
Met. It has been found that these metal ions cannot form effective shallow electron traps when incorporated as bare metal ion dopants. This is due to the fact that LUMO has an energy level lower than the lowest energy level conduction band of the silver halide crystal lattice.

However, when a coordination complex of Ga ³⁺ and In ³⁺ is used as a dopant in addition to these Group 8 metal ions, an effective shallow electron trap can be formed. The requirement that the frontier orbitals of the metal ions be satisfied satisfies the criterion (1). For satisfactory criterion (2), at least one of the ligands forming the coordination complex must be more electron withdrawing than the halide (ie, the halide ion with the highest electron withdrawing property). Must be more electron withdrawing than fluorine ions).

One common method for evaluating electron withdrawing properties is Inorganic Chemistry: Pr.
includes of Structure and
Reactivity, James E.L. Huhee
y, 1972, Harper and Row, New York and Absorption Spectra an
d Chemical Bonding in Com
plexes, C.I. K. Jorgensen, 1962
Reference is made to the spectrochemical series of the ligands obtained from the absorption spectra of the metal ion complexes in solution referred to in Pergamon Press, London, 2005. As is clear from these references, the order of ligands in the spectrochemical series is as ^{follows: I - <Br - <S} 2- <SCN - <Cl - <NO 3 - <
^{F - <OH <ox 2- <} H 2 O <NCS - <CH 3 CN
_{^{- <NH 3 <en <dipy}} <phen <NO 2 - <p
hosph << CN ^- <CO.

The abbreviations used are as follows: ox
= Oxalate, en = ethylenediamine, dipy =
Dipyridine, phen = o-phenatroline, and ph
osph = 4-methyl-2,6,7-trioxa-1-
Phosphabicyclo [2.2.2] octane. In the spectrochemical series, the ligands are in electron-withdrawing order, with the first (I ⁻ ) ligand in the series being the least electron-withdrawing and the last (CO) ligand being the most electron-withdrawing. . The ability of the ligand to increase the LUMO value of the dopant complex is that the ligand atom that binds to the metal is Cl
It increases as it changes in the order of S, O, N, C. Thus, the ligands CN ^- and CO are particularly preferred. Other preferred ligands are thiocyanate (NCS ^-),
Selenocyanate (NCSe ^-), cyanate (NCO
^-), tellurocyanate (NCTE ^-) and azide (N
₃ ^-) it is.

Just as the spectrochemical series can be applied to ligands of coordination complexes, they can be applied to metal ions. The spectrochemical series of the following metal ions is Absorbtio
nSpectra and Chemical Bon
ding, C.I. K. Jorgensen, 1962,
Pergamon Press, reported in London: Mn ²⁺ <Ni ²⁺ <Co ²⁺ <Fe ²⁺ <C
r ³⁺ , V ³⁺ (substantially the same as Cr ³⁺ ) <Co ³⁺ <Mn ⁴⁺ <M
o ³⁺ <Rh ³⁺ , Ru ²⁺ (substantially the same as Rh ³⁺ ) <Pd ⁴⁺ <
Ir ³⁺ <Pt ⁴⁺ This does not include all metal ions specifically intended for use in the coordination complex as dopants, but the position of the remaining metals in the spectrochemical series depends on the period of the element. As the position of the ions in the table increases from the fourth period to the fifth and sixth periods, the position of the ions in the series is the smallest electronegative metal M
It can be confirmed from the shift from n ⁺² to the metal Pt ⁺⁴ having the largest electronegative property. That is, Os ²⁺ which is the sixth cycle ion is more electronegative than ion Pd ^{+ 4} which is the most electronegative in the fifth cycle, but ion Pt ^{+ 4 which} has the smallest electronegative in the sixth cycle. Electronegative is smaller than that.

From the above description, Rh ³⁺ , Ru ²⁺ , Pd ⁴⁺ ,
Ir ³⁺ , Os ²⁺ and Pt ⁴⁺ are particularly preferred metal ions because they are obviously the most electronegative metal ions that satisfy the frontier orbital requirement (1). In order to satisfy the LUMO requirement of the criterion (2), a charged frontier orbital polyvalent metal ion of Group VIII is incorporated into a ligand-containing coordination complex. At least one, most preferably at least three, optimally at least four of these are more electronegative than the halide, and the remaining ligand (s) are halide ligands. When a metal ion such as Os ²⁺ is itself very electronegative, only a single large electronegative ligand such as carbonyl is required to satisfy LUMO requirements. If the metal ion itself is relatively electronegative, such as Fe ^+2, then selecting one in which all of the ligands are highly electronegative can be done by LUM
It is necessary to satisfy O requirement. For example, Fe (I
I) (CN) ₆ is a specifically preferred shallow electron trapping dopant. Indeed, coordination complexes containing six cyano ligands are representative of a generally preferred preferred class of shallow electron trapping dopants.

Ga ³⁺ and In ³⁺ are H as bare metal ions.
OMO and LUMO requirements can be satisfied,
When incorporated into a coordination complex, it can contain ligands ranging in electronegativity from halide ions to more electronegative ligands that are useful for Group VIII metal ion coordination complexes. In the case of Group VIII metal ions and ligands with intermediate levels of electronegativity, certain metal coordination complexes satisfy LUMO requirements, and therefore, metals and ligand electronegativities that serve as shallow electron traps Can be easily determined as to whether they contain the appropriate combination of This can be done by using electron paramagnetic resonance (EPR) spectroscopy. This analytical technique is widely used as an analytical method, and Electron S
pinResonance: A Comprehens
live Treatment on Expertimen
tal Technologies, 2nd edition, Charles
sP. Poole, Jr. (1983), Jone
Wiley & Sons, New York.

The photoelectrons in the shallow electron trap produce an EPR signal very similar to that observed for photoelectrons at the conduction band energy level of the silver halide crystal lattice. EPR signals from shallowly captured electrons or conduction band electrons are referred to as electronic EPR signals. Electronic EP
The R signal is characterized by a parameter commonly called the g-factor. A method for calculating the g-factor of an EPR signal is described in the above C.I. P. It is described in Poole. The g-factor of the electron EPR signal in the silver halide crystal lattice depends on the type of halide ion (s) near the electron. That is, R.I. S. Eachus,
M. T. Olm, R.A. Jane and M.S. C. R. Sym
ons, Physica Status Solidi
(B), Volume 152 (1989), 583-592
As reported by the page, the g-factor of the electronic EPR signal in AgCl crystals is 1.88 ± 0.001 and the g-factor of the electronic EPR signal in AgBr is 1.4.
9 ± 0.02.

The coordination complex dopant forms a shallow electron trap in the practice of the present invention if it enhances the magnitude of the electronic EPR signal by at least 20% in the test emulsion described below as compared to the corresponding undoped control emulsion. It is found to be useful for Undoped control emulsions are described in U.S. Pat. No. 4,937,180 (Marchetti).
Etc.) as described for Control 1A, with an edge length of 0.45 ± 0.05 μm precipitated (but
(No further sensitization is carried out). M
archetti et al. in Example 1B [Os (CN
₆ )] except that instead of ^4- , a metal coordination complex is used at the concentration intended for use in the emulsions of the invention.
Test emulsions are prepared similarly.

After the precipitation, each liquid emulsion is first centrifuged,
Prepare test and control emulsions for electronic EPR signal measurement by removing the supernatant, replacing the supernatant with an equal volume of warm distilled water, and resuspending the emulsion. This operation is repeated three times, and after the final centrifugation step, the obtained powder is air-dried. These operations are performed under safe light conditions. The EPR test is to cool three samples of each emulsion to 20, 40 and 60 ° K, respectively, expose each sample to filtered light from a 200 WHg lamp with a wavelength of 365 nm and measure the EPR electronic signal during exposure Performed by If at any of the selected viewing temperatures, the intensity of the electronic EPR signal increases significantly in the doped test emulsion sample relative to the undoped control emulsion (ie,
If it increases measurably above the signal noise), the dopant is a shallow electron trap.

As a specific example of the test performed as described above,
A commonly used shallow electron trap dopant [F
e (CN) ₆ ] ^4- was added at a concentration of 50 × 10 ⁻⁶ mole per mole of silver during precipitation as described above,
The R signal strength was increased by a factor of 8 when tested at 20 ° K compared to the undoped control emulsion. Hexa coordination complexes are preferred coordination complexes for use in the practice of the present invention. These complexes contain a metal ion and six ligands that replace silver ions and six adjacent halide ions in the crystal lattice. One or two of the coordination sites
Although it can be occupied by neutral ligands such as carbonyl, aquo or amine ligands, the remainder of the ligand must be anionic to facilitate efficient incorporation of the coordination complex into the crystal lattice structure. Examples of hexa-coordination complexes are described in U.S. Pat. No. 5,037,732 (McDuggle et al.), U.S. Pat. No. 4,937,1.
Nos. 80, 5,264,336 and 5,268,264 (Marchetti)
Et al.), U.S. Pat. No. 4,945,035 (Kee
vert, etc.) and Japanese Patent Application No. 2-249588 (M
urakami). Useful neutral and anionic organic ligands for hexacoordination complexes are disclosed in U.S. Patent No. 5,360,712 (Olm et al.). Through careful scientific investigation, R.E. S. Eachu
s, R.S. E. FIG. Graves and M.E. T. Olm, J.M. C
hem. Phys. 69, 4580-7 (1
978) and Physica Status Sol
idi A, Vol. 57, pp. 429-37 (1980)
It has been found that the Group VIII hexahalo coordination complex forms a deep (desensitized) electron trap, as described in (1).

In a particular preferred embodiment, it is intended to use as a dopant a hexacoordination complex satisfying the following formula (IV):

(IV) [ML ₆ ] ⁿ (where M is a charged frontier orbital polyvalent metal ion, preferably Fe ²⁺ , R
u ²⁺ , Os ²⁺ , Co ³⁺ , Rh ³⁺ , Ir ³⁺ , Pd ⁴⁺ or Pt ⁴⁺ ; L ₆ represents _six independently selectable coordination complex ligands With the proviso that at least four of the ligands are anionic ligands and at least one (preferably at least three and optimally at least four) of the ligands is more electronegative than any halide ligand; and n ² -, 3 ^- or 4
^- .

Specific examples of dopants that can provide a shallow electron trap are as follows: SET-1 [Fe (CN) ₆ ] ^4- SET-2 [Ru (CN) ₆ ] ^4- SET-3 [Os (CN) ₆ ] ^4- SET-4 [Rh (CN) ₆ ] ^3- SET-5 [Ir (CN) ₆ ] ^3- SET-6 [Fe (pyrazine) (CN) ₅ ] ^4- SET-7 [ RuCl (CN) ₅ ] ^4- SET-8 [OsBr (CN) ₅ ] ^4- SET-9 [RhF (CN) ₅ ] ^3- SET-10 [IrBr (CN) ₅ ] ^3- SET-11 [FeCO ( CN) ₅ ] ^3- SET-12 [RuF ₂ (CN) ₄ ] ^4- SET-13 [OsCl ₂ (CN) ₄ ] ^4- SET-14 [RhI ₂ (CN) ₄ ] ^3- SET-15 [IrBr ₂ (CN) _4] ^3- SET-16 [Ru (CN) ₅ (OCN)] ^4-SET- 7 _{[Ru (CN) 5 (N 3} ) ] ^4-SET-18 [Os (CN) ₅ (SCN)] ^4-SET-19 [Rh (CN) ₅ (SeCN)] ^3- SET-20 [Ir ( CN) ₅ (HOH)] ^2- SET-21 [Fe (CN) ₃ Cl ₃ ] ^4- SET-22 [Ru (CO) ₂ (CN) ₄ ] ^2- SET-23 [Os (CN) Cl ₅ ] ^4- SET-24 [Co (CN) ₆ ] ^3- SET-25 [Ir (CN) ₄ (oxalate)] ^3- SET-26 [In (NCS) ₆ ] ^3- SET-27 [Ga (NCS) ₆ ^3- ) Further, US Pat. No. 5,024,931 (Ev
and the use of oligomeric coordination complexes to increase speed (sensitivity) is also contemplated.

The dopants are effective at normal concentrations, where the concentrations are based on the total silver in the grains. Generally, it is intended that the shallow electron trap-forming dopant be incorporated at a concentration of at least 1 × 10 ^-6 mole per silver mole to the solubility limit (typically a concentration of about 5 × 10 ^-4 mole per silver mole or less). Is done. The preferred concentration is
The range is from about 10 ^-5 to 10 ^-4 mole per silver mole. The effect of the dopant is enhanced by locally disposing the dopant in the silver chloride region or at a latent image forming site at the interface between the silver chloride region and the silver bromide layer or the silver iodobromide layer.

In order to produce the grains of the emulsion of the present invention,
Separate methods known per se, such as forming tabular grains, depositing silver chloride regions on tabular grains,
This can be achieved by combining a method of forming a shallow electron trap in a particle, a method of incorporating a metal dopant in a particle, and the like.

The silver chlorobromide or silver iodobromochloride tabular grain emulsions preferred in the present invention can be prepared by various methods. Preparation of host tabular grain emulsions is usually
It consists essentially of three steps: nucleation, ripening and growth.
Here, host grain means silver bromide or silver iodobromide grains on which silver chloride is to be deposited. In the step of nucleation, US Pat. No. 4,713,320 and US Pat.
Use of gelatin having a low methionine content described in No. 120, high pBr described in US Pat. No. 4,914,014.
The nucleation in a short time described in JP-A-2-222940 is extremely effective in the nucleation step of tabular grain emulsion preferred in the present invention. The aging step is performed in the presence of a low-concentration base described in US Pat. No. 5,254,453, US Pat.
Performing at a high pH described in No. 41 may be effective in the ripening step of the host tabular grain emulsion of the present invention. In the growth step, the growth is performed at a low temperature described in US Pat. No. 5,248,587, and US Pat. No. 4,672,027.
And the use of silver iodide fine grains described in US Pat. No. 4,693,964 are particularly effective in the step of growing emulsion grains of the present invention.

In the step of producing the emulsion grains of the present invention, after the growth step of silver bromide or silver iodobromide host grains during the formation of silver iodobromide or silver bromide grain emulsions, a silver chloride region is formed on the surface of the host grains. Is deposited in an amount of from 0.3 mol% to 50 mol%, based on the total silver halide of the finished grains. Preferably, 0.5 mol% to 20 mol% is deposited. Most preferably, 0.75 mol% to 10 mol% is deposited. The deposition of silver chloride is preferably performed in the presence of a spectral sensitizing dye. The deposition site is most preferably the outermost surface of the emulsion grains of the present invention. In this case, silver chloride may be uniformly deposited on the entire surface of the host grain as the outermost layer, but in the case of tabular grains, it is deposited intensively at the edge. It is preferable to deposit intensively on corners. Methods for depositing silver chloride regions at specific locations are described, for example, in US Pat. No. 4,463,08.
No. 7.

The silver halide emulsion of the present invention contains a dopant that can increase photographic speed by forming a shallow electron trap. The dopant can be incorporated in the silver chloride region or at the interface between the silver chloride region and the silver iodobromide or silver bromide layer. When the silver chloride region is not on the outermost surface of the grain, the interface between the silver chloride region and the silver iodobromide layer or silver bromide layer in the center direction (inside) of the grain is opposite to the center of the grain ( It may be an interface with the silver iodobromide layer or the silver bromide layer on the inside. Most preferably, a dopant is incorporated at the interface between the silver iodobromide layer or the silver bromide layer and the silver chloride region. Here, the “interface” is opposite to the center of the grain from the position in the center direction of the 200 angstrom grain from the position where the silver chloride region contacts the other region and from the position where the silver chloride region contacts the other region from the position where the silver chloride region contacts the other region. Direction up to 200 angstroms.

The metal compound to be doped into the emulsion grains of the present invention is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent. To stabilize the solution, an aqueous solution of hydrogen halide (eg, HCl, HBr, etc.) or an alkali halide (eg, KCl, NaCl, KB)
r, NaBr, etc.). If necessary, an acid or alkali may be added.
The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, it can be added to a water-soluble silver salt (eg, AgNO ₃ ) or an aqueous solution of an alkali halide (eg, an aqueous solution of NaCl, KBr, or KI, or a mixture of these aqueous solutions) and added continuously during the formation of silver halide grains. Further, a solution independent from the water-soluble silver salt and the aqueous alkali halide solution may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

In the present invention, a silver chloride fine grain emulsion having a metal dopant as described above may be added to the silver iodobromide or silver bromide host tabular grain emulsion to form a silver chloride region. In particular, when the silver chloride region is deposited uniformly or locally on the outermost surface of the host grains, it can be achieved by adding silver chloride fine particles to the post-ripening step (after the desalting step) after the formation of the host grains. The temperature of the system at the time of addition is 4
The temperature is preferably from 0 ° C to 90 ° C, particularly preferably from 50 ° C to 80 ° C.

The above silver chloride fine grain emulsion is preferably produced by a double jet addition method of a silver salt aqueous solution and a chloride salt aqueous solution, in which the grains are formed with a constant pAg value during grain formation. Here, pAg is the logarithm of the reciprocal of the Ag ⁺ ion concentration of the system. There are no particular restrictions on the temperature, pAg, pH, the type and concentration of protective colloid such as gelatin, the presence or absence, type, and concentration of a silver halide solvent. 10 μm or less is convenient for the present invention. The lower limit of the particle size is the manufacturing limit of 0.005 μm. Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less. The size and size distribution of the silver chloride fine particle emulsion are determined by placing silver chloride fine particles on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size. Particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver chloride fine particles in the present invention have a particle size of 0.10 μm or less and 0.08 μm.
As described above, the variation coefficient of the particle size distribution is 20% or less.

The silver amount of the layer grown after the formation of the silver chloride region is preferably from 0 to 50, when the silver amount of the host tabular grain emulsion is 100. More preferably, it is 0 or more and 30 or less. It is even more preferably 0 or more and 10 or less. Most preferably, it is 0. The halogen composition of the layer grown after forming the silver chloride region may be the same as or different from that of the host grains. The temperature, pH and pAg for forming this layer are not particularly limited, but the temperature is 40 ° C.
The temperature is usually 90 ° C. or less and the pH is 2 or more and 9 or less. More preferably, a temperature of 50 ° C. or more and 80 ° C. or less, and a pH of 3 or more and 7 or less are used.

In the emulsion grains of the present invention, the grains preferably have dislocation lines. The dislocation lines show KI during the grain formation.
By adding a solution and an AgNO ₃ solution or by adding (dumping) AgI fine particles, silver iodide is precipitated on the surface of the particles formed so far, and the lattice is incorrectly formed with silver halide thereafter. The introduction of dislocation lines contributes to higher sensitivity.

The dislocation lines of tabular grains are described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11,5
7, (1967); Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
(1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more on average per grain. More preferably, an average of 20 per particle
More than a book. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as the number average by counting the number of dislocation lines for 100 particles or more.

The tabular grains may have dislocation lines almost uniformly over the entire outer periphery or may have dislocation lines at local positions on the outer periphery. That is, in the case of hexagonal tabular silver halide grains, dislocation lines may be limited only to the vicinity of six vertices, or dislocation lines may be limited to only one of the vertices. Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices. Further, it may be limited to an outer periphery, a main plane, or a local position, or may be formed by combining these. That is, they may be present simultaneously on the outer periphery and on the main plane.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
16, P30 (1966), and enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The silver halide grains of the present invention may be subjected to at least one of noble metal sensitization such as sulfur sensitization, selenium sensitization, or gold sensitization or palladium sensitization, or reduction sensitization in the step of producing a silver halide emulsion. It can be applied in any process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. The emulsion of the present invention can select the location of the chemical sensitization nucleus according to the purpose,
Generally preferred is the case where at least one type of chemical sensitizing nucleus is formed near the surface.

One of the chemical sensitizations that can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described in TH James, The Photographic Process, Fourth Edition, Macmillan. Published, 1977
Year, (THJames, The Theory of the Photographic Proc
ess, 4th ed, Macmillan, 1977), using active gelatin, as described in pages 67-76, and by Research Disclosure, Vol.
Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, and 3; 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757;
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 mol to 1 × 10 ^-7 mol, more preferably 1 × 10 ^-5 mol to 5 × 10 ^-7 mol, per mol of silver halide.
The preferred range of the palladium compound is 1 × 10 ⁻³ mol to 5 × 10 ⁻⁷ mol. The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² mol to 1 mol.
× 10 ^-6 mol.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
The amount is from 10 ^-4 mol to 1 x 10 ^-7 mol, more preferably from 1 x 10 ^-5 mol to 5 x 10 ^-7 mol.

Selenium sensitization is a preferred sensitization method for the emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization. Selenium sensitization is most preferably used in combination with sulfur sensitization and noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method in which a reduction sensitizer is added to a silver halide emulsion, and pAg1 to silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-7 mol to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2Na
_{CO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2
Na ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxyacid salt (for example, K ₂ S ₂ O ₈ ), K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ )
, Peroxy complex compounds (for example, K ₂ [Ti (O ₂ )
C ₂ O _{4] · 3H 2 O, 4K 2 SO} 4 · Ti (O 2)
_{OH · SO 4 · 2H 2 O} , Na 3 [VO (O ₂₎ (C _{2
H 4) 2 · 6H 2 O} ), permanganate (e.g., KM
oxyacid salts such as nO ₄ ) and chromate (eg, K ₂ Cr ₂ O ₇ ); halogen elements such as iodine and bromine; and perhalates (eg, potassium periodate); For example, potassium hexacyanoferrate) and thiosulfonate.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B).

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitizer and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The emulsion of the present invention may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. , A negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is disclosed in
No. 133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28660 can be used. One of the preferred compounds is disclosed in
There is a compound described in JP-A-3-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye includes, as nuclei having a ketomethylene structure, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-2,4-dione nucleus, and thiazolidine-2,4-nucleus.
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862 and 4,026,707, British Patent Nos. 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-5
Nos. 2-110618 and 52-109925. The sensitizing dye is usually 1 × 10 ⁻⁵ mol / mol Ag.
１1 × 10 ⁻² mol / mol Ag can be added.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
It can be used at 10 ^-6 mol to 8 × 10 ^-3 mol,
More preferred silver halide grain size 0.2 to 1.2 μm
In the case of m, about 5 × 10 ⁻⁵ mol to 2 × 10 ⁻³ mol is more effective.

The various techniques and inorganic and organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same are generally described in Research Disclosure No. 308119 (19
89), No. 37038 (1995) can be used.

In addition to this, more specifically, for example,
The techniques and inorganic / organic materials which can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following portions of European Patent 436,938A2 and the patents cited below. I have.

Item Applicable part 1) Yellow coupler, page 137, line 35 to page 146, line 33, page 149, lines 21 to 23, 2) Magenta coupler, page 149, lines 24 to 28; European Patent No. 421,453A1, page 3, line 5 to page 25, line 3) Cyan Coupler, page 149, lines 29 to 33; European Patent 432,804A2, page 3, line 28 4) Polymer coupler, page 34, lines 34 to 38; EP 435,334A2, page 113, line 39 to page 123, line 37 5) Colored coupler 53 Page 42, line 137 to line 34, page 149, line 39 to line 45 6) Other functionality Page 7, line 1 to page 53, line 41, coupler 14 page 9, line 46 ~ Page 150, line 3; European Patent No. 35, 334A2, page 3, line 1 to page 29, line 7 7) Preservatives, fungicides, page 150, lines 25 to 28 8) Formalin scavenger, page 149, lines 15 to 17 9 ) Other additives, page 153, lines 38 to 47; EP 421,453A1, page 75, line 21 to page 84, line 56, line 27, line 40 to page 37, 40 Line 10) Dispersion method, page 150, lines 4 to 24 11) Support, page 150, lines 32 to 34 12) Film thickness / film properties Page 150, lines 35 to 49 13) Coloring Developing / Black and White, page 150, line 50 to page 151, line 47 Developing and fogging; Process 34 of EP 442,323 A2, page 11 to line 54, page 35, line 14 to line 22 Line 14) desilvering process, page 151, line 48 to page 152, line 53 15) Dynamic developer No. 152, line 54 to page 153, line 2 16) Washing and stabilizing step Page 153, lines 3 to 37 Hereinafter, the present invention will be described in more detail by way of examples. The invention is not limited to these. Example 1 Preparation of Emulsion Em-a 0.9 N of potassium bromide, 50 g of inert gelatin, and 4.5 g of ammonium nitrate dissolved in 1 L of distilled water were stirred well with 1N sodium hydroxide.
4 cc was added, and a 2.7% aqueous potassium bromide solution containing 0.16 g of potassium iodide in 100 cc and a 4% aqueous silver nitrate solution were added over 10 minutes by the double jet method. During this time, the temperature was kept at 72 ° C and the pAg was kept at 7.1. (This addition (1) consumed 10% of the total silver).
Subsequently, a 13.5% aqueous potassium bromide solution containing 0.8 g of potassium iodide in 100 cc by a double jet method, and
A 20% aqueous silver nitrate solution was added over a period of 37 minutes while maintaining the temperature at 72 ° C. and the pAg at 6.9 (70% of the total silver was consumed in this addition (2)). Further, a 13.5% aqueous potassium bromide solution containing 0.8 g of potassium iodide in 100 cc and a 20% aqueous silver nitrate solution were added by a double jet method over 10 minutes while maintaining the temperature at 72 ° C. and the pAg at 7.4 ( With this addition (3), 20% of the total silver
Consumed). Subsequently, the emulsion was washed with water by a known flocculation method at 35 ° C., and gelatin was added thereto to adjust the pH to 5.7 and the pAg to 8.6 at 40 ° C., and the average grain diameter was 0.40 μm. CuBr AgBrI (A
(gI = 4.0 mol%) Emulsion Em-a was obtained. Preparation of Emulsion Em-b In Em-a, emulsion Em-b was prepared by increasing the iodine amount in steps (2) and (3) so that AgI = 15 mol% in the whole grains. Emulsion Em-b was a cubic AgBrI having an average grain diameter of 0.41 μm (AgI = 15.
0 mol%). Preparation of Emulsion Em-c In Em-a, a 13.5% aqueous solution of potassium bromide containing 0.8 g of potassium iodide in 100 cc used in the process (3) (hereinafter referred to as “KBr solution” in Example 1) ) Was added 50% after 2% of SET-2 was added.
Emulsion Em-c was prepared in the same manner as in Em-a, except that an amount corresponding to ^-5 mol / mol Ag (mol per mol of the completed grains) was uniformly added by a KBr solution. Emulsion Em-c is a cubic AgBrI (AgI = 4.0 mol%) grain emulsion having an average grain diameter of 0.40 μm. Preparation of Emulsion Em-d In the case of Em-a, SET
-2 in an amount corresponding to 2 × 10 ^-5 mol / mol Ag in KBr
Emulsion Em-d was prepared in the same manner as Em-a except that the solution was uniformly added. Emulsion Em-d is a cubic AgBrI having an average grain diameter of 0.40 μm (AgI = 4.
0 mol%) grain emulsion. Preparation of Emulsion Em-e In Em-b, the addition of the KBr solution of (3) was 50%.
After proceeding, Em-2 was added except that SET-2 was uniformly added in an amount corresponding to 2 × 10 ⁻⁵ mol / mol Ag with a KBr solution.
Emulsion Em-e was prepared in the same manner as in -a. Emulsion Em-
e is a cubic AgB having an average particle diameter of 0.41 μm.
This is an rI (AgI = 15.0 mol%) grain emulsion. Preparation of Emulsion Em-f In Em-c, a NaCl solution (corresponding to 2 mol%) was added after the completion of the process (2), and then an AgNO ₃ solution (2 mol%) was added.
After the addition of the KBr solution of (3) has progressed by 50%, SET-2 was uniformly added in an amount corresponding to 2 × 10 ⁻⁵ mol / mol Ag with the KBr solution. Emulsion E so that the silver content of Emulsion E was the same as that of Em-c.
mf was prepared. Emulsion Em-f is a cubic AgClBrI (AgI =
(4.0 mol%, AgCl = 2.0 mol%). Preparation of Emulsion Em-g In Em-c, a NaCl solution (corresponding to 2 mol%) was added after the completion of the process (2), and then an AgNO ₃ solution (2 mol%) was added.
1%), and SET-2 was immediately added to 2 ×
An amount corresponding to 10 ⁻⁵ mol / mol Ag was added, and E was added thereto.
The process of (3) is continued similarly to the case of mc, and the total silver amount becomes E.
Emulsion Em-g was prepared in a manner similar to that of mc. Emulsion Em-g has an average grain diameter of 0.40 μm.
CuCl AgI (AgI = 4.0 mol%)
It is a grain emulsion. Preparation of Emulsion Em-h In Em-b, the NaCl solution (2
mol%), AgNO ₃ solution (corresponding to 2 mol%) was added, and SET-2 was immediately added to 2 × 10
An amount equivalent to ^-5 mol / mol Ag was uniformly added by a KBr solution, and then the process of (3) was carried out in the same manner as in Em-b so that the total silver amount became the same. Was prepared. Emulsion Em-h has an average grain diameter of 0.41 μm.
Is a cubic AgClBrI (AgI = 15.0 mol%) emulsion. Preparation of Agent Em-i A tabular emulsion (average aspect ratio: 4.5) having the same silver halide composition as Em-d was prepared and designated as Em-i. E
After forming a silver chloride layer as in the case of Em-d, SET-2 was rapidly and uniformly added in an amount corresponding to 2 × 10 ⁻⁵ mol / mol Ag using a KBr solution. Preparation of Emulsion Em-j An emulsion Em-j was obtained in the same manner as Em-i except that the metal to be doped in Em-i was set to SET-1. Preparation of Emulsion Em-k An emulsion Em-k was obtained in the same manner as Em-i except that the metal to be doped in Em-i was set to SET-5. Preparation of Emulsion Em-1 Emulsion Em-a was prepared by increasing the amount of iodine in the steps (2) and (3) so that AgI = 7 mol% in the whole grains. Emulsion Em-1 has a cubic AgBrI (AgI = 7.0) having an average grain diameter of 0.40 μm.
Mol%) of the emulsion. Preparation of Emulsion Em-m In Em-a, the NaCl solution (2
mol%), AgNO ₃ solution (corresponding to 2 mol%) was added, and SET-1 was immediately added to 2 × 10
An amount equivalent to ^-5 mol / mol Ag was uniformly added by a KBr solution, and subsequently the process of (3) was performed in the same manner as in Em-a so that the total silver amount was the same, and the average particle diameter was reduced. Cubic AgClBrI of 0.40 μm (AgI =
(7.0 mol%) of Em-m was prepared.

Table 1 shows the iodine content, the variation coefficient of the grain size, the chloride content, the metal doping amount and the metal doping position in the emulsions Em-a to Em-m.

[0079]

[Table 1] Emulsions Em-a to Em-m were optimally chemically sensitized with sodium thiosulfate, sodium chloroaurate and potassium thiocyanate in the presence of sensitizing dye S-4, and the following compounds were added, Coating was carried out together with a protective layer on a triacetylcellulose film support having an undercoat layer by a simultaneous extrusion method to obtain samples 101 to 113, respectively. The structural formula of the sensitizing dye S-4 is shown in Example 2 below. (1) Emulsion layer Emulsion Emulsion Em-a to Emulsion Em-m (Sample 101 to
113 stabilizer) ・ Stabilizer 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (2) Protective layer ・ Gelatin These samples were exposed to light through Fuji Filter SC50 for appropriate sensitometric exposure ( (1 second), and subjected to black-and-white development processing at 20 ° C. for 10 minutes using a developer having the following composition D-19. The composition of the treatment liquid is shown below. Metol _{2. 2g Na 2 SO 3 · 7H} 2 O 96 g height Bu hydroquinone _{8. 8g Na 2 CO 3 56 g} KBr 5. 1. 0 liters pH = 10.1 sensitivity by adding 0g water of the sum of fog and maximum density The value was defined as the reciprocal of the exposure amount giving half the density, and was shown as a relative value with the value of sample 101 being 100. The sensitivity and fog values are shown in Table 2 below.

[0080]

[Table 2] Table 2 shows that the sensitivity was increased by introducing a silver chloride layer containing a relatively small amount of iodine and doping the metal near the interface, and tabular grains were more effective. (Example 2) (Preparation of seed emulsion) KBr 4.5 g, average molecular weight 1500
1600 ml of an aqueous solution containing 7.9 g of gelatin at 40 ° C.
And stirred. AgNO ₃ ) (8.9 g) aqueous solution and K
An aqueous solution of KBr (6.2 g) containing 6.3% by weight of I was added by a double jet method over 40 seconds. Gelatin 38
After the addition of g, the temperature was raised to 58 ° C. AgNO ₃ )
(5.6 g) After adding the aqueous solution, 0.1 mol of ammonia was added, and 15 minutes later, the mixture was neutralized with acetic acid to adjust the pH to 5.0. An aqueous solution of AgNO ₃ ) (219 g) and an aqueous KBr solution were added over 40 minutes while accelerating the flow rate by a double jet method. At this time, the silver potential was kept at -10 mV with respect to the saturated calomel electrode. After desalting, 50 g of gelatin was added, the pH was adjusted to 5.8 and the pAg was adjusted to 8.8 at 40 ° C. to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 80 g of gelatin per kg of the emulsion, and has an average equivalent circle diameter of 0.
62 μm, coefficient of variation of equivalent circle diameter 16%, average thickness 0.
These were tabular grains having a particle diameter of 103 μm and an average aspect ratio of 6.0. (Preparation of Emulsion Em-1) 134 g of seed emulsion, KBr1.
1200 ml of an aqueous solution containing 9 g and 38 g of gelatin at 78 ° C.
And stirred. AgNO ₃ ) (87.7 g) aqueous solution and KBr aqueous solution while accelerating flow rate by double jet method.
Added over 6 minutes. At this time, the silver potential was kept at -40 mV with respect to the saturated calomel electrode. Then, AgNO ₃
(42.6 g) Aqueous solution and KBr aqueous solution were added by a double jet method over 17 minutes. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. After this, Ag
At the same time, 7.1 g of NO ₃ and an equimolar amount of KI were quantitatively added thereto, and subsequently, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were controlled by the double jet method while controlling the potential to 0 mV. Added over 10 minutes.
Perform normal water washing, add gelatin, and add pH at 40 ° C.
5.7, adjusted to pAg 8.7, average circle equivalent diameter 1.17
μm, variation coefficient of circle equivalent diameter 26%, average thickness 0.23μ
m, average aspect ratio 5.3, average sphere equivalent diameter 0.77μ
m-emulsion Em- comprising tabular grains (I = 2.0 mol%)
1 was prepared. Also, grains having an aspect ratio of 5 or more accounted for 65% or more of the total projected area. (Preparation of Emulsion Em-2) In the preparation of Emulsion Em-1,
AgNO ₃ after the simultaneous addition of AgNO ₃ solution and KI solution and K
When 1/3 of the Br solution addition is completed (at the time when the addition of 80% of the total silver to be added for the grain formation is completed), the addition is stopped once, and the NaCl solution is 1.56 g in NaCl amount. After the addition, 4.53 g of AgNO ₃ (A
2 mol% as gCl based on the total silver halide of the finished grains
AgNO ₃ and KBr in an equimolar amount to this AgNO ₃ were again added so that the silver amount became the same as Em-1. This was washed with water similarly to Em-1, and gelatin was added to prepare Em-2. (Preparation of Emulsion Em-3)
aCl solution, AgNO ₃ solution and SET
Em-3 was prepared in the same manner as Em-2, except that -2 was added at 1 × 10 ⁻⁵ mol / mol Ag (same definition as in Example 1). (Preparation of Emulsion Em-4) In the preparation of Emulsion Em-3,
Em-4 was prepared in the same manner as Em-3, except that SET-2 was added at 2 × 10 ⁻⁵ mol / mol Ag. (Preparation of Emulsion Em-5) In the preparation of Emulsion Em-1,
AgNO ₃ after the simultaneous addition of AgNO ₃ solution and KI solution and K
In the process of adding the Br solution, 98% of the total silver
At the end of the addition of silver, the addition of NaCl
The solution was added with 1.56 g of NaCl and then AgNO was added.
4.53 g (equivalent to 2 mol% as AgCl) of ₃ was added, washed with water, and gelatin was added to prepare Em-5. (Preparation of Emulsion Em-6) In the preparation of Emulsion Em-5,
Immediately before adding the NaCl solution, SET-2 was added to 2 × 10 ^−5.
E / E was added in the same manner as in Em-5 except that mol / mol Ag was added.
m-6 was prepared. (Preparation of Em-7) In the preparation of emulsion Em-1, Ag
AgNO ₃ and KBr after simultaneous addition of NO ₃ solution and KI solution
In the addition of the solution, when the addition of 90% of the total silver of the finished particles is completed, the addition is stopped and the NaCl solution is changed
After adding 7.8 g in 2 liters, 22.7 g of AgNO ₃ was added.
(Equivalent to 10 mol% as AgCl), washed with water and added with gelatin to prepare Em-7. (Preparation of Em-8) In the preparation of the emulsion Em-7,
Immediately before the addition of the Cl solution, SET-2 was added to 2 × 10 ^−5.
E / E was added in the same manner as in Em-7 except that mol / mol Ag was added.
m-8 was prepared. (Preparation of Em-9) In the preparation of emulsion Em-7, Na
Em-10 was prepared in the same manner as Em-7 except that SET-2 was added at 2 × 10 ⁻⁵ mol / mol Ag at the time when the addition of AgNO _{3 was performed} after the addition of the Cl solution. (Preparation of Em-10) In the preparation of emulsion Em-6,
Em-10 was prepared in the same manner except that sensitizing dyes S-4, S-5 and S-9 were present in an amount required to obtain optimum sensitivity before adding ET-2. Sensitizing dye S-
The structural formulas of 4, S-5 and S-9 are given below. (Preparation of Em-11) In the preparation of emulsion Em-10,
5 × 10 ^-4 mol / mol Ag SE before adding the sensitizing dye
Em-11 was prepared in the same manner except that T-2 was added. (Preparation of Em-12) In the preparation of Emulsion Em-1,
AgNO ₃ and KB after simultaneous addition of gNO ₃ solution and KI solution
In the addition of the r solution, SET-2 was added at 2 × 10 ⁻⁵ mol / mol Ag at the time when the addition of 90% of the total silver amount of the finished grains was completed.
Em-12 was prepared in the same manner except that it was added. (Preparation of Em-13) In the preparation of emulsion Em-1,
AgNO ₃ and KB after simultaneous addition of gNO ₃ solution and KI solution
When 90% of the r solution addition is completed, SET-2
Was added in the same manner except that 5 × 10 ⁻⁵ mol / mol Ag was added.
m-13 was prepared.

Table 3 summarizes the structural characteristics of the emulsions Em-1 to Em-13. In each of the emulsion grains, dislocation lines were present on the outer periphery of the tabular grains.

The amount of silver chloride incorporated in the grains was determined from the concentration of chloride ions present in the supernatant of the emulsion before washing.

[0083]

[Table 3] Emulsions Em-1 to Em-13 were heated to 50 or 60 ° C., and sensitizing dyes S-4, S-5 and S-9 described later except for emulsions Em-10, Em-11 and Em-12. Using
Potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Preparation of Coating Sample 201 A multilayer color light-sensitive material comprising the following layers was prepared on an undercoated 127 μm-thick cellulose triacetate film support,
Sample 201 was obtained. The numbers indicate the amount added per square meter. The effect of the added compound is not limited to the use described. First layer: Antihalation layer Black colloidal silver 0.10 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g Dye E -1 Microcrystalline solid dispersion 0.10 g Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling organic solvent Oil-3 0.10 g Dye D-4 0.80 mg Third layer: Intermediate layer Fine grain silver iodobromide emulsion with fogged surface and inside (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.050 g Yellow colloidal silver Silver amount 0.030 g gelatin 0.40 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.30 g emulsion B silver amount 0.20 g gelatin 0.80 g coupler C-1 0.15 g coupler C-2 0.050 g coupler C-3 0.050 g coupler C -9 0.05 0 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High-boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g Fifth layer: Medium-sensitivity red-sensitive emulsion layer Emulsion B silver amount 0.20 g Emulsion C silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g Sixth layer: Highly sensitive red-sensitive emulsion layer Emulsion D silver amount 0.40 g gelatin 1.10 g coupler C-1 0.30 g coupler C-2 0.10 g coupler C-3 0.70 g additive P-1 0.10 g seventh layer: intermediate layer gelatin 0.60 g additive M-1 0.30 g Inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High-boiling organic solvent Oil-1 0.020 g Eighth layer: Intermediate layer Surface and interior fogged iodobromide Silver emulsion (average particle size 0.06 μm, variation coefficient 16 , AgI content 0.3 mol%) Silver content 0.020 g Yellow colloidal silver Silver content 0.020 g Gelatin 1.00 g Additive P-1 0.20 g Color-mixing inhibitor Cpd-A 0.10 g Compound Cpd-C 0.10 g 9th layer: low sensitivity Green-sensitive emulsion layer Emulsion E silver amount 0.10 g emulsion F silver amount 0.20 g emulsion G silver amount 0.20 g gelatin 0.50 g coupler C-4 0.10 g coupler C-7 0.050 g coupler C-8 0.10 g compound Cpd-B 0.030 g compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-1 0.10 g High boiling organic solvent Oil-2 0.10 g 10th layer: Medium-sensitive green-sensitive emulsion layer Emulsion G Silver content 0.50 g Emulsion H silver content 0.10 g Gelatin 0.60 g Coupler C-4 0.070 g Coupler C-7 0.050 g Coupler C-8 0.050 g Compound Cpd-B 0.030 g Compound Cpd- D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g Compound Cpd-L 0.050 g High-boiling organic solvent Oil-2 0.010 g High-boiling organic solvent Oil-4 0.050 g 11th layer: high-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 1.00 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.050 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg Compound Cpd-L 0.020 g High-boiling organic solvent Oil-1 0.020 g High-boiling organic solvent Oil-2 0.020 g 12th layer: middle layer Gelatin 0.60 g Compound Cpd-L 0.050 g High-boiling organic solvent Oil-1 0.050 g 13th Layer: Yellow filter layer Yellow colloidal silver Silver amount 0.020 g Gelatin 1.10 g Color mixing inhibitor Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling organic solvent Oil-1 0.01 0 g Microcrystalline solid dispersion of dye E-2 0.030 g Microcrystalline solid dispersion of dye E-3 0.020 g Fourteenth layer: intermediate layer Gelatin 0.60 g Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.30 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-10 0.40 g 16th layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.30 g Emulsion M Silver amount 0.30 g Gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g 17th layer: high-sensitivity blue-sensitive emulsion layer Emulsion N silver amount 0.20 g Emulsion O silver amount 0.20 g gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.10 g 18th layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30g Compound C d-G 0.050 g Formalin scavenger Cpd-H 0.40 g Dye D-1 0.15 g Dye D-2 0.050 g Dye D-3 0.10 g High boiling organic solvent Oil-3 0.10 g 19th layer: 2nd protective layer Colloidal silver Silver Amount 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, silver iodide content 1 mol%) Silver amount 0.10 g Gelatin 0.40 g 20th layer: third protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μm 0.10 g Copolymer of 4: 6 methyl methacrylate and acrylic acid (average particle size 1.5 μm) 0.10 g Silicon oil SO-1 0.030 g Surfactant W-1 3.0 mg Surfactant W-2 0.030 g In all emulsion layers, in addition to the above composition, additive F-
1-F-8 were added. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer.

Further, phenol and 1,1 are used as antiseptic and antifungal agents.
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added. Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a wet cake of a dye containing 30% of methanol, followed by stirring to obtain a slurry having a dye concentration of 6%. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the slurry was baked at a peripheral speed of 10 m / sec at a discharge rate of 0.5 l / min for 8 hours. Crushed. The beads were removed by filtration, diluted with water by adding water to a dye concentration of 3%, and heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained fine dye particles was 0.60 μm, and the width of the particle size distribution (particle size standard deviation × 100 / average particle size) was 18%.

Similarly, solid dispersions of dyes E-2 and E-3 were obtained. Average particle size is 0.54 μm and 0.56 μm
Met.

The structural formulas and the like of the compounds used in the examples are shown below.

[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

Embedded image The silver iodobromide emulsion used for Sample 201 is as follows.

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6] Sample 202 was prepared by substituting Em-1 to Em-13 for Green-sensitive high-sensitivity emulsion I used to prepare Sample 201.
To 214 were obtained. Evaluation of Samples (a) Evaluation of sensitivity and fogging
Using a white light source having a color temperature of 4800K for 0 seconds, wedge exposure was performed, and after performing the following development processing, the sensitivity was measured by a relative value of a reciprocal of a relative exposure amount giving magenta densities of 0.5 and 2.0. . The standard is shown in Table 7 with 100 as the sample 202. The fact that the sensitivity of 0.5 is higher than that of the density of 2.5 means that the gradation is hard. Fog also appears as a reduction in the maximum magenta density. The higher the degree of decrease, the higher the fog.

[0104]

[Table 7] (Processing process and processing solution of standard development process) Processing process Time Temperature Tank capacity Refilling amount First development 6 minutes 38 ° C 12 liters 2200 ml / m Washing water 2 minutes 38 ° C 4 liters 7500 ml / m Inversion 2 minutes 38 ° C 4 liters 1100 ml / m Color development 6 minutes 38 ° C 12 liters 2200 ml / m Pre-bleaching 2 minutes 38 ° C 4 liters 1100 ml / m Bleaching 6 minutes 38 ° C 12 liters 220 ml / m Fixed 4 minutes 38 8 liters of 1100 ml / m washing with water 4 minutes 38 degrees Celsius 8 liters 7500 ml / m final rinsing 1 minute 25 degrees Celsius 2 liters 1100 ml / m The composition of each treatment liquid was as follows. [First developer] Tank solution Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g potassium hydroquinone monosulfonate 20 g 20 g potassium carbonate 15 g 20 g sodium bicarbonate 12 g 15 g 1-phenyl-4-methyl-4-hydroxymethyl 1.5 g 2.0 g -3-pyrazolidone potassium bromide 2 1.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to the mixture, and the resulting mixture was adjusted to 1,000 ml with a pH of 9.60 and 9.60. The pH was adjusted with sulfuric acid or potassium hydroxide. [Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid / pentasodium salt 3.0 g Tank liquid Same as 1.0 g of stannous chloride / dihydrate 0.1 g of p-aminophenol 8 g of sodium hydroxide Glacial acetic acid 15 ml Water 1000 ml by adding water pH 6.00 pH was adjusted with acetic acid or sodium hydroxide. [Color developing solution] Tank solution Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazinic acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Aminoaniline / 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml. PH 11.80 12.00 The pH was adjusted to sulfuric acid or Adjusted with potassium hydroxide. [Pre-bleaching] Tank liquid Replenisher Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Sodium bisulfite formaldehyde adduct 30 g 35 g 1000 ml with water pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide. [Bleaching solution] Tank solution Replenisher Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water Was added, and the pH was adjusted with nitric acid or sodium hydroxide. [Fixing solution] Tank solution Replenisher solution Ammonium thiosulfate 80 g Tank solution 5.0 g of sodium sulfite was added to 5.0 g of water, and the same sodium bisulfite solution was added. The pH was adjusted with acetic acid or ammonia water. [Final rinse liquid] Tank liquid Replenisher 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g polymaleic acid ( (Average molecular weight: 2,000) 0.1 g 0.15 g Water was added to 1000 ml, pH 7.0 7.0 (b) RMS granularity Next, RMS granularity at magenta concentrations of 0.5 and 2.5 was measured. Table 8 shows the results in which the RMS granularity was represented by a relative value with respect to the sample 202 being 100. The smaller the value, the better the granularity. The sample of the present invention has a concentration of 0.
It can be seen that the granularity is improved in both the region of 5 and the concentration of 2.5.

[0105]

[Table 8] According to Table 8, the emulsion into which the silver chloride layer was introduced cannot provide sufficient performance by itself, but the presence of the metal complex (SET-2) near the interface between the silver chloride layer and the silver bromide layer provides a high sensitivity. It was found that a high-contrast emulsion was obtained. The most preferable result is that a relatively small amount of the silver chloride layer is locally formed on the surface. The sample doped with the metal complex without the silver chloride layer also tended to have high sensitivity and high contrast, but required a large amount of doping, and as shown in Table 8, the graininess was caused by the presence of the silver chloride layer. It was inferior to the one. The amount of metal incorporated into the sample relative to the amount of dopant metal added during grain production was examined by atomic absorption spectroscopy. As a result, the better the result, the higher the unexpected result.

Sample No. 212 (Em-11) was the best result, but the metal doping amount to Em-11 was 1
It was found that the same performance was obtained even with × 10 ⁻⁴ mol / mol Ag. (Example 3) A sample was prepared in the same manner as in Example 2 for the red photosensitive layer of Sample 201 of Example 2, and the same evaluation was performed. When the effect of the present invention on the red photosensitive layer was confirmed, the same result as in Example 2 was obtained. Example 4 For the blue photosensitive layer of the sample 201 of Example 2, a sample was prepared in the same manner as in Example 2, and the same evaluation was performed. When the effect of the present invention on the blue photosensitive layer was confirmed, the same results as in Example 2 were obtained.

[0107]

As described above, the silver halide color light-sensitive material of the present invention exhibits properties superior in sensitivity, gradation and graininess to conventional products.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/035 G03C 1/035 Z

Claims (7)

[Claims] 1. A silver chloride region having a silver chloride content of 0.3 mol% or more and 50 mol% or less with respect to the total silver amount, wherein Ga, In and
A silver halide photographic emulsion comprising silver chlorobromide or silver iodobromochloride grains containing at least one ion of the group consisting of ions of metals belonging to Group 9, 9 and 10. 2. The emulsion according to claim 1, wherein said grains contain silver iodide in an amount of from 1 mol% to 7 mol%. 3. The emulsion according to claim 1, wherein the emulsion has a parallel (111) plane as a principal plane and 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 3 or more. The emulsion according to claim 1. 4. The grains locally contain Ga, In, and at least one ion of the group consisting of ions of metals of groups 8, 9 and 10 at the interface of the silver chloride region. 4. The method according to claim 1, wherein
The emulsion described in the item. 5. The emulsion according to claim 1, wherein the silver chloride region is present on the outermost surface of the grain. Wherein the said metal ion, Group 8, a Group 9 or 10 metal ions, the ions of the metal as a center metal, 1 to 6 of the CN ^- metal complex consisting of ligand The emulsion according to any one of claims 1 to 5, which is present as: 7. The emulsion according to claim 1, wherein the metal complex is a 6-cyano complex.