JPH05313292A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material capable of undergoing ultrahigh-speed processing without deteriorating development progress and storage stability with the lapse of time by incorporating a thiocyanate compound, a specified sensitizing dyestuff, and a specified compound each in a specified amount. CONSTITUTION:The silver halide photographic sensitive material contains in an emulsion layer the thiocyanate in an amount of 2.5X10<-3>-2X10<-2>mol per mol of silver halide and the sensitizing dyestuff of formula I in an amount of >=1X10<-4>mol per mol of silver halide and the compound of formula II in an amount of 1X10<-3>-1X10<-1>mol per mol of this sensitizing dyestuff. In formulae I, each of R1 and R2 is alkyl, alkenyl, or aryl; R3 is alkyl; X<-> is a counterion for neutralizing electric charge in the molecule; (n) is a number necessary to neutralize it; and each of Z1 and Z2 is a nonmetallic atomic group necessary to form an optionally substituted benzeneor naphthalene ring, and in formula II, each of R1-R4 is alkyl; X<->, (n), Z1, and Z2 are same as each in formula I, but when an intramolecular salt is formed, both of (n) is 0.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material capable of rapid processing. In particular, the present invention relates to a photographic light-sensitive material which has high sensitivity and is excellent in development progress even when subjected to an ultra-rapid processing with a development time of 20 seconds or less, and which can maintain stable photographic performance even during natural aging.

[0002]

2. Description of the Related Art For silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), a technique for preparing a silver halide emulsion having the same size and higher sensitivity has been continuously pursued. On the other hand, in recent years, high-temperature rapid processing has rapidly spread in the developing process of photosensitive materials, and even in the automatic developing machine processing of various photosensitive materials,
The processing time has been greatly reduced. For this purpose, development of a silver halide emulsion and a light-sensitive material which are excellent in development progress is desired.

For the purpose of improving the above viewpoints, a technique utilizing tabular grains is disclosed in US Pat. No. 4,439,520.
No. 4,425,425 and the like. Further, in JP-A-63-305343 and JP-A-1-77047, the progress of development is controlled by controlling the development start point of a silver halide grain having a (111) plane to the vertex of the grain and / or the acid and its vicinity. And a technique for improving the sensitivity / fog ratio are disclosed. These known techniques are excellent techniques and have high utility values, but further improvements have been desired for the purpose of further reducing the processing speed.

The present invention relates to a technique for positively adhering a thiocyanic acid compound to silver halide grains and a light-sensitive material in order to further increase the sensitivity and improve the development progress. U.S. Pat. No. 4,332,887 discloses a technique in which thiocyanate is used as a silver halide emulsion to obtain a preferable grain shape, but it is intended to remove the solvent effect after the grain formation which eliminates the need. Therefore, the effect of the present invention was not exhibited. In addition, JP-A-59-162
No. 540 discloses a technique for increasing the sensitivity by forming silver thiocyanate on the edges of silver halide host grains such as silver bromide or silver iodobromide grains. However, this technique was intended to form epitaxial growth on silver halide host grains by limiting the site. Therefore, the deposition amount of silver thiocyanate which gave the increase in sensitivity disclosed in the examples was 5 × 10 ^-2 mol per mol of silver.

The present invention differs from JP-A-59-162540 in that the epitaxial formation of thiocyanate cannot be confirmed at least by observation with an electron microscope. Further, when 5 × 10 ^-2 mol of silver thiocyanate as described in the patent is adhered on the silver halide grains, photographic fog increase and desensitization of the light-sensitive material with natural aging are remarkably realized. It did not have the performance as a material.

Further, as described above, in order to enable rapid processing, the replenishment of processing solution is reduced, and development, fixing, washing, and
The time for each drying step must be shortened. In such a system, iodine causes (1) developer fatigue and (2)
Problems such as residual color due to rough damage from desorption of dye and (3) improper fixing are problems that cannot be ignored. In order to reduce the fatigue of the developing solution and the development inhibiting effect of iodine ions, the replenishment amount must be increased. Further, as described in detail in JP-A-2-68,540, the dye adsorption is enhanced by iodine, but the residual color due to the spectral sensitizing dye is increased. To prevent this, the fixing and washing time must be increased. The same applies to poor fixing. However,
As is well known in the art, it has been considered that the use of iodine as a part of the halogen composition is an essential technique for producing a silver halide emulsion having high sensitivity and excellent development progress. .. These are, for example, Japanese Patent Publication No. 63-3
Details are described in JP-A-8692 and JP-A-63-305343.

On the other hand, the inventors of the present invention have found a means for obtaining a higher sensitization than when a large amount of iodine is used and a rapid development progress when a small amount of iodine is used. A method of adding a small amount of dye having a lower oxidation potential to improve the color sensitization rate has been known in the art for a long time as a supersensitization technique. For example, by James, Theory of Photographic Process No. 1
Chapter 0, JP-A-2-47647 and JP-A-1-15843.
This method is effective for a dye whose reduction potential is lower than the conduction band edge of the silver halide used, as described in detail in No. 6. However, many of the compounds represented by formula (I) were usually considered to exhibit a sufficiently high spectral sensitization rate without using these supersensitization methods. However,
When the iodine content of the particles becomes low, the spectral sensitization rate decreases with the change in the adsorption state of the dye (adsorption becomes weaker), and the latent image forming efficiency (inherent sensitivity) also decreases significantly. I will end up. In such a case, the present inventors can prevent a decrease in the spectral sensitization rate and a decrease in the intrinsic sensitivity by using a small amount of a dye, preferably 0.2 eV or more, which is more base of oxidation potential, in combination. I was found to be done. This phenomenon is a peculiar phenomenon that occurs in emulsions having a low iodine content and the dyes of the general formula (I), and was completely unexpected.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material having high sensitivity, low fog and excellent development progress even when subjected to ultra-rapid processing, and capable of maintaining stable photographic performance even during natural aging. Is to provide.

[0009]

The objects of the present invention are as follows.
It was achieved by (1)-(4). (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer is 2.5 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol per mol of silver. The sensitizing dye containing the thiocyanic acid compound and represented by the general formula (I) is 1 × 10 1 per mol of silver halide.
^-4 mol or more and containing 1 × 10 ⁻³ mol or more and 1 × 10 ⁻¹ mol or less of the compound of general formula (II) with respect to the compound of general formula (I), a silver halide photographic light-sensitive material ..

[0010]

[Chemical 3]

[Wherein R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and at least _one of R ₁ and R ₂ Is a sulfoalkyl group or a carboxyalkyl group. R ₃ represents an alkyl group. X ⁻ represents a counter ion necessary for neutralizing the charge of the molecule, and n represents a number necessary for neutralization. Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. (However, n is 0 when forming an intramolecular salt.)]

[0012]

[Chemical 4]

[Wherein R ₁ to R ₄ are each a substituted or unsubstituted alkyl group, X ⁻ represents a counter ion necessary for neutralizing the charge of the molecule, and n represents a number necessary for neutralization. .. Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. (However, n is 0 when forming an inner salt.) (2) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, halogen in the emulsion layer The amount of the thiocyanic acid compound present on the silver halide grain surface is 2 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol per 1 mol of silver, and the sensitizing dye represented by formula (I) is 1 mol per 1 mol of silver halide A silver halide photograph characterized by containing 1 × 10 ^-3 mol or more and 1 × 10 ^-1 mol or less of the compound of general formula (II) with respect to the compound of general formula (I), in an amount of × 10 ^-4 mol or more. Photosensitive material. (3) The silver halide photographic light-sensitive material as described in (1) or (2), wherein the silver iodide of the silver halide grain is locally present on the grain surface. (4) The oxidation potential of the compound of the general formula (II) is
The silver halide photographic light-sensitive material described in (1) to (3) above, which is 0.2 eV or more less base than the oxidation potential of the compound.

The specific structure of the present invention will be described in detail below. As the thiocyanic acid compound used during the preparation of the silver halide emulsion in the present invention, a water-soluble salt such as metal thiocyanate or NH ₄ SCN can be generally used. Care should be taken to use metal elements that do not adversely affect, and KSCN, NaSCN and the like are preferable. A poorly soluble salt such as AgSCN may be added in the form of fine particles. In this case, A
The size of the gSCN fine particles is preferably 0.2 μm or less in diameter, and particularly preferably 0.05 μm or less.

The thiocyanic acid compound may be added at any time during the emulsion preparation, but it is preferably added both before the desalting step and during the chemical sensitization. The amount added is 3.0 × 10 ⁻³ mol or more and less than 5 × 10 ⁻² mol, and preferably 5 × 10 ⁻³ mol or more, per mol of silver halide, as the total amount added from the time of grain formation to the end of chemical sensitization. Less than × 10 ^-2 mol, and 3.0 × 10 per mol of silver halide in the final light-sensitive material or emulsion as a result of being removed in the desalting step.
^-3 mol 2 × 10 ^-2 mol less, and particularly preferably 4 × 10 ^-3 content below mol to 1.5 × 10 ^-2 mol.

The method of adding the thiocyanic acid compound before the desalting step is the preferred method for the present invention. In this case, the thiocyanic acid compound may be added at any time during grain formation. The addition amount is preferably 1 × 10 ⁻³ mol or more and less than 5 × 10 ⁻² mol, and more preferably 2 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol, per mol of silver halide.
Depending on the case where a part is removed in the desalting step and a part is added during the chemical sensitization, 3.0 × 10 ⁻³ mol or more per mol of silver halide in the final photographic material or emulsion. Less than × 10 ^-2 mol, especially 4 × 10 ^-3 mol or more 1.5 ×
A content of less than 10 ^-2 mol is preferred. Further, the total amount of the thiocyanic acid compound attached to the surface of the silver halide grains contained in the final light-sensitive material or emulsion is 2 × 10 ⁻³ mol or more and 2 × 10 ⁻² mol per mol of silver halide.
The amount of adhesion is preferably less than 2.5 mol, particularly 2.5 × 10 ⁻³ mol or more and less than 1 × 10 ⁻² mol. The thiocyanic acid compound added at the time of chemical sensitization may be used as a ligand of the gold sensitizer and added.

PB when adding thiocyanate compound
r is particularly important, and when it is too low, the amount of the thiocyanate compound adsorbed on the silver halide grains is remarkably reduced, and when it is too high, fogging occurs, which is not preferable. A preferable pBr that can be utilized during grain formation in the presence of a thiocyanate compound is 2.0 or more and 4.5 or less, and particularly 2.3
It is preferably not less than 4.0 and not more than 4.0.

[Method for Quantifying Thiocyanic Acid Compound in Sensitive Material and Emulsion] In order to achieve the effect of the present invention, the amount of thiocyanic acid compound in the finally obtained finished emulsion or sensitive material is defined by the claim 1 of the present application. It is necessary to control such as ~ 5. Whether or not the desired state has been achieved can be confirmed by the following method (see Examples for details of the centrifuge and ion chromatography models actually used, measurement conditions, etc.).

1. Determination of thiocyanate ion in emulsion before coating 1% KB for emulsion containing 1.5 × 10 ^-2 mol of silver halide
10 cc of aqueous solution was added and stirred at 40 ° C. for 30 minutes. The emulsion is centrifuged to completely separate the emulsion, and the supernatant is diluted 100 times. After the ultrafiltration of the diluted solution, the thiocyanate ion in the diluted solution is quantified by ion chromatography. For the quantification, a calibration curve prepared in advance using a thiocyanic acid compound aqueous solution is used.

2. Determination of thiocyanate ion on the surface of silver halide grains in emulsion before coating Distilled water 1 in an emulsion containing 1.5 × 10 ^-2 mol of silver halide
Add 0 cc and stir at 40 ° C. for 30 minutes. The emulsion is centrifuged to completely separate the emulsion, and the supernatant is diluted 100 times. After ultrafiltration of the diluted solution,
The thiocyanate ion in the diluted solution is quantified by ion chromatography. For the quantification, a calibration curve prepared in advance using a thiocyanic acid compound aqueous solution is used. By subtracting the value thus obtained from the value of all thiocyanate ions in the emulsion previously obtained, the amount of thiocyanate ions attached to the target grain surface is obtained.

3. Quantification of thiocyanate ion in the product form of the sensitive material The target emulsion layer containing 1 g of silver was peeled from the sensitive material. 4
Immerse in 9 cc of distilled water. To this solution, 1 cc of 5% KBr aqueous solution was added, and then ultrasonically stirred at 40 ° C. for 30 minutes. After centrifuging this solution, the supernatant is filtered. The filtered supernatant is diluted 10-fold and then the thiocyanate ion contained therein is quantified by ion chromatography. For the quantification, a calibration curve prepared in advance using a thiocyanic acid compound aqueous solution is used.

4. Quantitative determination of thiocyanate ion on the surface of silver halide grains in the product form sensitive material The target emulsion layer containing 1 g of silver was peeled from the sensitive material 5
Immerse in 0 cc of distilled water. This solution is ultrasonically stirred at 40 ° C. for 30 minutes. After centrifuging this solution, the supernatant is filtered. The filtered supernatant is diluted 10-fold and then the thiocyanate ion contained therein is quantified by ion chromatography. By subtracting the value thus obtained from the previously obtained value of thiocyanate ions in the photosensitive material, the amount of thiocyanate ions attached to the target particle surface is obtained. Even in the case of a multi-layer coated product light-sensitive material, if this operation is performed after peeling layers by layer, accurate information on the emulsion of the target layer can be obtained.

Further, in the light-sensitive material of the present invention, the compound of the general formula (I) is 1 × 10 ^-4 per mol of silver halide.
A compound represented by the general formula (I
The compound (I) is contained in an amount of 1 × 10 ^-3 mol or more and 1 × 10 ^-1 mol or less. The general formula (I) will be described in detail. In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and at least _one of R ₁ and R ₂ is a sulfoalkyl group. Alternatively, it is a carboxyalkyl group. R ₃ represents an alkyl group.
X ⁻ represents a counter ion necessary for neutralizing the charge of the molecule, and n represents a number necessary for neutralization. Z ₁ and Z ₂ may each have a substituent. It represents a group of non-metal atoms necessary for completing a benzene ring or a naphtho ring. (However, n is 0 when forming an intramolecular salt.) R ₁ and R in the above formula
₂ may be the same or different, and is an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.). As a substituted alkyl group, a substituent (eg, halogen atom, hydroxy group, etc. is substituted). 1 to 4 carbon atoms
And an alkenyl group having up to 4 carbon atoms (eg, allyl group, 2-butenyl group, etc.). Also, R ₁
One of R ₂ and R ₂ is a sulfoalkyl group or a carboxyalkyl group, and the sulfoalkyl group has 2 to 2 carbon atoms.
4 (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group,
2- [3-sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group, etc.). As a carboxyalkyl group,
(For example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group, etc.) are mentioned. R ₃ is an alkyl group having 1 to 2 carbon atoms and represents a methyl group or an ethyl group. X ⁻ is an anion, for example, a halogen atom (I, Br, Cl, etc.), Z ₁ and Z ₂
Is a non-metal atom group necessary for forming a benzene ring or a naphthalene ring which may have a substituent in a condensed ring, and a substitutable group (for example, a halogen atom, a cyano group, an alkyl group,
Alkoxy group, aryl group, trifluoromethyl group, alkoxycarbonyl group, acyl group, etc.) may be substituted. n is 1 or 2, and n is 1 when the dye forms an intramolecular salt. In addition, when R ₁ and R ₂ are a sulfoalkyl group or a carboxyalkyl group, each is R—SO.
₃ may form a salt in the form of M group, or R-COOM group,
M represents a hydrogen atom, an alkali metal atom (for example, Na, K, etc.) or an ammonium group.

Next, the general formula (II) will be described in detail. In the formula, R ₁ to R ₄ are each a substituted or unsubstituted alkyl group, X ⁻ represents an ion necessary for neutralizing the charge of the molecule, and n represents a number necessary for neutralization. Z ₁ and Z
Each ₂ represents a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. (However, n is 0 when forming an inner salt.) R ₁ in the above formula
To R ₄ are hydroalkyl, alkoxyalkyl, halogen, alkoxycarbonylalkyl, acyloxyalkyl, carboxyalkyl, sulfo as a substituted alkyl group having an alkyl group having 1 to ₄ carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.). Alkoxy such as alkyl (2-methoxyethyl, 2-ethoxyethyl, etc.). Halogen (2-chloroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl) alkoxycarbonyl (methoxycarbonylmethyl, 2-methoxycarbonylethyl) aloxy (2-
Acetyloxyethyl, 3-acetyloxyethyl) sulfoalkyl group, carboxyalkyl group is R-SO ₂ M
Alternatively, a salt of -COOM may be formed. Z ₁ and Z ₂
Is a group of non-metal atoms necessary for forming a benzene ring which may have a substituent in the condensed ring or a naphthalene ring, and as a substituent (for example, Cl, Br as a halogen atom, a fluoro group, etc.) trifluoro Methyl group or -COOM
A group (R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and an aryl group such as a phenyl group) and a cyano group. X and n have the same meanings as those in formula (I).
The amount of the dye of the general formula (II) used is preferably 10 ^-3 to 10 ^-1 mol, and particularly preferably 10 ^-3 to 10 ^-2 mol, based on the amount of the dye of the general formula (I) used. This is because, as described in the prior art, when the amount is too large, desensitization due to a dye called intrinsic desensitization occurs. For example, when used as a medical X-ray sensitive material, fog under safelight. Is easily increased. The dyes may be added at any of grain formation, chemical sensitization step, and coating, or they may be added together or separately. These dyes may be used by dissolving them in a solvent such as methanol, or may be used by being dispersed in gelatin in a microcrystalline state. Specific examples of the general formulas (I) and (II) of the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

Next, the emulsion grains used in the present invention will be described. The diameter of a sphere having the same volume as the emulsion grains (hereinafter referred to as sphere-equivalent average grain size) is preferably 0.4 μm or more and less than 2.0 μm, and particularly preferably 0.5 or more and less than 1.5 μm. The particle size distribution should be narrow. The silver halide grains in the emulsion are cubic, octahedral, 14
It may have a regular crystal form such as a face piece, or may have an irregular crystal form such as a spherical shape, a plate shape, or a potato shape. It may consist of a mixture of particles of various crystal forms. When a monodisperse emulsion is used as an emulsion in the practice of the present invention, the rate of addition of the aqueous silver nitrate solution and the water-soluble halide can be increased with the growth of silver halide grains in the preparation of the monodisperse emulsion. By increasing the addition rate, the particle size distribution can be made more monodisperse, and the addition time can be shortened, which is advantageous for industrial production. Further, it is also preferable in that the chance of structural defects being formed inside the silver halide grain is reduced.

As a method of accelerating the addition rate, as described in JP-B-48-36890, JP-A-52-16364, and JP-A-55-142329, the addition rate of the silver salt aqueous solution and the halide aqueous solution is added. May be increased continuously or stepwise. The upper limit of the addition rate may be a rate just before the generation of new grains, and the values are temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, inter-grain distance, or protection. It changes depending on the type and concentration of colloid. A method for producing a monodisperse emulsion is known, and for example, J. Phot. Sci. 12, 242-251.
(1963), JP-B-48-36890, 52-1.
6364 and JP-A-55-142329, and the technology described in JP-A-57-179835 can be employed.

When a monodisperse emulsion is used as an emulsion in the practice of the present invention, a known method can be used for producing the polydisperse emulsion. For example, TH James's “The Theory
Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled double method described in the documents of the of the Photographic Process, 4th edition, Macmillan (1977), pages 38-104. Jet method,
It can be manufactured by applying a method such as a conversion method or a core / shell method.

Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention (for details, RE
SEARCH DISCLOSURE Volume 225 Item 22534, p.20
~ 58, January issue, 1983, and JP-A-58-127.
921 and 58-113926). The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are described by Cugnac and Chateau, "Development of Morphology of Silver Bromide Crystals During Physical Ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Reinforcement) "Sanence et Industrie Photography, 33, No. (196
2) pp.121-125, Duffin, "Photographic emulsion chemistry (Photographi
c emulsion Chemistry) '' Focal Press (Focal P
ress), New York, 1966, p.66-72, A.
PH Trivelli, WF Smith Photographic Journal, 80
Vol., Page 285 (1940) and the like, but JP-A-58-127,921 and JP-A-58-113,92.
7, JP-A-58-113,928, U.S. Pat. No. 4,
It can be easily prepared by referring to the method described in 439,520. The projected area diameter of the tabular emulsion of the present invention is 0.
It is preferably 3 to 2.0 μm, and particularly preferably 0.5 to 1.2 μm. The distance between the flat surfaces (particle thickness) is 0.05 μm to 0.3 μm, particularly 0.1 to 0.25 μm.
It is preferable that the aspect ratio is 3 or more and 20 or more.
It is preferably less than 4, and more preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more account for 50% or more (projected area) of all grains,
In particular, it is preferable that 70% or more is present, and the average aspect ratio of the tabular grains is 3 or more, particularly 4 to 8. Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. Details of the structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are described in JP-A-63-151618.
Follow the description of the issue.

As the halogen composition of the silver halide emulsion of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used in order to realize high sensitivity. Further, the silver chloride content is preferably 10 mol% or less. The silver halide grains may be composed of a uniform layer, but it is preferable that the inside and the surface layer have different halogen compositions, particularly 80% or more of silver bromide, 90% or more of silver bromide, and 95% of silver bromide. It is particularly preferable that at least the outermost surface of the silver halide grains of mol% or more is a silver iodide-containing layer. As described in the prior art, it is necessary to keep the silver iodide content of silver halide grains low in order to realize rapid processing. This request is a problem that is not compatible with the enhancement of the sensitivity of photosensitive materials. In order to solve this problem, it is desirable to use iodine only when forming the final grain surface. The composition of the silver halide grains at the time of forming the surface of the silver halide grains is preferably pure silver bromide or silver chlorobromide. More preferably, it is pure silver bromide.

The silver iodide content of each emulsion grain is, for example, X.
It can be measured by analyzing the composition of each silver halide grain using a line microanalyzer. The term "coefficient of variation of the silver iodide content of individual grains" as used herein means, for example, the silver iodide content of at least 100 emulsion grains measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the standard deviation by the average silver iodide content by 100. The 5th Photographic Society of Japan
Volume 3 Issue 2 (J. Soc. Photogr. Sci. Technol. Japan Vo
L.53, No. 2, 1990), pages 125-128, the results of measuring the silver iodide content for each internal structure of each silver halide grain by an analytical electron microscope are reported. .. JOURNAL OF I
MAGING SCIENCE Vol. 31, No. 1, 1987, 15-
On page 26, the intragranular microstructure relating to the halogen composition of tabular grains is described in Low-temperature luminescenc
The method of observing using e miroscopy) has been reported in detail. Also, JOURNAL OF IMAGING SCIENCE Vol. 3
2, No. 4, 1988, pages 160 to 177, when silver chloride is deposited on silver iodobromide having an intragranular silver iodide distribution, silver iodide determines the location of silver chloride deposition (site direct). Has been reported in detail. Furthermore, it has been reported from page 213 of the Journal of the Photographic Society of Japan, Vol. 35, 1972, that the nonuniformity of the halogen composition in the grains can be observed by directly observing the grains at a low temperature using a transmission electron microscope. If the above method is used, silver halide grains 1
The fine structure of each silver halide composition can be observed.

Next, a method for forming a silver iodobromide layer on the grain surface will be described. In forming the final grain surface, it is necessary to supply iodine so as to eliminate the inter-grain distribution of the surface iodine content of individual grains. The method for forming the silver iodobromide layer on the grain surface is described in, for example, British Patent No. 63.
There are so-called halogen conversion methods as described in US Pat. No. 5,841, and US Pat. No. 3,622,318. As a method for forming a silver iodobromide layer on the grain surface, a method of simultaneously adding a silver nitrate solution and an iodine ion-containing solution, AgI and / or
Alternatively, a method of adding fine silver halide grains having a composition of AgBrI, a method of dissolving potassium iodide or potassium iodide and potassium bromide in a gelatin solution, and then cooling and setting it to a solid state can be applied. Among them, a method of simultaneously adding a silver nitrate solution and a solution containing iodine ions,
The method of adding fine silver halide grains having AgI and / or AgBrI composition is a more preferable method for the present invention. Further, an organic compound containing iodine as described in JP-A-63-220187 may be added to the bulk liquid in the reaction vessel. Representative compounds include, but are not limited to, the following.・ ICH ₂ CH ₂ COOH ・ ICH ₂ COOH ・ ICH ₂ CN

In the light-sensitive material of the present invention, at least one photosensitive silver halide emulsion layer may be provided on one side of the support, or at least one layer may be provided on both sides of the support. Good. The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the light-sensitive silver halide emulsion layer, if desired. For example, a surface protective layer is preferably provided. In the light-sensitive material of the present invention, the amount of gelatin on the side having the hydrophilic colloid layer including the light-sensitive silver halide emulsion layer is preferably in the range of 1.70 to 2.50 g / m ² . If the photosensitive emulsion layer is present only on one side of the support, the amount of gelatin on that side is preferably within the above range, and if the photosensitive emulsion layer is on both sides of the support, the amount of gelatin on both sides is Is preferably within the above range. When there is no hydrophilic colloid layer other than the photosensitive emulsion layer, the amount of gelatin in the photosensitive emulsion layer is within the above range. Gelatin content is more preferably in the range of 1.80~2.40g / m ^2, in particular in the range of 1.90~2.30g / m ² is desirable.

Various additives and the like used in the photographic light-sensitive material of the present invention are not particularly limited and, for example, those described in the following relevant parts can be used. Items Applicable places 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, bottom 6 to its production line, page 10 upper right column, line 12, and 3-245 37 gazette No. 2 Page 10, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11 lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggants and Stabilizers JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column .. 4) Color improver JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 6) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 plasticizer, from the same upper right column, line 10, from page 14, lower left column, line 10 to lower right column, line 1 7) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 8) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 9) Support, JP-A-2-68539, page 13, upper right column, line 7 to line 20. 10) Crossover JP-A-2-264944, page 4, upper right column, line 20: From cut method, page 14 upper right column. 11) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 12) Polyhydroxyben JP-A-3-39948, page 11, upper left column to genus, page 12, lower left column, EP Patent No. 452772A. 13) Layer structure JP-A-3-198041. 14) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10 Hereinafter, the present invention will be described in more detail with reference to examples.

[0039]

【Example】

Example 1 (Preparation of tabular silver iodobromide grains (grain 1) containing pure silver bromide as the core and silver iodide (total silver iodide content 0.2 mol%) in the outermost layer) in 1 liter of water 6 g of potassium bromide and 7 g of gelatin were added to, and while stirring in a container kept at 55 ° C., 37 cc of an aqueous silver nitrate solution (4.00 g of silver nitrate) and 38 cc of an aqueous solution containing 5.7 g of potassium bromide were used for 37 seconds by the double jet method. Added in. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 89 cc of silver nitrate aqueous solution (silver nitrate 9.8 g) was added over 22 minutes. 25 here
% Aqueous ammonia solution (7 cc) was added, the mixture was physically aged at the same temperature for 10 minutes, and then 100% acetic acid solution was added to 6.5 cc.
Was added. Subsequently, an aqueous solution containing 153.0 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method over 35 minutes while keeping the pAg at 8.5.
After the addition was completed, 0.2 mol% of silver iodide fine particles having a diameter of 0.07 μm was added to the total amount of silver. Then, pBr was adjusted to 2.8 using an aqueous solution of silver nitrate, and then 2 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.2 mol%, the average projected area diameter was 1.11 μm, the thickness was 0.164 μm, and the diameter variation coefficient was 1.
8.0% of monodisperse tabular grains were obtained. After that, soluble salts were removed by a sedimentation method. The temperature was raised to 40 ° C. again, 30 g of gelatin, 2.35 g of phenoxyethanol, and 0.8 g of sodium polystyrene sulfonate as a thickener.
Was added, and the pH was adjusted to 5.90 with sodium hydroxide solution and caustic soda.
It was adjusted to Ag 8.25.

(Preparation of particles 2) Particles 2 were prepared in the same manner as particles 1 except that the amount of 2N potassium thiocyanate added was 15 cc. Thus, the total silver iodide content was 0.2 mol%, the average projected area diameter was 1.12 μm, and the thickness was 0.163.
Monodisperse tabular grains having a diameter variation coefficient of 18.0% were obtained.

(Preparation of Emulsions 1-2: Chemical Sensitization) Next, the grains 1 and 2 were chemically sensitized while being kept at 56 ° C. with stirring. First, thiourea dioxide 0.043
mg was added and held for 20 minutes for reduction sensitization. next,
20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 400 mg of Exemplified sensitizing dye I-4
Was added. Furthermore, 0.83 g of an aqueous calcium chloride solution was added. Subsequently, 1.3 mg of sodium thiosulfate, 3.4 mg of selenium compound-1, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. Thus, the preparation of Emulsions 1-2 was completed.

[0042]

[Chemical 10]

(Preparation of Emulsions 3 to 4: Chemical Sensitization) Except for adding the above-mentioned sensitizing dye II-4 and 94.2 mg of the sensitizing dye II-4 to the grains 1 and 2 in the same manner as above. Prepared. Thus, the preparation of emulsions 3 to 4 was completed.

(Preparation of Emulsion Coating Layer) The following chemicals were added to chemically sensitized emulsions 1 to 4 per mol of silver halide to prepare a coating solution (type A). -2-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg-trimethylolpropane 9 g-dextran (average molecular weight 39,000) 18.5 g-potassium polystyrene sulfonate (average molecular weight 600,000) 1.8 g-Compound (E-1) 3.4 mg-Compound (E-2) 4.8 g-Snowtex C (Nissan Chemical Co., Ltd.) 29.1 g-Gelatine The total amount applied to one side is 2.4 g / It was prepared to be m ² . Hardener (1,2-bis (vinylsulfonylacetamide) ethane Prepared to have a swelling ratio of 230%.

[0045]

[Chemical 11]

(Preparation of Surface Protective Layer Coating Solution) A surface protective layer coating solution was prepared and prepared so that each component had the following coating amount.・ Gelatin 0.966 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.023 ・ Compound (P-1) 0.013 ・ Compound (P-2) 0.045 ・ Compound (P-3) 0 0.0065 compound (P-4) 0.003 compound (P-5) 0.001 compound (P-6) 0.0012 polymethylmethacrylate (average particle size 3.7 μm) 0.087 proxel 0 0.0005 (adjusted to pH 7.4 with NaOH)

[0047]

[Chemical formula 12]

(Preparation of Support) (1) Preparation of Dye K for Undercoat Layer The following dyes were ball milled by the method described in JP-A-63-197943.

[0049]

[Chemical 13]

434 ml of water and 6.7 of Triton X200® surfactant (TX-200®).
% Aqueous solution (791 ml) was placed in a 2 liter ball mill. 20 g of dye were added to this solution. 400 ml of zirconium oxide (ZrO) beads (2 mm diameter) were added and the contents were crushed for 4 days. After this, 12.5% gelatin 16
0 g was added. After defoaming, the ZrO beads were removed by filtration. When observing the obtained dye dispersion,
The particle size of the crushed dye has a wide distribution from 0.05 to 1.15 μm in diameter, and the average particle size is 0.37 μm.
It was m. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion K was obtained.

(2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoat liquid having the following composition was applied at an amount of 5.1 cc / m ² . Was applied by a wire bar coater so as to obtain the above, and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained 0.04 wt% of the dye having the following structure.

[0052]

[Chemical 14]

* Butadiene-styrene copolymer latex solution (solid content 40% Butadiene / styrene weight ratio = 31/36 79 cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20. 5cc-Distilled water 900.5cc * The following emulsifying dispersants were used in the latex solution.

[0054]

[Chemical 15]

A second undercoat layer having the following composition was applied on each of the above-mentioned first undercoat layers one by one so that the coating amount would be the amount described below, and 150 on each side by a wire bar coater system. Coated and dried at ℃.・ Gelatin 160 mg / m ²・ Dye Dispersion K (26 mg / m ² as a solid dye component)

[0056]

[Chemical 16]

(Preparation of photographic material) On the support prepared as described above, the above emulsion layer and the surface protective layer were coated on both sides by the simultaneous extrusion method. The amount of coated silver per side is 1.75 g.
/ M ² . Thus, samples 1 to 7 were obtained.

(Evaluation of Photographic Performance) The photographic material was exposed for 0.05 seconds from both sides using X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. After exposure
The following processing was performed and sensitivity was evaluated. The sensitivity was based on Sample 1, and indicated by the reciprocal of the ratio of the exposure dose that gives a density of 1.0 in addition to fogging.

[Treatment] An automatic processor CEPROS manufactured by FUJIFILM Co., Ltd. was modified to speed up the transfer speed. Preparation of Concentrated Solution <Developer> Part Agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) ethyl-5-mercaptotetrazole 0. 75 g Hydroquinone 450 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 60 g Water was added to give 4125 ml.

Part Agent B Diethylene glycol 525 g 3,3′-Dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 2-Nitroindazole 3.75 g 1-Phenyl-3-pyrazolidone 34.5 g Water 750 ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water added 750 ml

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-diethylamine) -ethyl-5-mercapto Tetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water was added to it 6000 ml pH 4.68

Preparation of processing liquid The above developing solution was filled in the following container for each parts agent. In this container, the partial containers of the parts agents A, B, and C are connected together by the container itself. Also,
The fixer concentration was also filled in the same kind of container. First, 54 g of acetic acid and 5 parts of potassium bromide were used as a starter in the developing tank.
300 ml of an aqueous solution containing 5.5 g was added. Put the above-mentioned treatment agent container upside down and insert it into the perforation blade of the treatment liquid stock tank mounted on the side of the automatic processing machine to break the sealing film of the cap and put each treatment agent in the container into the stock tank. Filled. The developing agent and the fixing tank of the developing machine were filled with the respective processing agents at the following ratios by operating the pumps installed in the developing machine. In addition, the sensitive material is 8 in size
The stock solution of the treating agent and water were mixed and replenished in the treating tank of the automatic developing machine in this proportion every time the sheet was processed.

Developer solution Part solution A 55 ml Part solution B 10 ml Part solution C 10 ml Water 125 ml pH 10.50 Fixing solution Concentration 80 ml Water 120 ml pH 4.62 The wash tank was filled with tap water.

As a water stain inhibitor, 0.4 g of actinomycetes supported on pearlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene pin (the pin opening was covered with a 300-mesh nylon cloth. Prepare 3 pieces filled with water and germs from cloth), 2 of them are at the bottom of the washing tank, and 1 is at the bottom of the stock tank of washing water (liquid volume 0.2 liters). I sunk each. Processing speed and processing temperature Current image 35 ° C 8.8 seconds Settling 32 ° C 7.7 Washing with water 17 ° C 3.8 Squeeze 4.4 Drying 58 ° C 5.3 Total 30 Replenishing amount Developer 25ml / 10 × 12 inches Fixer 25ml / 10 x 12 inches

(Evaluation of Development Progression) The above-mentioned evaluation of photographic property was carried out at processing speeds of Dry to Dry of 30 seconds and 45 seconds of the automatic developing machine, and the sensitivities of both were compared. The results are shown in Table 1.

(Quantification of thiocyanate compound) It was determined according to 1 and 2 (quantification of thiocyanate ion in the emulsion before coating) of the thiocyanate compound. That is, to an emulsion containing 1.5 × 10 ^-2 mol of silver halide, 10 cc of a 1% KBr aqueous solution (when quantifying thiocyanate ion in the emulsion) or distilled water (when quantifying thiocyanate ion in the binder) is used. In addition, the mixture was stirred at 40 ° C for 30 minutes. Then, centrifugation was performed at 10,000 rpm for 10 minutes using Hitachi Centrifuge 20RP-5. The supernatant liquid was diluted 100 times and then subjected to ultrafiltration using an air breath 30 manufactured by Tosoh Corporation. Next, the filtrate was subjected to chromatographic measurement using the following CR system manufactured by Tosoh Corporation. Column; TS IC-Anion SW column temperature; 40 ° C detector; UV detector (210 nm) eluent; 7.5 mM Na ₂ HPO ₄ and 7.5 mM
Solution containing NaH ₂ PO ₄ (pH 7.0), flow rate; 0.7 ml / min calibration curve; 0.1 ppm to 10 ppm potassium thiocyanate aqueous solution.

[0068]

[Table 1]

As shown in Table 1, when the incorporation amount of the thiocyanic acid compound into the emulsion layer was 3 mmol / mol-Ag or more, and when the amount of the thiocyanic acid compound on the grain surface was 2 mmol.
/ mol-Ag or more, and when the sensitizing dye of the present invention is used, the sensitivity is very high and the advanceability is excellent.

Example 2 (Preparation of particles 3) Particles 2 were prepared in the same manner as particles 2 except that pBr was set to 3.8 immediately before the addition of potassium thiocyanate during particle formation. Thus, monodisperse tabular grains having a total silver iodide content of 0.2 mol%, an average projected area diameter of 1.08 μm, a thickness of 0.159 μm and a diameter variation coefficient of 17.5% were obtained.

Coating samples were prepared in the same manner except that the grains 1 and 2 of Example 1 and the newly prepared grains 3 were added to the sensitizing dyes I-4 and II-9 in the amounts shown in Table 2. 5-8
Was prepared. The following storability test was performed on these samples. The results are shown in Table 2.

(Evaluation of Storage Stability) A coated sample was placed in a closed container containing a saturated aqueous solution of sodium nitrate at the bottom (the sample does not come into contact with the aqueous solution). This container at 50 ℃ 5
It was aged for a day (at this time, the humidity in the container was kept at 68%). After that, the same processing as that used for the evaluation of photographic properties was performed, and the density sensitization of the fogged portion was measured.

[0073]

[Table 2]

As shown in Table 2, the content of the thiocyanic acid compound was 2 × 1 regardless of the presence or absence of the sensitizing dye II-9.
It can be seen that when the content exceeds 0 ^-2 mol / mol Ag, the storage stability is impaired and the occurrence of fogging increases with time. Therefore, the incorporation amount of the thiocyanic acid compound should be within the range shown in this patent, otherwise the commercial value will be significantly impaired.

Example 3 A coated sample 9 was prepared in the same manner as in Example 1 except that the type and addition amount of the sensitizing dye were changed as shown in Table 3 using the particle 2 of Example 1.
-17 were prepared and evaluated for sensitometry in the same manner as in Example 1. The relative sensitivity of the coated sample 1 of Example 1 at the treatment time of 90 seconds was expressed as 100. The results are shown in Table 3.

[0076]

[Table 3]

As is apparent from Table 3, the use of the dyes described in this patent enabled the sensitivity to be further increased without impairing the excellent developing property.

Example 4 Coating samples 18 to 24 were prepared in the same manner as in Example 1, except that the amounts of the sensitizing dyes I-4 and II-9 added were changed as shown in Table 3 using the particles 2 of Example 1. When sensitometry was evaluated in the same manner as in Example 1, the results shown in Table 4 were obtained. As is clear from the table, it was revealed that the limitation on the amount of dye used is one of the important factors in the present invention. Here, the evaluation of the sensitivity is also shown by the relative sensitivity according to the example.

[0079]

[Table 4]

Example 5 (Preparation of pure silver bromide tabular grains (grain 4)) In the preparation of grain 1 of example 1, except that no iodide was added before adjusting pBr to 2.8. Adjusted in exactly the same way. Thus, monodisperse pure silver bromide tabular grains having an average projected area diameter of 1.10 μm, a thickness of 0.170 μm and a diameter variation coefficient of 18.5% were obtained.

(Preparation of tabular uniform silver iodobromide grains (grain 5) containing 0.3 mol% of silver iodide) 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water and kept at 55 ° C. 37cc of silver nitrate aqueous solution (silver nitrate 4.
00 g) and potassium bromide 5.7 g and potassium iodide 0.0
38cc of an aqueous solution containing 12g was prepared by the double jet method.
Added in 7 seconds. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 89 cc of silver nitrate aqueous solution (silver nitrate 9.8 g) was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added, and 10
After physically aging for minutes, 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution containing 153 g of silver nitrate and 0.3
Add an aqueous solution of potassium bromide containing mol% potassium iodide to p
While maintaining Ag of 8.5, the mixture was added by the control double jet method over 35 minutes. Next, using an aqueous silver nitrate solution,
After adjusting the pBr to 2.8, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.25 mol%, the average projected area diameter was 1.17 μm, the thickness was 0.165 μm, and the diameter variation coefficient was 1.
9.0% of monodisperse tabular grains were obtained. After that, soluble salts were removed by a sedimentation method. The temperature was raised to 40 ° C. again, 30 g of gelatin, 2.35 g of phenoxyethanol, and 0.8 g of sodium polystyrene sulfonate as a thickener.
Was added, and the pH was adjusted to 5.90 with sodium hydroxide solution and caustic soda.
It was adjusted to Ag 8.25.

(Preparation of tabular silver iodobromide grains (grain 6) containing 0.6 mol% silver iodide in the core and having a shell of pure silver bromide and a core / shell ratio of 1: 1) in 1 liter of water 6 g of potassium bromide and 7 g of gelatin were added, and 37 cc of silver nitrate aqueous solution (4.00 g of silver nitrate) was added to the container kept at 55 ° C with stirring.
38 cc of an aqueous solution containing 5.7 g of potassium bromide and 0.024 g of potassium iodide was added by the double jet method in 37 seconds. Next, after adding 18.6 g of gelatin,
The temperature is raised to 0 ° C and the aqueous solution of silver nitrate is 89cc (silver nitrate 9.8g).
Was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added and physically aged for 10 minutes at the same temperature, and then 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution containing 69.6 g of silver nitrate and 0.57 mol%
PAg of an aqueous solution of potassium bromide containing potassium iodide
1 by the control double jet method while maintaining at 8.5
Added over 6 minutes. Subsequently, an aqueous solution containing 83.4 g of silver nitrate and an aqueous potassium bromide solution were added by the control double jet method over 19 minutes while maintaining pAg of 8.5. Then, using an aqueous solution of silver nitrate, pBr was adjusted to 2.8.
After adjusting to 2, 2N potassium thiocyanate solution 15
cc was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.3 mol%, an average projected area diameter of 1.20 μm, a thickness of 0.162 μm and a diameter variation coefficient of 19.3% were obtained. After that, soluble salts were removed by a sedimentation method. The temperature was raised again to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution.

(Core is pure silver bromide and shell is 0.9 mol%
Silver iodobromide containing a silver iodide of 2: 1 with a core / shell ratio of 2: 1.
Preparation of tabular silver iodobromide grains (grain 7)) To 1 liter of water was added 6 g of potassium bromide and 7 g of gelatin, and the mixture was heated to 55 ° C.
While stirring, 37 cc of an aqueous silver nitrate solution (4.00 g of silver nitrate) and 38 cc of an aqueous solution containing 5.7 g of potassium bromide were added to the container kept at 37 ° C. for 37 seconds by the double jet method.
Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 89 cc of silver nitrate aqueous solution (silver nitrate 9.8 g) was added over 22 minutes. Here, 7cc of 25% aqueous ammonia solution
Was added and physically aged for 10 minutes at the same temperature,
6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution containing 97.4 g of silver nitrate and an aqueous solution of potassium bromide were added to p.
It was added by the control double jet method over 23 minutes while maintaining Ag of 8.5. Subsequently, silver nitrate 55.6
An aqueous solution containing g and an aqueous solution of potassium bromide containing 0.9 mol% of silver iodide were added over 12 minutes by the control double jet method while keeping pAg at 8.5. Next, the pBr was adjusted to 2.8 using an aqueous solution of silver nitrate, and then 2N
15 cc of potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.3 mol%, an average projected area diameter of 1.12 μm, a thickness of 0.165 μm and a diameter variation coefficient of 18.3% were obtained. After that, soluble salts were removed by a sedimentation method. 40 ℃ again
Heat to 30 g gelatin and phenoxyethanol 2.
35 g and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted with caustic soda and silver nitrate solution.
5.90, pAg 8.25.

(Preparation of tabular silver iodobromide grains (grain 8) containing pure silver bromide as the core and containing silver iodide in the outermost layer (total silver iodide content 0.3 mol%)) Preparation of grain 4 At pB
Before adjusting r to 2.8, 0.3 mol% based on the total amount of silver
It was prepared in exactly the same manner except that potassium iodide was added. Thus, monodisperse tabular grains having an average projected area diameter of 1.10 μm, a thickness of 0.165 μm and a variation coefficient of diameter of 17.5% were obtained.

(Preparation of tabular silver iodobromide grains (grain 9) in which the core is pure silver bromide and the outermost layer contains silver iodide (total silver iodide content 0.3 mol%)) Instead of potassium iodide, silver iodide fine particles having a diameter of 0.07 μm were prepared in exactly the same manner except for 0.3 mol% based on the total silver amount. Thus, monodisperse tabular grains having an average projected area diameter of 1.12 μm, a thickness of 0.165 μm and a variation coefficient of diameter of 18.0% were obtained.

(Preparation of Emulsion; Chemical Sensitization) Emulsions were prepared in exactly the same manner as in Example 1 using the newly prepared grains 4-9. Separately, grains 4 were prepared, and 0.3 mol% of silver iodide fine particles having a diameter of 0.07 μm was added to the total amount of silver before the addition of the sensitizing dye.

A coated sample was prepared in exactly the same manner as in Example 1, and the thiocyanate compound was quantified and the sensitometry was evaluated in the same manner. The results shown in Table 5 were obtained. Here, the evaluation of the sensitivity is also shown in the relative sensitivity in the same manner as in Example 1.

[0088]

[Table 5]

As shown in Table 5, in all the samples, high sensitivity and good development progress were obtained. On the other hand, silver iodide has a high sensitivity when it is more present on the grain surface, and has a higher sensitivity when it is present on the outermost surface. Among them, the method of redispersing fine silver iodide grains to form a silver iodide phase on the outermost surface of the grains has the highest sensitivity and is the most preferable form (method) among the same amount of silver iodide. is there.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 2, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

The silver iodide content of each emulsion grain is, for example, X.
It can be measured by analyzing the composition of each silver halide grain using a line microanalyzer. The term "coefficient of variation of the silver iodide content of individual grains" as used herein means, for example, the silver iodide content of at least 100 emulsion grains measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the standard deviation by the average silver iodide content by 100. The 5th Photographic Society of Japan
Volume 3 Issue 2 (J. Soc. Photogr. Sci. Technol. Japan Vo
L.53, No. 2, 1990), pages 125-128, the results of measuring the silver iodide content for each internal structure of each silver halide grain by an analytical electron microscope are reported. .. JOURNAL OF I
MAGING SCIENCE Vol. 31, No. 1, 1987, 15-
On page 26, the intragranular microstructure relating to the halogen composition of tabular grains is described in Low-temperature luminescenc
The method of observing using e miroscopy) has been reported in detail. Also, JOURNAL OF IMAGING SCIENCE Vol. 3
2, No. 4, 1988, pages 160 to 177, when silver chloride is deposited on silver iodobromide having an intragranular silver iodide distribution, silver iodide determines the location of silver chloride deposition (site direct). Has been reported in detail. Furthermore, it has been reported from page 213 of the Journal of the Photographic Society of Japan, Vol. 35, 1972, that the nonuniformity of the halogen composition in the grains can be observed by directly observing the grains at a low temperature using a transmission electron microscope. If the above method is used, silver halide grains 1
The fine structure of each silver halide composition, for example, the structure of silver iodide, can be observed. X-ray electron spectroscopy (XPS: X-ray Photoelectron
Spectroscopy).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

Next, a method for forming a silver iodobromide layer on the grain surface will be described. In forming the final grain surface, it is necessary to supply iodine so as to eliminate the inter-grain distribution of the surface iodine content of individual grains. The method for forming the silver iodobromide layer on the grain surface is described in, for example, British Patent No. 63.
There are so-called halogen conversion methods as described in US Pat. No. 5,841, and US Pat. No. 3,622,318. The particle surface in the present invention means a particle surface formed by the method described below. The silver iodobromide layer on the grain surface is formed by simultaneously adding a silver nitrate solution and an iodide ion-containing solution, by adding fine silver halide grains having an AgI and / or AgBrI composition, or by adding potassium iodide or iodide to a gelatin solution. A method in which potassium bromide and potassium bromide are dissolved and then cooled and added in a solid state can be applied. Among them, a method of simultaneously adding a silver nitrate solution and a solution containing iodine ions, AgI and / or AgBr
The method of adding silver halide fine grains having the composition I is a more preferable method for the present invention. In addition, JP-A-63-2
An organic compound containing iodine as described in No. 20187 may be added to the bulk liquid in the reaction vessel. Representative compounds include, but are not limited to, the following.・ ICH ₂ CH ₂ COOH ・ ICH ₂ COOH ・ ICH ₂ CN

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The emulsion layer is 2.5 × 10 ⁻³ mol or more and 2 × per mol of silver.
It contains less than 10 ^-2 mol of a thiocyanic acid compound, the sensitizing dye of the general formula (I) is 1 × 10 ^-4 mol or more per mol of silver halide, and is generally based on the compound of the general formula (I). 1 × 10 ⁻³ mol or more of the compound of formula (II) is added to 1 × 10 ^−1.
A silver halide photographic light-sensitive material characterized by containing less than or equal to mol. [Chemical 1] [Wherein, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and at least R ₁
Either of R ₂ and R ₂ is a sulfoalkyl group or a carboxyalkyl group. R ₃ represents an alkyl group. X ⁻ represents a counter ion necessary for neutralizing the charge of the molecule, and n represents a number necessary for neutralization. Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. (However, n is 0 when forming an intramolecular salt.)] [Wherein R ₁ to R ₄ are each a substituted or unsubstituted alkyl group, X ⁻ represents a counter ion necessary for neutralizing the charge of the molecule, and n represents a number necessary for neutralization. Z ₁ and Z
Each ₂ represents a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. (However, n is 0 when forming an intramolecular salt.)] 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The amount of the thiocyanic acid compound present on the surface of silver halide grains in the emulsion layer is 2 × 10 ⁻³ mol or more and 2 × per mol of silver.
The amount of the sensitizing dye of the general formula (I) is less than 10 ⁻² mol, and the sensitizing dye of the general formula (I) is 1 × 10 ⁻⁴ mol or more per mol of the silver halide, and 1 x 1
2. The silver halide photographic light-sensitive material according to claim 1, wherein the content is 0 ^-3 mol or more and 1 × 10 ^-1 mol or less. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver iodide of the silver halide grain is present only on the outermost surface of the grain. 4. The oxidation potential of the compound of general formula (II) is 0.2 eV or more baser than the oxidation potential of the compound of general formula (I). Silver halide photographic light-sensitive material.