JPH05204067A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and development speed and to reduce fog even in the case of ultrarapid development and to maintain stable photographic performance with the lapse of time without taking any countermeasure by incorporating a specified amount of thiocyanic acid compound with respect to silver halide and a tricarboxylic acid or its salt in an emulsion layer. CONSTITUTION:This silver halide photosensitive material is provided on a support with at least one of the silver halide emulsion layer containing the thiocyanic acid compound in an amount of 3X10<-2> to 2X10<-2>mol/mol of silver halide and the tricarboxylic acid or its salt. The thiocyanic acid compound is added at any time of preparation of the silver halide emulsion, preferably, both before a desalting stage and at the time of chemical sensitization, and as the thiocyanic acid compound, a metal salt of the thiocyanic acid, such as the salt of a metal not adversely affecting photographic performance, and NH4SCN, and the like are used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rapidly processable silver halide photographic light-sensitive material (hereinafter referred to as "sensitive material") and a silver halide photographic emulsion (hereinafter referred to as emulsion). Especially when subjected to rapid processing with a development time of 20 seconds or less, high sensitivity and low fog,
The present invention relates to a light-sensitive material and an emulsion which have excellent development progress and can maintain stable photographic performance even after natural aging.

[0002]

2. Description of the Related Art For a light-sensitive material, 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 development processing step of the light-sensitive material, and the processing time thereof has been greatly shortened even in the automatic developing machine processing of various light-sensitive materials. For this purpose, development of a silver halide emulsion and a light-sensitive material having excellent development progress is desired.

For the purpose of improving the above viewpoints, a technique utilizing tabular grains is disclosed in US Pat. No. 4,439,52.
0, 4,425,425 and the like. Further, in JP-A-63-305343 and JP-A-1-77047, development progress and sensitivity are controlled by controlling the development start point of a silver halide grain having a (111) face to the vertex and / or peak of the grain and the vicinity thereof. A technique for improving the / fog ratio is disclosed. These known techniques are excellent techniques and have high utility values, but further improvement has 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. As a technique for utilizing a thiocyanic acid compound, a method of obtaining highly sensitive particles by allowing a thiocyanate to exist at the time of grain formation in US Pat. Nos. 2,222,264, 3,320,069 and JP-A-62-18538. Is listed. However, the techniques disclosed in these patents have a silver iodide content of 1 mol% or more or pure silver chloride grains. As a result of studies by the present inventors, it has been found that when the silver iodide content is high, the development progress is not sufficiently improved, and pure silver chloride has a problem in sensitivity and color sensitization due to a sensitizing dye.

Further, in Japanese Patent Laid-Open No. 62-89953, when the thiocyanate ion is analyzed by infrared absorption spectroscopy,
A method for obtaining sensitive grains with an emulsion having an absorption of 052 cm ⁻¹ and containing a tricarboxylic acid is described. However, the thiocyanate ion 2052
In order to prepare an emulsion having an absorption of cm ⁻¹ , it is necessary that at least a thiocyanate be present before the completion of silver halide grain formation. There is a problem such that tabular grains having a ratio of 5 or more) cannot be obtained.

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention provides a light-sensitive material which has high sensitivity and low fog even when subjected to ultra-rapid development, is excellent in development progress, and is capable of maintaining stable photographic performance even after natural aging. To provide.

[0007]

The above objects of the present invention are as follows: (1) In a silver halide light-sensitive material having at least one silver halide emulsion layer on a support, the amount of silver halide in the emulsion layer is 3 per mol of silver. Sensitive material containing a thiocyanic acid compound in an amount of 0.times.10.sup.- ³ mol or more and less than 2.times.10.sup.- ² mol and containing a tricarboxylic acid or a salt thereof (2) Present on the surface of silver halide grains The content of thiocyanate compound is 2 × 10 ⁻³ mol or more per mol of silver 2 × 10
-Silver halide emulsion containing less than ² mol and containing tricarboxylic acid or a salt thereof (3) The average silver iodide content of silver halide grains contained in the silver halide emulsion is 1 mol% The content of the thiocyanic acid compound present on the surface of the silver halide grain is 2 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol per mol of silver, and the tricarboxylic acid or a salt thereof is contained. Achieved by the characteristic silver halide emulsion.

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 a 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, and particularly preferably 0.05 μm or less.

The thiocyanic acid compound may be added at any time during the preparation of the emulsion, but it is preferably added both before the desalting step and during the chemical sensitization. The amount of addition is 3.0 × 10 ⁻³ mol or more and less than 5 × 10 ⁻² mol, 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 thiocyanic acid compound attached to 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 light-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 light-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 actually used centrifugal separator and ion chromatography model, measurement conditions, etc.).

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

2. Quantification of thiocyanate ion on the surface of silver halide grains in coating solution emulsion 10 cc of distilled water was added to an emulsion containing 1.5 × 10 ^-2 mol of silver halide 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 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. 1 cc of 5% KBr aqueous solution was added to this solution, and then ultrasonic agitation was performed 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. Product form Quantification of thiocyanate ion on the surface of silver halide grains in the photographic material The target emulsion layer containing 1 g of silver was peeled from the photographic material 5
Immerse in 0 cc of distilled water. The 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 thus obtained value from the previously obtained value of thiocyanate ion in the photosensitive material, the amount of thiocyanate ion attached on the target particle surface is obtained. Even in the case of a multi-layer coated product light-sensitive material, if this operation is carried out after peeling by layers, the information on the emulsion of the target layer can be accurately obtained.

The tricarboxylic acid or its salt used in the present invention can be used in any of the steps of particle formation, after particle formation, desalting step (washing step), chemical aging (post-ripening), and immediately before coating. Can also be added to all steps. It is also used for ordinary pH adjustment. It is a well-known fact in the art that controlling pH during precipitation formation and post-ripening in emulsion preparation is one of the factors that greatly influences the performance of the emulsion, and it is adopted during desalting. In the precipitation method, which is the mainstream of the methods described above, inorganic salts of polyvalent anions such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic compounds) are used. Acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) is used and pH is adjusted in parallel with it (usually pH = 3 to 4.5). More usually, the emulsion is finally adjusted to a pH in the range 5-8. In that sense, acid is commonly used for emulsion preparation. In the present invention, the substituent of tricarboxylic acid or a salt thereof, which is an acid used for adjusting pH, includes a halogen atom (chlorine, bromine, etc.), a hydroxyl group and the like. Also, as the salt,
Examples thereof include alkali metal salts such as sodium and potassium, ammonium salts and the like. The representative compounds of the above-mentioned tricarboxylic acids are shown below, but the present invention is not limited to these exemplified compounds.

[0018]

[Chemical 1]

The amount of the acid of the present invention to be used depends on the pH buffer capacity of the system at that time (for example, acid-base polymer such as gelatin, acid-base additive such as NH ₃ as silver halide solvent, etc.). Depends on the amount), it is usually used in an amount of 2.0 mol to 1.0 × 10 ⁻³ mol per mol of silver halide as a pH changing amount of 1 or more. When it is used before the desalting step, the amount thereof is finally 1/10 to 1/10 ³ due to the diluting action of the desalting step. In the finished emulsion, those acids usually exist as salts such as potassium salt and ammonium salt.
2.0 mol to 1 × 10 ⁻⁶ mol of polyvalent carboxylic acid or salt thereof per mol of silver halide present in the emulsion can be easily detected by a method using ordinary liquid chromatography. That is, the water-soluble component is extracted from the emulsion with water, and if the concentration is low, it is concentrated by a freeze-drying method or the like if necessary. The extract is then analyzed using various chromatographies. At this time, when there are many interfering components, it is preferable to adsorb, desorb, and separate the polyvalent carboxylate ions with an ion exchange resin or ion exchange cellulose. ODS for chromatographic analysis
Reverse phase chromatography using (octadecyl silica) or ion chromatography using a 2010ion type machine manufactured by Dionex can be used.

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, 1
It may have a regular crystal form such as a tetrahedron,
It may also have an irregular crystal form such as a sphere, a plate, or a potato. 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, in the preparation of the monodisperse emulsion, the addition rate of the aqueous silver nitrate solution and the water-soluble halide should be increased along with the growth of silver halide grains. You can 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 for 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 flow 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, distance between grains, 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), Japanese Examined Patent Publication No. 48-36890, 52-1.
6364 and JP-A-55-142329, and the technique described in JP-A-57-179835 can be employed. The silver halide emulsion used in the present invention may be a core / shell type monodisperse emulsion, and these core / shell emulsions are disclosed in JP-A-54-4.
It is known from No. 8521 and the like. When a polydisperse emulsion is used as an emulsion in carrying out the present invention, a known method can be used for producing the polydisperse emulsion. For example THJa
"The Theory of the Photographic Process" 4th edition by mes, Neutral method, Acid method, Ammonia method, etc. described in Macmillan (1977) pages 38-104.
Forward mixing, back mixing, double jet method, controlled
It can be manufactured by applying a method such as a double jet method, a conversion method, a core / shell method or the like.

Further, tabular grains having a grain size not less than 5 times the grain thickness are preferably used in the present invention (more specifically, RESE).
ARCH DISCLOSURE Volume 225 Item 22534 p. 20-
p.58, January issue, 1983, and JP-A-58-127.
No. 921 and No. 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, "The evolution of the morphology of silver bromide crystals during physical ripening (Evolution of the Morphology of Silver Promide Crystals).・ Dualing physical reinning) "Science & Industry Photography, Volume 33, No. (19
62) pp. 121-125, Duffin, "Photographic Emulsion Chemistry (Photogra
phic emulsion Chemistry) "Focal Press (Foca
Press), New York, 1966, p.66-p.7.
2. APH Trivelli, WF Smith Photographic Journal,
Volume 80, page 285 (1940) and the like, but JP-A-58-127,921, JP-A-58-113,
It can be easily prepared by referring to the methods described in No. 927, JP-A-58-113,928, and US Pat. No. 4,439,520. The projected area diameter of the tabular emulsion of the present invention is preferably 0.3 to 2.0 .mu.m, more preferably 0.5 to 1.2 .mu.m. The distance between the planes of the flat plates (particle thickness) is 0.05 μm to 0.3 μm, particularly 0.1 to 0.25.
The thickness is preferably μm, and the aspect ratio is preferably 3 or more and less than 20, particularly 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 are present in an amount of 50% (projected area) or more, especially 70% or more of all grains, and the average aspect ratio of the tabular grains is It is preferably 3 or more, and particularly preferably 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-63-1516.
As described in No. 18.

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 70 mol% or less. Further, the silver iodide content needs to be less than 1 mol%, preferably less than 0.5 mol%, particularly preferably 0.01 mol% or more and 0.3 mol in order to achieve both rapid development progress and high sensitivity. Less than% is good. The silver halide grains may consist of a uniform layer,
It is preferable that the inside and the surface layer have different halogen compositions, and it is particularly preferable that at least the outermost surface of the silver halide grains is a silver iodide-containing layer.

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 silver iodide content of individual grains" used herein means, for example, at least 1 by X-ray microanalyzer.
The value obtained by dividing the standard deviation of the silver iodide content of the 00 emulsion grains by the average silver iodide content was 10
It is a value obtained by multiplying by 0. Journal of the Photographic Society of Japan, Vol. 53, No. 2 (J.Soc.Photogr.Sci.Technol Japan.Vol.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 IMAGING S
CIENCE Vol. 31, No. 1, 1987, pp. 15-26, describes the intragranular microstructure relating to the halogen composition of tabular grains by low-temperature luminescence micros
The method of observing using (copy) is reported in detail. Also, JOURNAL OF IMAGING SCIENCE Vol. 32, N
o.4, pp. 160-177, 1988, when silver chloride is deposited on silver iodobromide having an intragranular silver iodide distribution, silver iodide determines the location of silver chloride deposition (side direct).
It has been reported in detail. Furthermore, the Journal of the Photographic Society of Japan 3
Vol. 5, No. 4, 1972, pp. 213, it is reported 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. By using the method as described above, it is possible to observe the fine structure of the silver halide composition for each silver halide grain.

Next, the method for forming the 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 each grain. 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 the method for forming the silver iodobromide layer on the surface of the grain, a method of simultaneously adding a silver nitrate solution and a solution containing iodine ion, AgI and / or
Alternatively, a method of adding fine silver halide grains having an AgBrI composition, 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 layer may be provided on one side of the support of the photosensitive silver halide emulsion layer, 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 in the above range. If the photosensitive emulsion layer is on both sides of the support, the amount of gelatin on both sides is preferable. Are preferably in the above ranges. 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.

The melting time of the light-sensitive material of the present invention is preferably set to 8 minutes or longer and 45 minutes or shorter. The menting time referred to in the present invention means that when a sensitive material cut into 1 cm × 2 cm is dipped in a 1.5 wt% sodium hydroxide aqueous solution at 50 ° C., at least one layer of silver halide constituting the sensitive material is formed. It is the time until the emulsion layer begins to melt.

In order to effectively use the effects of the present invention,
It is preferable that a silver halide-adsorptive substance be present during chemical sensitization during the emulsion preparation process as in JP-A-2-68539. This silver halide adsorptive substance, during grain formation,
It may be added immediately after grain formation, before or after the start of post-ripening, but before the addition of a chemical sensitizer (eg, gold or sulfur sensitizer) or at the same time as the chemical sensitizer. It is preferable that it is present at least in the process of progress of chemical sensitization. As a condition for adding the silver halide adsorptive substance, the temperature may be any temperature from 30 ° C to 80 ° C, but 50 ° C to 80 ° C for the purpose of enhancing the adsorptivity.
The range of ° C is preferred. The pH and pAg may be arbitrary, but at the time of chemical sensitization, it is preferably pH 5 to 10 and pAg 7 to 9.

In the present invention, the silver halide adsorbing material means a sensitizing dye or a class of photographic performance stabilizers. That is, azoles {eg benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds {eg mercaptothiazoles , Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazole, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines and the like}; for example, oxa Thioketo compounds such as drinthione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy Conversion (1,3,3a, 7) tetraazaindenes), pentaazaindenes such like);
Many compounds known as antifoggants or stabilizers such as can be mentioned as the silver halide adsorbing material. Further, purines or nucleic acids, or polymer compounds described in JP-B-61-36213, JP-A-59-90844, etc. are also adsorbable substances that can be used. Of these, azaindenes, purines, and nucleic acids are particularly preferable and can be used in the present invention. The addition amount of these compounds is 10 to 300 per mol of silver halide.
mg, preferably 20-200 mg.

As the silver halide adsorbing material of the present invention,
Sensitizing dyes can achieve favorable effects. As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholer cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are described in, for example, US Pat. Nos. 3,522,052 and 3,619,
No. 197, No. 3,713,828, No. 3,615,6
No. 43, No. 3,615, 632, No. 3,617, 29
No. 3, No. 3,628,964, No. 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,632,349, No. 3,677,765
No. 3,370,449, No. 3,770,440
No. 3, ibid. 3,769,025, ibid. 3,745,014
No. 3,567,458, No. 3,625,698
Nos. 2,526,632 and 2,503,776
No. 48-76525, Belgian Patent No. 69
No. 1,807 and the like. The addition amount of the sensitizing dye is 200 mg or more and less than 1000 mg, preferably 300 mg or more and less than 500 mg per mol of silver halide. Specific examples of the sensitizing dye effective in the present invention are shown below.

[0031]

[Chemical 2]

[0032]

[Chemical 3]

The combined use of the sensitizing dye and the above-mentioned stabilizer is a preferred embodiment. The sensitizing dye used in the present invention may be added after chemical sensitization and before coating. The chemical sensitization method of the silver halide emulsion used in the present invention may be a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a gold sensitization method, etc. in the presence of the above-described silver halide adsorbing substance. Known methods can be used, either alone or in combination.
The selenium sensitization method is a particularly important means for the present invention.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, JP-A-2-130976, Japanese Patent Application No. 2-22930.
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium Etc. The preferred types of labile selenium compounds are described above, but are not limiting. Speaking to those skilled in the art as an unstable selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-53-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Specific examples of the compound will be shown below, but the present invention is not limited thereto.

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, and the like.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-5 mol or less. The temperature of chemical ripening when the selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide pH range of 4 to 9.

Polyhydroxybenzenes are preferably added to the light-sensitive material of the present invention for the purpose of improving pressure characteristics. Regarding the technique of adding polyhydroxybenzenes to a light-sensitive material, JP-A-54-40629 and JP-A-56-1
936, JP-A-62-21143, etc. In particular, JP-A-62-21143 discloses that the presence of a polyhydroxy-substituted benzene compound in a concentration of less than 5 × 10 ^-2 mol per mol of silver can reduce the pressure sensitivity. .. Also, JP-A-64-7214
In the system 1, the pressure sensitivity was improved by adding a polyhydroxy-substituted benzene compound in an amount less than 10 ^-1 mol per mol of silver in a system in which tabular silver halide grains having an aspect ratio of 3 or more were color-sensitized. It has been shown that it can be reduced. Typical examples of polyhydroxy-substituted benzene compounds that can be preferably used in the present invention are shown below.

[0041]

[Chemical 8]

Preferred substituents for X are --H and --O.
H, -Cl, -Br, -COOH, -CH 2 CH 2 CO
_{OH, -CH (CH 3) 2} , -CH 3, -C (CH 3) 3,
_{-OCH 3, -CHO, -SO 3 Na} , -COONa,
-SO ₃ K, such as -COOK and the like. _{-SO 3 Na, -COONa, -SO 3} K Of these compounds,
-COOK is particularly preferred for the present invention. The polyhydroxy-substituted benzene compound may be added at either the silver halide emulsion layer or another hydrophilic colloid layer. The addition amount is less than 10 ^-1 mol per mol of silver in the light-sensitive material, and particularly preferably in the range of 1 × 10 ^-3 or more and less than 6 × 10 ^-2 mol.

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention, and for example, those described in the following relevant parts can be used. Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, line 6 from the bottom or its manufacturing method, page 10 upper right column, line 12, line 3-24537 Gazette, page 2, 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 same left upper column, line 16, Japanese Patent Application No. 3-105035. 3) Antifoggant / stability JP-A-2-68539, page 10, lower left column, line 17 to the same agent, 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-3-94249, page 6, lower left column, line 15 to 11 Page top right column, line 19. 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant / antistatic From JP-A-2-68539, page 11, upper left column, line 14 to the same, page 12 upper left column, line 9

7) Matting agent, slip agent, JP-A-2-68539, page 12, upper left column, line 10 to the same right plasticizer, upper column, line 10, page 14 left lower column, line 10 to the same lower right column 1 Line. 8) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 9) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 10) Supports JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover bracket JP-A-2-264944, page 4, upper right column, line 20 to the same method, page 14, upper right column. 12) 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. 13) Layer structure JP-A-3-198041. 14) Development processing method JP-A-2-03037, 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

[0045]

EXAMPLES Next, the present invention will be described in detail based on examples. Example 1 [Preparation of emulsion] 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and an aqueous solution of 4 g of silver nitrate and 5.7 g of potassium bromide were stirred into a solution kept at 55 ° C.
Was added by the double jet method for 37 seconds. Then, after adding 18.6 g of gelatin,
The temperature was raised to 0 ° C., and an aqueous solution containing 9.9 g of silver nitrate was added over 15 minutes. Here, 7 ml of 25% aqueous ammonia solution was added, and the mixture was physically aged at the same temperature for 10 minutes, and then acetic acid was added to lower the pH to 6.0. Followed by silver nitrate 13
An aqueous solution of 3 g and an aqueous solution of potassium bromide were added over 30 minutes by the control double jet method while maintaining pBr of 1.8. The flow rate at this time was accelerated so that the flow rate at the end of addition was 6.7 times the flow rate at the start of addition. Next, after adjusting the pBr to 2.8 using an aqueous solution of silver nitrate,
20 cc of 2N potassium thiocyanate solution was added, the temperature of the emulsion thus obtained was lowered to 35 ° C., 2.5 g of formalin condensate of naphthalene sulfonic acid was added by 2.5 g, and various acids shown in Table 1 were used. Adjust the pH to 3.9,
Desalted by sedimentation method for 2 hours (dilution ratio of water-soluble substance: 1/400), heated to 40 ° C, and 30 g of gelatin
And 2.35 g of 2-phenoxyethanol and sodium polystyrene sulfonate are added, and an aqueous silver nitrate solution is added.
The pAg was adjusted to 8.20. The prepared silver halide grains are tabular and have an average projected area circle equivalent diameter of 1.08.
μm, average particle thickness 0.19 μm, diameter variation coefficient 1
It was 6.5% of monodisperse tabular grains. Then emulsion 56
The temperature was raised to 0 ° C., the pH was adjusted to 5.9, 0.043 mg of thiourea dioxide was first added, and the mixture was held for 22 minutes to carry out reduction sensitization, and then 4-hydroxy-6-methyl-1, 20 mg of 3,3a, 7-tetraindene, 400 mg of sensitizing dye 1 and 30 mg of sensitizing dye 2 were added. After 10 minutes, 1.3 mg of sodium thiosulfate, 2.7 mg of selenium compound-1, 90 mg of potassium thiocyanate and 2.6 mg of chloroauric acid were added, and chemical sensitization was performed to obtain Emulsions 1 to 8.

[0046]

[Chemical 9]

Emulsions 9 to 11 were carried out in the same manner as Emulsions 1 to 8 except that the pBr when potassium thiocyanate was added was set to 1.8 and a desalting step was carried out using the acids shown in Table 1.
Got

(Preparation of Emulsion Layer Coating Solution) The following chemicals were added to chemically sensitized emulsions 1 to 11 per mol of silver halide to prepare coating solutions. 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg trimethylolpropane 9 g dextran (average molecular weight 39,000) 18.5 g sodium 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 Gelatin so that the total amount applied to one side is 2.4 g / m ^2. It was adjusted. (1,2-Bis (vinylsulfonylacetamido) ethane) The swelling ratio was adjusted to 230%.

[0049]

[Chemical 10]

(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 g / m ² Compound (P-1) 0.013g / m 2 Compound (P-2) 0.045g / m 2 Compound (P -3) 0.0065g / m ² compound (P-4) 0.003g / m 2 compound (P-5) 0.001g / m 2 compound (P-6) 0.0012g / m 2 polymethyl methacrylate (average Particle size 3.7 μm) 0.087 g / m ² 1,2-benzisothiazoline 0.0005 g / m ² (adjusted to pH 7.4 with NaOH)

[0051]

[Chemical 11]

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

[0053]

[Chemical formula 12]

6. 434 ml of water and 6. of Triton X200® surfactant (TX-200®).
791 ml of a 7% aqueous solution 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. Observation of the resulting dye dispersion showed that the particle size of the crushed dye was 0.37 μm. 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 ml / m ² Was applied by a wire barter and the coating was dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0056]

[Chemical 13]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69 79 cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc H ₂ O 900.5 cc However, the following emulsifying dispersant was used in the latex solution.

[0058]

[Chemical 14]

A second undercoat layer having the following composition was applied onto each of the above-mentioned first undercoat layers one by one so that the coating amount would be the amount described below, and both sides at 150 ° C. by a wire bar coater method. It was applied and dried. Gelatin 160 mg / m ² dye dispersion K (26 mg / m ² as dye solid content)

[0060]

[Chemical 15]

(Preparation of Sensitive 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, Dyes 1 to 11 were obtained.

(Evaluation of Coated Samples) The prepared coated samples 1 to 11 were stored for 12 hours at a temperature and humidity of 40 ° C. and 60% RH, and then evaluated as follows. (Sensitometry) Each sample is Fuji Photo Film Co., Ltd.
X Ray Orthoscreen HR-4 manufactured by K.K. was used and both sides were exposed for 0.05 seconds. After the exposure, the following processing was performed to evaluate the sensitivity. The sensitivity was represented by the reciprocal of the ratio of the exposure dose that gives a density of 1.0 in addition to the fog, with reference to Sample 1.

(Processing) <Automatic developing machine> SRX-501 manufactured by KONICA CO., LTD. (The driving motor and gears were modified to speed up the transportation speed. <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriamine pentaacetic acid treatment 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83.3 g Diethylene glycol 40 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 22.0 g 5-Methylbenzotriazole 2 g Compound (D-1) 0.6 g Make up to 1 liter with water (adjusted to pH 10.60).

[0064]

[Chemical 16]

<Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10 g Sodium hydroxide 24 g Water is adjusted to 1 liter (pH is adjusted to 5.10 with acetic acid).

When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 333 ml of the above concentrated developer solution, 667 ml of water and 10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. Fixing tank: 200 ml of the above-mentioned stabilizing solution concentrate and 800 ml of water The processing speed ... Dry to Dry was adjusted to a predetermined time. Development temperature: 35 ° C Fixing temperature: 32 ° C Drying temperature: 45 ° C Replenishing amount: Developer: 22 ml / 10 x 12 inches Fixer: 30 ml / 10 × 12 inches

(Evaluation of Development Progression) The above-mentioned evaluation of photographic property was carried out for processing speeds of the automatic developing machine of Dry to Dry 30 seconds and 45 seconds, 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 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. After that, centrifugation was performed at 10,000 rpm for 10 minutes using Hitachi Centrifuge 20RP-5. The supernatant was diluted 100 times and then subjected to ultrafiltration using an air press 30 manufactured by Tosoh Corporation. Next, the chromatographic measurement of the filtrate was performed using the CP system manufactured by Tosoh Corporation below. Column; TS IC-Anion SW column temperature; 40 ° C detector; UV detector (210 nm) solvent; 7.5 mM Na ₂ HPO ₄ and 7.5 mM N.
a ₂ H aqueous solution containing ₂ PO ₄ (pH7.0) Flow rate; 0.7 ml / min calibration curve;. was made by measurement of 0.1ppm potassium thiocyanate aqueous solution of 10 ppm.

[0069]

[Table 1]

As shown in Table 1, when the incorporation amount of the thiocyanic acid compound into the emulsion surface was 2 mmol / mol Ag or more, the developing speed was high, and by using the acid of the present invention, High sensitivity can be achieved.

Example 2 [Preparation of emulsion] 6 g of potassium bromide and 9 g of gelatin were added to 1 liter of water, and an aqueous solution of 4 g of silver nitrate and 5 g of potassium bromide were added to a solution kept at 55 ° C with stirring. 0.7 g
Was added by the double jet method for 37 seconds. Then, after adding 18.6 g of gelatin,
The temperature was raised to 0 ° C., and an aqueous solution containing 9.9 g of silver nitrate was added over 15 minutes. Here, 7 ml of 25% aqueous ammonia solution was added, and the mixture was physically aged at the same temperature for 10 minutes, and then acetic acid was added to lower the pH to 6.0. Followed by silver nitrate 10
An aqueous solution of 6 g and an aqueous solution of potassium bromide were added over 30 minutes by the control double jet method while maintaining the pBr at 2.8. The flow rate at this time was accelerated so that the flow rate at the end of addition was 6.7 times the flow rate at the start of addition. Next, an aqueous solution of 13.3 g of silver nitrate and an aqueous solution of potassium bromide were added to pB.
While maintaining r at 3.8, it was added by the control double jet method. Subsequently, an aqueous solution of 13.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method while keeping pBr at 2.8. Then, 20 cc of 2N potassium thiocyanate solution was added, the temperature of the emulsion thus obtained was lowered to 35 ° C., 2.5 g of formalin condensate of naphthalenesulfonic acid was added in increments of 2.5, and various acids shown in Table 2 were added. The pH was adjusted to 3.9 using the method and desalted by sedimentation for 2 hours (dilution ratio of water-soluble substance: 1/40).
0), the temperature was raised to 40 ° C., 30 g of gelatin, 2.35 g of 2-phenoxyethanol and sodium polystyrene sulfonate were added, and pAg of 8.2 was obtained with an aqueous solution of silver nitrate.
Adjusted to 0. The prepared silver halide grains were tabular, and had a diameter corresponding to an average projected area circle of 1.21 μm, an average grain thickness of 0.2 μm, and a monodisperse tabular grain having a diameter variation coefficient of 15.5%. Next, the emulsion was heated to 56 ° C. and p
Adjust to H = 5.9, and then first add 0.022 of thiourea dioxide.
Add mg and hold it for 22 minutes to carry out reduction sensitization,
Then 4-hydroxy-6-methyl-1,3,3
80 mg of a, 7-tetraindene and 35 parts of the sensitizing dye 1
0 mg was added. After a further 10 minutes, sodium thiosulfate 3.3 mg, potassium thiocyanate 90 mg, chloroauric acid 0.
Emulsions 12 to 14 were obtained by adding 8 mg and performing chemical sensitization.

Emulsion 15 was obtained in the same manner as Emulsion 14, but after the formation of silver halide grains and before the desalting step, the amount of potassium thiocyanate added was 2 cc. Same as Emulsions 12 to 18 except that the amount of gelatin added first was 4 g, and the average projected area circle equivalent diameter was 0.9 μm, the average grain thickness was 0.14 μm, and the variation coefficient of diameter was 16.5%. Tabular grain emulsions 16-18 were obtained. Similar to Emulsion 18,
However, after forming the silver halide grains and before the desalting step, the amount of potassium thiocyanate added was adjusted to 2 cc to obtain Emulsion 19.
Table 2 summarizes the acids used in the desalting step of these emulsions and the content of thiocyanic acid compounds in the emulsions.

[0073]

[Table 2]

[Preparation of First Layer Emulsion Coating Solution] The following chemicals were added to the above emulsion per mol of silver halide to prepare a coating solution. Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 5.0 g Hardener 1,2-bis (vinylsulfonylacetamido) ethane 3.4 g Potassium hydroquinone monosulfonate 9.6 g Sodium polyacrylate (average) Molecular weight 41,000) 1.7 g 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 90 mg Dextran (average molecular weight 39,000) 28 g [Preparation of second layer emulsion coating solution] ] Silver halide 1 in the above emulsion
The following chemicals were added per mol to prepare a coating liquid. Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 5.0 g Hardener 1,2-bis (vinylsulfonylacetamido) ethane 3.4 g Hydroquinone potassium monosulfonate 9.6 g Sodium polyacrylate (average) Molecular weight 41,000) 1.7 g 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 90 mg Dextran (average molecular weight 39,000) 28 g [Preparation of coating solution for third layer] The anthraquinone dye used in the support in Example 1 was emulsified and dispersed in gelatin to prepare a coating solution. [Preparation of Surface Protective Layer Coating Solution] The following chemicals were added to 100 g of gelatin to prepare a coating solution. Matting agent Polymethylmethacrylate (average particle diameter 2.5 μm) 7.2 g Sliding agent Liquid paraffin 10 g Coating aid t-octylphenoxyethoxyethanesulfonic acid sodium salt 1.2 g Antistatic agent C ₈ F ₁₇ SO ₃ K 7g C ₈ F ₁₇ SO ₃ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 70 mg Sodium polyacrylate (average molecular weight 410,000) 2.2 g 1,2-benzisothiazoline 20 mg Water was added to make 1.2 liters.

It was prepared by the manufacturing method described in JP-A-62-115035, the undercoating process was applied to the emulsion coating side in advance, and the back surface side was prepared.

[0076]

[Chemical 17]

[0077] was applied to the coating solution to a blue colored triacetyl cellulose support on which coated with a diacetyl cellulose 143 mg / m ² of silicon oxide 5 mg / m ^2. At this time, the coating amount of each layer was as follows. First layer (emulsion A layer) coated silver amount 1.1 g / m ² gelatin amount 1.0 g / m ² Second layer (emulsion B layer) coated silver amount 1.6 g / m ² gelatin amount 2.1 g / m ² Third layer Gelatin amount 0.3 g / m ² Fourth layer (surface protective layer) Gelatin amount 0.5 g / m ^{2 In} this way, coated samples 12 to 20 were prepared. After storing each coated sample at 40 ° C. and 60% RH for 16 hours,
The following evaluation was performed.

[Sensitometry] Monochromatic light having a peak at 545 nm was used to perform exposure for 1/10 seconds through an optical wedge. Next, an automatic developing machine FPM-5000 (manufactured by Fuji Photo Film Co., Ltd.), a developing solution RD-3 and a fixing solution Fuji F were used, and the developing solution temperature was Dry to D at 31 ° C and 33 ° C.
ry Processed for 90 seconds. At this time, the fixing solution temperature was 30 ° C. and the washing water temperature was 20 ° C. Measure the density and cover +
The sensitivity was calculated with an exposure amount that gives an optical density of 0.3 and fog + 1.5, and the relative sensitivity was shown with the value of Sample 12 as 100. The results are summarized in Table 3.

[0079]

[Table 3]

As is apparent from Table 2, the sample of the present invention is a highly sensitive sample, and the sensitivity is less sensitive to the temperature change of the developing solution, and a stable photographic image can be obtained. I understand.

Claims (3)

[Claims] 1. A silver halide light-sensitive material having at least one silver halide emulsion layer on a support, and in the emulsion layer, 3.0 × 10 ⁻³ mol or more and 2 × per mol of silver.
^Contains less than 10 ^-2 mol of thiocyanate compound,
A silver halide photographic light-sensitive material containing a tricarboxylic acid or a salt thereof. 2. The content of the thiocyanic acid compound present on the surface of the silver halide grain is 2 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol per 1 mol of silver.
Silver halide photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the average silver iodide content of the silver halide grains contained in the silver halide emulsion is less than 1 mol%.