JPH05273686A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and development progression at the time of ultrahigh-speed processing by specifying the content of a thiocyanate compound in an emulsion layer chemically sensitized with a selenium compound and incorporating polyhydroxy-benzenes in the photosensitive material. CONSTITUTION:The photosensitive material provided on a support with at least one silver halide emulsion layer containing the thiocyanate compound, such as water-soluble salts like metal salt, preferably, KSCN or NaSCN, and NH4SCN, in an amount of 3.0X10<-3>-2X10<-2>mol per 1mol of silver and this layer is chemically sensitized with the selenium compound, and thin photosensitive material contains the polyhydroxybenzenes, thus permitting the obtained photosensitive material and the silver halide emulsion to be high in sensitivity and low in fog and superior in development progression even when processed at ultrahigh-speed and to maintain stable photographic performances with the lapse of time in a state left as it is.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material and a silver halide emulsion capable of rapid processing.
In particular, even when subjected to ultra-rapid processing with a development time of 20 seconds or less, the sensitivity is high, fog is low, the development progress is excellent, and stable photographic performance can be maintained even during natural aging. The present invention relates to a photographic light-sensitive material and a silver halide emulsion that are less likely to be blackened by an external force or pressure.

[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 processing of automatic developing machines for various photosensitive materials,
The processing time has been greatly reduced. 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 points, 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) face to the vertex of the grain and / or the acid and the vicinity thereof. And a technique for improving the sensitivity / fog ratio are disclosed. These known techniques are excellent techniques and have high utility value. Therefore, the present inventors have examined 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, US Pat. No. 2,222,264,
No. 3,320,069 and JP-A No. 62-18538 disclose a method of obtaining a highly sensitive particle by allowing a thiocyanate to be present at the time of particle formation.

However, when these technologies are put into practical use, the photographic material becomes very sensitive to various external forces and pressures applied during handling, which causes fatal blackening and desensitization in the image area. I found out that Further, compared to the conventional photographic materials, it is desired to greatly reduce the binder such as gelatin or polymer which protects the silver halide grains in order to secure a quick drying ability, but this is notable for the above undesirable phenomenon. Had been turned into. Therefore, when the introduction of polyhydroxybenzenes was attempted in order to reduce the sensitivity to external force and pressure, the purpose was achieved, but conversely, there was a dilemma that the photographic sensitivity was significantly impaired. At that time, the chemical sensitization of the photographic emulsion was gold and sulfur sensitization, but as a result of diligent studies by the present inventors, by using a selenium sensitizer for chemical sensitization, escape from the above dilemma, that is, We succeeded in reducing sensitivity to external force and pressure while maintaining high sensitivity. At that time, it was possible to achieve a rapid progress of development which has never been achieved.
The present invention is a fact that was first clarified by positively containing the thiocyanate ion in the emulsion, and cannot be easily imagined from the prior art.

Regarding the technique of adding polyhydroxybenzenes to a light-sensitive material, JP-A-54-40629 and JP-A-5-40629 are incorporated.
Nos. 6-1936 and 62-21143 are disclosed.

Regarding the selenium sensitization method, US Pat. Nos. 1,574,944, 1,602,592 and 162 are also incorporated.
No. 3499, No. 3297446, No. 329744
No. 7, No. 3320069, No. 3408196,
No. 3409197, No. 3442653, No. 3
No. 420670, No. 3591385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 5
2-34491, 52-34492, 53-2
95, 57-22090, and JP-A-59-1805.
No. 36, No. 59-185330, No. 59-18133.
No. 7, No. 59-187338, No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
JP-A-1-287380, 1-250950, 1-254441, 2-334090, and 2-11.
No. 0558, No. 2-130976, No. 2-13918
No. 3, No. 2-229300, and British Patent No. 255.
No. 846, No. 861984, and HESpencer et al., Journal of Photographic Science, Vol. 31, 1
58 to 169 (1983) and the like.

US Pat. No. 4,332,887 discloses a technique in which thiocyanate is used as a silver halide emulsion to obtain a preferable grain shape. However, the solvent effect is removed after the grain formation which becomes unnecessary. Therefore, the effect of the present invention was not exhibited. In addition, JP-A-59
No. 162652 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 gives the increase in sensitivity disclosed in the examples is 5 × per mol of silver.
It was 10 ^-2 mol.

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.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material and a halogen which have high sensitivity even when subjected to ultra-rapid processing, have low fog, have excellent development progress, and can maintain stable photographic performance even during natural aging. It is to provide a silver halide emulsion.

[0010]

The objects of the present invention are as follows (1)
And (2). (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer is 3.0 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol per mol of silver. A silver halide photographic light-sensitive material containing a thiocyanate compound, the emulsion being chemically sensitized with a selenium compound, and containing polyhydroxybenzenes in the light-sensitive material. (2) In 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 the silver halide grains is 2 × 10 ⁻³ mol or more per mol of silver. A silver halide photographic light-sensitive material characterized in that it is less than 2 × 10 ^-2 mol, that the emulsion is chemically sensitized with a selenium compound, and that the light-sensitive material contains polyhydroxybenzenes.

The specific construction 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 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 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. However, even if the pBr is 2.0 or less, by adding a large amount of the thiocyanate compound, the effect of the present invention will be exhibited if the content or the amount of adhesion is the above-mentioned preferable amount.

[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 as follows. 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 for 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 the ultrafiltration of the diluted solution, 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 the emulsion before coating: To an emulsion containing 1.5 × 10 ^-2 mol of silver halide, 10 cc of distilled water 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 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.

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, 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 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 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), 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 grains used in the present invention may be core-shell type monodisperse emulsions, and these core-shell emulsions are disclosed in JP-A-54-4.
It is known from No. 8521 and the like. 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 THJ
ames, "The Theory of the Photographic Process" 4th edition, published by Macmillan (1977), pages 38-104, etc., neutral method, acidic method, ammonia method,
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 whose grains are 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, "The evolution of the 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 (Photograph
ic 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, especially 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 iodide content is preferably less than 1.5 mol%, particularly 0.0
It is preferably 1 mol% or more and less than 0.5 mol%. 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.

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 "variation coefficient of the silver iodide content of individual grains" as used herein means, for example, the silver iodide content when the silver iodide content of at least 100 emulsion grains is measured by an X-ray microanalyzer. 1 divided by the standard silver iodide content
It is a value obtained by multiplying by 00. The 53rd Photographic Society of Japan
Volume 2 (J.Soc.Photogr.Sci.Technol.Japan Vol. 5
3, No. 2, 1990), pages 125 to 128, the results of measuring the silver iodide content of each internal structure of each silver halide grain by an analytical electron microscope are reported. JOURNAL OF IMAGI
NG SCIENCE Vol.31, No.1, 1987, pp. 15-26 describes the intragranular microstructure related to the halogen composition of tabular grains by Low-temperature luminescence miroscopy.
The means for observing by using is reported in detail. Also, JOURNAL OF IMAGING SCIENCE Vol. 32, No. 4,
In 1988, pages 160 to 177, it is reported in detail that when silver chloride is deposited on silver iodobromide having an intragranular silver iodide distribution, silver iodide determines the deposition site of silver chloride (site direct). There is. Furthermore, Japan Society of Photography 35, 19
It is reported from page 72, page 213, 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 grain surface, a method of simultaneously adding a silver nitrate solution and a solution containing iodide ions, 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 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 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,
As in JP-A-2-68539, it is preferable that a silver halide-adsorptive substance is present during chemical sensitization during the emulsion preparation process. This silver halide-adsorptive substance may be added at any time during grain formation, immediately after grain formation, before or after the start of post-ripening, but a chemical sensitizer (for example, gold or sulfur sensitizer) is added. It is preferable to be added before or at the same time as the chemical sensitizer, and it must be present at least in the process of the 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 for the purpose of enhancing the adsorptivity.
The range of -80 ° C is preferred. pH and pAg may be arbitrary,
At the time of chemical sensitization, it is preferable that pH is 5 to 10 and pAg is 7 to 9.

In the present invention, the silver halide-adsorptive substance means a sensitizing dye and a class of photographic performance stabilizers. That is, azoles {eg, benzothiazolium salt, benzimidazolium salt, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds (eg mercaptothiazoles, Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines and the like}; for example, oxadrine Thioketo compounds such as thione; 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 and JP-A-59-90844 are also adsorbable substances that can be used. Among them, azaindenes, purines, and nucleic acids can be preferably used in the present invention. The amount of these compounds added is 10 to 300 m per mol of silver halide.
g, 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
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807. The amount of sensitizing dye added is 2 per mol of silver halide.
00 mg or more and less than 1000 mg, preferably 300 mg or more 5
Less than 00 mg is good. Specific examples of the sensitizing dye effective in the present invention are shown below.

[0031]

[Chemical 1]

[0032]

[Chemical 2]

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 And so on. 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.

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-2.
No. 64443 is added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and the selenium sensitizers described above
One or more species can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. 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 1 × 10 ⁻⁵ mol or more per mol. It is 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 50 ° C or higher and 80 ° C
It is below. pAg and pH are arbitrary. For example p
The effect of the present invention can be obtained in a wide range of H from 4 to 9. The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Precious metals other than gold,
For example, platinum, palladium, iridium, and other complex salts may be contained. A specific example is US Pat. No. 2,448,
No. 060, British Patent 618,061 and the like. As the sulfur sensitizer, various sulfur compounds, such as thiosulfates, thioureas, thiazoles, rhodanins, etc., can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat. No. 1,574,944.
Issue 2, Issue 2,278,947, Issue 2,410,689
No. 2, ibid. 2,728,668, ibid. 3,501,313
No. 3,656,955.
The combined use of sulfur sensitization with thiosulfate and gold sensitization can effectively exert the effect of the present invention. As the reduction sensitizer, a primary tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used.

The photographic emulsion used in the present invention has a chemical sensitization step of the present invention for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Various compounds can be contained in addition to the silver halide-adsorptive substance. That is, azoles (eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, Tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc.}; Benzenethios Acid, benzene sulfinic acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds. Particularly, the nitrones and their derivatives described in JP-A-60-76743 and JP-A-60-87322, and JP-A-60-8083.
No. 9, the mercapto compound described in JP-A-57-16.
The heterocyclic compound described in Japanese Patent No. 4735 and a complex salt of a heterocyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole silver) can be preferably used. Even when a sensitizing dye is used as the silver halide adsorbing substance in the chemical sensitization step, a spectral sensitizing dye in another wavelength range may be added if necessary.

Polyhydroxybenzenes are added to the light-sensitive material of the present invention for the purpose of improving pressure characteristics. Techniques for adding polyhydroxybenzenes to a light-sensitive material are disclosed in JP-A-54-40629, JP-A-56-1936, JP-A-62-21143, and the like. 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. .. Further, in JP-A-64-72141, an amount of a polyhydroxy-substituted benzene compound in a system in which tabular silver halide grains having an aspect ratio of 3 or more is color-sensitized is less than 10 ^-1 mol per mol of silver. It has been shown that the pressure sensitivity can be reduced by containing The following polyhydroxy-substituted, which can be preferably used in the present invention,
Representative examples of benzene compounds are shown.

[0045]

[Chemical 11]

Preferred substituents for X are --H and --O.
H, -Cl, -Br, -COOH, -CH 2 CH 2 COO
_{H, -CH (CH 3) 2} , -CH 3, -C (C
_{H 3) 3, -OCH 3,} -CHO, -SO 3 Na, -C
OONa, -SO ₃ K, such as -COOK and the like.
In particular, hydroquinone derivatives are preferably used in the present invention. -SO ₃ Na, -CO Among these compounds
_{ONa, -SO 3 K, -COOK,} -Cl, preferred -Br particularly 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 preferably less than 10 ^-1 mol per mol of silver in the light-sensitive material.

There are no particular restrictions on other various additives 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) Color tone improving agent 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 From line 15 to page 11, upper right column, line 19. 2) Surfactants / antistatics JP-A-2-68539, page 11, upper left column, line 14 to the same, page 12 upper left column, line 9 3) 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, line 1. 4) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 5) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 6) Supports JP-A-2-68539, page 13, upper right column, lines 7 to 20. 7) Crossover cup JP-A-2-264944, page 4, upper right column, line 20 to the same method, page 14 upper right column. 8) 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. 9) Layer structure JP-A-3-198041. 10) 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 Hereinafter, the present invention will be described in more detail with reference to examples.

[0048]

【Example】

(Tabular grains having a silver iodide content of 1.0 mol% (preparation of grains 1 and 2) 4.5 g of potassium bromide, 15.0 g of gelatin, and thioether HO (CH ₂ ) ₂ S (CH ₂ ) in 1 liter of water. ₂ S (CH ₂ ) ₂ OH
5% aqueous solution (2.5 cc) was added to a container kept at 60 ° C while stirring, and 37 cc of silver nitrate aqueous solution (3.43 g of silver nitrate) was added.
And potassium bromide 2.97 g and potassium iodide 0.363 g
33 cc of an aqueous solution containing P was added by the double jet method in 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added over 13 minutes. 25% here
15cc of aqueous ammonia solution was added at the same temperature for 2
After physically aging for 0 minutes, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and 1.0 mo
An aqueous solution of potassium bromide containing 1% of potassium iodide is pA.
While maintaining g 8.5, the mixture was added by the control double jet method over 35 minutes. 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 10 minutes at the same temperature, the temperature was lowered to 35 ° C. Grain 1 was a monodisperse tabular grain having an average projected area diameter of 0.95 μm, a thickness of 0.136 μm and a variation coefficient of diameter of 18.5%. The total silver iodide content of grains 1 and 2 is 1.00 mol%. After this, the soluble salts were removed by the 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.

(Preparation of Particles 3 to 6) Particles 3 to 6 were prepared in the same manner as Particle 1 except that the amount of 2N potassium thioacynate added was 15 cc. Average projected area diameter of grain 3 is 0.96
μm, thickness 0.137 μm, diameter variation coefficient 17.2%
Was a monodisperse tabular grain. The total silver iodide content of grains 3 to 6 is 1.00 mol%. After this, the soluble salts were removed by the 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 polyethylene sulfonate as a thickener were added, and pH was adjusted to 5.90 with a caustic soda and silver nitrate solution, pA.
The g was adjusted to 8.25.

(Chemical Sensitization A) Next, the particles 1 to 4 were chemically sensitized while being kept at 56 ° C. while being stirred. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 400 mg of sensitizing dye A were added. Furthermore, 0.83 g of an aqueous calcium chloride solution was added. Subsequently, 1.3 mg of sodium thiosulfate, 2.7 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 and 4 was completed.

[0051]

[Chemical formula 12]

(Chemical Sensitization B) Next, the particles 5 and 6 were subjected to chemical sensitization while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 400 mg of sensitizing dye A were added. Furthermore, 0.83 g of an aqueous calcium chloride solution was added. Subsequently, 2.6 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, at 35 ° C.
Cooled to. Thus, the preparation of emulsions 1 to 6 was completed.

(Preparation of Emulsion Coating Layer) The following chemicals were commonly added to chemically sensitized emulsions 1 to 6 per mol of silver halide. -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 (B) 3.4 mg-Snowtex C (Nissan Chemical Co., Ltd.) 29.1 g-Gelatin A total amount applied on one side was 2.4 g / m ² . Hardener (1,2-bis (vinylsulfonylacetamide) ethane Prepared to have a swelling ratio of 230%.

[0054]

[Chemical 13]

Here, 2.0 × 10 ^-2 mol of hydroquinone was added to 1 mol of silver only in Emulsions 2, 4, and 6 to prepare a coating solution.

(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 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)

[0057]

[Chemical 14]

(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.

[0059]

[Chemical 15]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X200® surfactant (TX-200®) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (Zr
400 ml (2 mm diameter) beads of O) were added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin 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 had a wide distribution ranging from 0.05 to 1.15 .mu.m in diameter, and the average particle size was 0.37 .mu.m. Furthermore, by performing a centrifugation operation, 0.9 μm
Dye particles of the above size were removed. 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.

[0062]

[Chemical 16]

• 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 emulsion dispersants were used in the latex solution.

[0064]

[Chemical 17]

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)

[0066]

[Chemical 18]

(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 coated silver amount per side is 1.75 g.
/ M ² . Thus, samples 1 to 6 were obtained.

(Evaluation of Photographic Performance) The photographic material was exposed for 0.05 seconds from both sides by 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 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 processor> ... SRX- manufactured by KONICA CO., LTD.
501 (The transport speed was increased by modifying the drive motor and the gear part.) <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid treatment 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83 0.3 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 Water to 1 liter (prepared to pH 10.60) ).

[0070]

[Chemical 19]

<Fixing Solution Concentrated Solution> 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 (adjusted to pH 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 fixing solution concentrate and 800 ml of water The processing speed ... Dry to Dry was adjusted to a predetermined time. Development temperature ・ ・ ・ 35 ℃ Fixing temperature ・ ・ ・ 32 ℃ Drying temperature ・ ・ ・ 45 ℃ Replenishing amount ・ ・ ・ Developer 22ml / 10 × 12 inches Fixer 30ml / 10 × 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) The amount of thiocyanate compound was determined according to 1 and 2 (quantification of thiocyanate ion in the emulsion before coating). That is, a 1% KBr aqueous solution (when quantifying thiocyanate ion in the emulsion) or distilled water (when quantifying thiocyanate ion in the binder) is added to an emulsion containing 1.5 × 10 ^-2 mol of silver halide. 10 cc was added and 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 breath 30 manufactured by Tosoh Corporation. Next, the filtrate was subjected to chromatographic measurement using the CR system manufactured by Tosoh Corporation below. Column; TS IC-Anion SW Column temperature: 40 ° C Detector: UV detector (210 nm) Dissolution solution: 7.5 mM Na ₂ HPO ₄ and 7.5 mM 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 was prepared.

Evaluation of Pressure Performance Samples 1 to 6 were conditioned under the conditions of 25 ° C. and 25% RH for 1 hour, and then bent 180 ° under the same conditions in accordance with a stainless pipe having a diameter of 6 mm. The bending speed was 180 ° for 1 second, and the original state was restored for the next 1 second. The evaluation was visually conducted on a scale of 5 levels. 5 is the best condition, and 1 is the worst condition. A level of 3 or higher is acceptable.

[0076]

[Table 1]

The results are summarized in Table 1. Samples 1 and 2 have incorporation amount of thiocyanic acid compound in the emulsion of 3 mmol / mol
Since it is Ag, the sensitivity is low and the progress of development is not satisfactory. The addition of hydroquinone improves the pressure performance, but hardly changes the sensitivity and the development progress. On the other hand, Sample 3 has a thiocyanate compound uptake of 3 mmol.
/ mol Ag or more, and high sensitivity and improved development progress, but poor pressure performance. The sample 4 of the present invention not only has improved pressure performance by addition of hydroquinone, but also has significantly improved sensitivity and good development progress. Sample 5,
No. 6 had a thiocyanate compound incorporated amount of 3 mmol / mol Ag or more as in Samples 3 and 4, the sensitivity was low and the development progress was not satisfactory unless a selenium compound was used for chemical sensitization. Sample 6 was improved in pressure performance by the addition of hydroquinone, but was greatly sacrificed in sensitivity and development progress. As described above, according to the present invention, it was possible to obtain a light-sensitive material having high sensitivity, excellent development progress, and excellent pressure performance in practical use.

Example 2 (1) Preparation of tabular pure silver bromide grains 7 to 8 In 1 liter of water, 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatic treatment of alkali-treated gelatin were added. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g of potassium bromide were added to the container kept at 55 ° C. for 45 seconds by the double jet method while stirring. Then, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C. and an aqueous solution of 11.11 g of silver nitrate was added in 12 minutes. Next, 6 ml of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% aqueous acetic acid was added to neutralize. Then, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while keeping the potential at pAg 8.5. The flow rate at this time was linearly accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. At the time when 23 minutes have passed since the start of this flow rate flow rate addition, 5 × 10 ⁻⁵ g of K ₃ IrCl ₆ was added.
Was added. After the addition by the control double jet method for 25 minutes was completed, 15 cc of 2N potassium thiocyanate solution was added. Then, the temperature was lowered to 35 ° C., the soluble salts were removed by the precipitation method, the temperature was raised to 40 ° C., 41 g of gelatin and 2.5 g of phenoxyethanol were added, and the pH was adjusted to 5.95 with NaOH. Thus, tabular pure silver bromide grains 7 and 8 were prepared. The obtained emulsion had a silver iodide content of 0.051 mol%, an average projected area diameter of 0.62 μm (standard deviation of 9.0%), and an average thickness of 0.
The aspect ratio was 6.2 at 10 μm.

(2) Preparation of tabular pure silver bromide grains 9 to 12 In 1 liter of water, 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating an alkali-treated gelatin were added to 55 ° C. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g of potassium bromide were added to the container kept under stirring for 45 seconds by the double jet method. Then, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C. and an aqueous solution of 11.11 g of silver nitrate was added in 12 minutes. Next, 6 ml of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% aqueous acetic acid was added to neutralize. Then, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining the potential at pAg of 8.8. The flow rate at this time was linearly accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. When 23 minutes have passed since the start of this accelerated flow rate addition, K ₃ IrCl ₆ was added at 5 × 10 ⁻⁵ g.
Was added. After the addition by the control double jet method for 25 minutes was completed, 15 cc of 8N potassium thiocyanate solution was added. Then, the temperature was lowered to 35 ° C., the soluble salts were removed by the precipitation method, the temperature was raised to 40 ° C., 41 g of gelatin and 2.5 g of phenoxyethanol were added, and the pH was adjusted to 5.95 with NaOH. Thus, tabular pure silver bromide grains 9 to 12 were prepared. The obtained emulsion had a silver iodide content of 0.051 mol%, an average projected area diameter of 0.62 μm (standard deviation of 9.0%), and an average thickness of 0.
The aspect ratio was 6.2 at 10 μm.

(Chemical Sensitization) Next, the particles 7 to 10 were chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 40 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 600 mg of sensitizing dye A were added. Furthermore, 0.83 g of an aqueous calcium chloride solution was added. Subsequently, 1.8 mg of sodium thiosulfate, 3.1 mg of selenium compound-2, 3.3 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. The emulsion was thus prepared.

[0081]

[Chemical 20]

(Chemical sensitization) Next, the particles 11 and 12 were added.
On the other hand, chemical sensitization was performed while maintaining the temperature at 56 ° C. with stirring. First, add 0.043 mg of thiourea dioxide and add 2.
It was held as it was for 2 minutes for reduction sensitization. Next, 4-
40 mg of hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 600 mg of sensitizing dye A were added. Furthermore, 0.83 g of an aqueous calcium chloride solution was added. Then, 3.0 mg of sodium thiosulfate, 3.3 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, 35
Cooled to ° C. Thus, the preparation of emulsions 7 and 12 was completed. (10) Preparation of emulsion coating solution The following chemicals were added to the emulsion per mol of silver halide to prepare a coating solution. Polymer latex poly (ethyl acrylate / methacrylic acid = 97/3) 9 g Hardener 1,2-bis (vinylsulfonylacetamide) ethane 1.5 g Gelatin 23 g 2,6-bis (hydroxyamino) -4- Diethylamino-1,3,5-triazine 67.5 mg

[0083]

[Chemical 21]

Dextran (average molecular weight 39,000) 16.7 g Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) 45 cc Sodium polystyrene sulfonate 1.8 g Here, only emulsions 8, 10 and 12 have the following structure. 3. The polyhydroxybenzene compound of 4. with respect to 1 mol of silver halide.
0 × 10 ^-2 mol was added to ^obtain a coating solution.

[0085]

[Chemical formula 22]

(11) Coating on Emulsion Layer Side The emulsion layer coating solution was coated simultaneously with the following emulsion protective layer coating solution on a blue dyed transparent polyethylene terephthalate support having a thickness of 175 μm by the coextrusion method. The coated silver amount was 2.5 g / m ² . The surface protective layer was prepared such that each component had the following coating amount. Contents of the surface protective layer Coating amount-Gelatin 0.65 g / m ² -Polyacrylamide (average molecular weight 45,000) 0.25 -Sodium polyacrylate (average molecular weight 400,000) 0.02 -pt-octylphenoxy Sodium salt of diglyceryl butyl sulphonate 0.02 ・ Poly (degree of polymerization 10) oxyethylene cetyl ether 0.035 ・ Poly (degree of polymerization 10) Oxyethylene-poly (degree of polymerization 3) Oxyglyceryl-p-octylphenoxy ether _{0.01 · C 8 F 17 SO 3} K 0.003

[0087]

[Chemical formula 23]

-Polymethylmethacrylate (average particle size 3.5 μm) 0.025-Poly (methylmethacrylate / methacrylate) (molar ratio 7: 3, average particle size 2.5 μm) 0.020-Proxel 0.001

(12) Preparation of Antihalation Layer A halation prevention layer and a surface protection layer of the antihalation layer were coated on the side on which the emulsion layer and the surface protection layer were coated, and on the side opposite to the support. Each layer was prepared so as to have the following coating amount. (Antihalation layer) ・ Gelatin 4.2 g / m ²・ Phosphoric acid 5.2 mg / m ²・ Colloidal silica (average particle size 0.03 μm) 0.5 g / m ²

[0090]

[Chemical formula 24]

[0091]

[Chemical 25]

· Potassium polystyrene sulfonate (average molecular weight 600,000) 25 mg / m ² · Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 0.53 g / m ² · Hardener 1,2- Bis (vinylsulfonylacetamide) ethane 54 mg / m ² (13) Surface protection layer for antihalation layer ・ Gelatin 1.25 g / m ²・ Polymethylmethacrylate (average particle size 3.5 μm) 65 mg / m ²

[0093]

[Chemical formula 26]

C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² · potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ² antihalation layer and its surface protection layer The simultaneous extrusion method was applied and dried simultaneously. Thus emulsions 7-12
To obtain photographic materials 7-12.

(14) Evaluation of Photographic Performance Each of the photographic materials 7 to 12 was exposed for 1 second from the emulsion layer side with white light using a tungsten lamp as a light source. After the exposure, the same processing as in Example 1 was performed. The sensitivity is indicated by the reciprocal of the ratio of the exposure amount that gives a density of fog +0.1 with the processing of 45 seconds of the photographic material 21 as the standard = 100.
The results are summarized in Table 2.

(15) Evaluation of development progress As in Example 1, the processing speed of the automatic processor was Dry to
Dry 45 seconds and 30 seconds (after the tip of the sensitive material was inserted until the tip comes out to the dry zone) were evaluated, and the sensitivities of both were compared.

(16) Quantitation of thiocyanic acid compound In the same manner as in Examples 1 and 2, quantification was performed on the emulsion layer side. (17) Evaluation of pressure performance The same evaluation as in Example 1 was performed.

[0098]

[Table 2]

The results are summarized in Table-2. Although a grain forming method, a selenium sensitizer, and a polyhydroxybenzene compound different from those in Example 1 were used, the effect of the present invention is remarkably exhibited also in this example.

Example 3 (Preparation of particles 13) Particle 3 was prepared in the same manner as particles 3 of Example 1 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 1.0 mol%, an average projected area diameter of 0.95 μm, a thickness of 0.138 μm and a diameter variation coefficient of 17.0% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was again raised 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.

(Preparation of tabular grains (grain 14)) To 1 liter of water was added 6 g of potassium bromide and 5 g of gelatin,
Aqueous silver nitrate solution 37 with stirring into a container kept at 55 ° C
33 cc of an aqueous solution containing cc (4.00 g of silver nitrate) and 5.7 g of potassium bromide was added by the double jet method in 37 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 to 22
Added over 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 153 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. Next, pBr was adjusted to 2.8 using an aqueous solution of silver nitrate, and then 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, monodisperse pure silver bromide tabular grains having an average projected area diameter of 0.94 μm, a thickness of 0.130 μm and a diameter variation coefficient of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was again raised 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. The temperature was raised again to 56 ° C., 0.05 mol of a silver iodide fine grain emulsion having an average diameter of 0.03 μm was added, and the mixture was allowed to stand for 10 minutes.

(Preparation of particles 15) Particles 15 were prepared in the same manner as particles 14 except that the pBr immediately before the addition of potassium thiocyanate during the formation of particles was 3.8. Thus, monodisperse pure silver bromide tabular grains having an average projected area diameter of 0.94 μm, a thickness of 0.131 μm and a diameter variation coefficient of 17.2% were obtained. After this, the soluble salts were removed by the 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.
It was adjusted to 5.90 and pAg 8.25. Temperature again 56
The temperature was raised to .degree. C., 0.05 mol of silver iodide fine grain emulsion having an average diameter of 0.03 .mu.m was added, and the mixture was allowed to stand for 10 minutes.

Next, the particles 13 to 15 were subjected to the same chemical sensitization and coating as in Sample 4 of Example 1 to obtain Samples 13 to 15. The following shelf life test was performed on these samples,
Samples 4 and 13-15 were compared. The results are shown in Table 3.

(Evaluation of Storage Stability) A coated sample was placed in a closed container having 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 fog portion was measured. The results are shown in Table 3.

As shown in Table 3, when the content of the thiocyanic acid compound exceeds 2 × 10 ^-2 mol / mol Ag, the storage stability is impaired and the occurrence of fogging with time increases. . 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.

[0106]

[Table 3]

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[Procedure amendment]

[Submission date] June 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

(Processing) <Automatic processor> ... SRX- manufactured by KONICA CO., LTD.
501 (The drive motor and the gear part were remodeled to speed up the conveyance speed.) <Developer concentrate> Potassium hydroxide 56.6 g Sodium sulfite 200 g Diethylenetriaminepentaacetic acid treatment 6.7 g Potassium carbonate 16.7 g Boric acid 10 g Hydroquinone 83 0.3 g diethylene glycol 40 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 22.0 g 5-methylbenzotriazole 0.2 g Compound (D-1) 0.6 g Water to 1 liter (pH 10.60) Prepared).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0078

[Correction method] Change

[Correction content]

Example 2 (1) Preparation of tabular pure silver bromide grains 7 to 8 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating alkali-treated gelatin were added to 1 liter of water. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g of potassium bromide were added to the container kept at 55 ° C. for 45 seconds by the double jet method while stirring. Then, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C. and an aqueous solution of 11.11 g of silver nitrate was added in 12 minutes. Then, 6% of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% aqueous acetic acid solution was added to neutralize. Then, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while keeping the potential at pAg 8.5. The flow rate at this time was linearly accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. When 23 minutes have passed since the start of this flow rate flow rate addition, K ₃ IrCl ₆ was added to 5 × 10 5.
^-5 g was added. After the addition by the control double jet method for 25 minutes was completed, 15 cc of 2N potassium thiocyanate solution was added. Then, the temperature is lowered to 35 ° C., the soluble salts are removed by a precipitation method, and then the temperature is raised to 40 ° C., and 41 g of gelatin and 2.5 parts of phenoxyethanol are added.
g and the pH was adjusted to 5.95 with NaOH.
Thus, tabular pure silver bromide grains 7 and 8 were prepared. The emulsion thus obtained had an average projected area diameter of 0.62 μm (standard deviation of 9.0%), an average thickness of 0.10 μm and an aspect ratio of 6.2.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

(2) Preparation of tabular pure silver bromide grains 9 to 12 In 1 liter of water, 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating an alkali-treated gelatin were added to 55 ° C. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g of potassium bromide were added to the container kept under stirring for 45 seconds by the double jet method. Then, after adding 20 g of gelatin having a normal molecular weight, the temperature was raised to 62 ° C. and an aqueous solution of 11.11 g of silver nitrate was added in 12 minutes. Then, 6% of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% aqueous acetic acid solution was added to neutralize. Then, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining the potential at pAg of 8.8. The flow rate at this time was linearly accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. When 23 minutes have passed since the start of this accelerated flow rate addition, K ₃ IrCl ₆ was added to 5 × 10 5.
^-5 g was added. After the addition by the control double jet method for 25 minutes was completed, 15 cc of 8N potassium thiocyanate solution was added. Then, the temperature is lowered to 35 ° C., the soluble salts are removed by a precipitation method, and then the temperature is raised to 40 ° C., and 41 g of gelatin and 2.5 parts of phenoxyethanol are added.
g was added and the pH was adjusted to 5.95 with NaOH. Thus, tabular pure silver bromide grains 9 to 12 were prepared. The emulsion thus obtained had an average projected area diameter of 0.62 μm (standard deviation of 9.0%), an average thickness of 0.10 μm and an aspect ratio of 6.2.

[Procedure correction 4]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction content]

[0098]

[Table 2]

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

[0106]

[Table 3]

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The emulsion layer is 3.0 × 10 ⁻³ mol or more and 2 × per mol of silver.
^Contains less than 10 ^-2 mol of thiocyanate compound,
And the emulsion is chemically sensitized with a selenium compound,
A silver halide photographic light-sensitive material characterized by containing polyhydroxybenzenes in the light-sensitive material. 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 the silver halide grains is 2 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol per mol of silver, and the emulsion is chemically sensitized with a selenium compound, and A silver halide photographic light-sensitive material characterized by containing polyhydroxybenzenes in the light-sensitive material.