JPH0457046A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity and low fog and to improve the developability of a latent image and shelf stability by incorporating silver halide particles of a specified average particle size into a silver halide emulsion layer and specifying the pH of a film surface on one side of a base on which the silver halide emulsion layer is present. CONSTITUTION:This sensitive material contains at least one kind of compd. represented by the formula (where each of R1 and R2 is lower alkyl or sulfoalkyl, R3 is methyl, X1 is an anion, each of Y2 and Y2 is a group of nonmetallic atoms required to form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring or a quinoline ring, each of n1 and n2 is 1 or 2, m1 is 1 or 0, and in the case of inner salt, m1 is 0). This sensitive material has at least one silver halide emulsion layer on the base and the emulsion layer contains silver halide particles of >=0.33mum average particle size. Silver chlorobromide or silver chloroiodobromide having >=60mol% silver chloride content is preferably used as the silver halide in the silver halide emulsion.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic material, and more specifically, a silver halide photographic material having high sensitivity, low capri, and improved 1vI image progression and storage stability. Regarding materials.

[Prior Art] As a recent trend, there has been a demand for higher sensitivity in photosensitive materials for newspaper facsimile plotters. However, when high sensitivity is achieved, there is a tendency for latent image stability, storage stability, etc. to deteriorate, posing a new problem.

[Problems to be solved by the invention] The present invention has been made to solve the above problems,
An object of the present invention is to provide a silver halide photographic material that has high sensitivity, low fog, and improved latent image progression and storage stability.

[Means for Solving the Problems] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer has an average grain size of 0. Contains silver halide grains of 33 μm or more, and
The pH of the film surface on the side with the silver halide emulsion layer is 4.0 or more and 7
．． θ or less, and containing at least one compound represented by the following general formula [I], wherein Yl and Y2 each represent a benzothiazole ring. , represents a group of nonmetallic atoms necessary to form a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring, and these heterocycles are lower alkyl groups,
It may be substituted with an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom.

R□ and R2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R8 represents a methyl group, an ethyl group, or a propyl group. X represents an anion.

n and n2 represent 1 or 2. ml represents 1 or O, and in the case of an inner salt, m□=0. The present invention will be explained in more detail below.

The silver halide photographic light-sensitive material of the present invention needs to have a pH of 4.0 or more and 7.0 or less, preferably 5.0 or less, on the side of the support that has the silver halide emulsion layer.
It is 7.0 or more, more preferably 6.0 or more and 70 or less. Adjustment of the film surface pH is preferably carried out using an emulsion layer coating solution or a protective film layer coating solution. Although the membrane surface pH may be adjusted at any time, it is preferable to adjust the membrane surface pH in a solution state before application of the coating solution. As a pH 1l adjuster,
For example, sodium carbonate, sodium hydroxide, citric acid,
Examples include, but are not limited to, acetic acid and the like. The membrane surface pH value was measured in an air-conditioned room at 23°C and 48% R, H using a pr-r meter HM-20E (manufactured by Toa Denpa Kogyo ■) and pH electrode G5-5013F (manufactured by Toa Denpa Kogyo ■). This is the value measured using

The silver halide photographic light-sensitive material of the present invention has the general formula [I
] Contains at least one compound represented by.

The compound represented by the general formula [I] used in the present invention will be explained below.

In the general formula [T], Y and Y2 each represent a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring,
Represents a group of nonmetallic atoms necessary to form a naphthoselenazole ring or a quinoline ring, and these heterocycles include lower alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.) , a hydroxyl group, an aryl group (eg, phenyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group), a halogen atom (eg, chlorine atom, bromine atom, etc.), or the like. R and R2 are lower alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), alkyl groups having a sulfo group (e.g., β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ- sulfobutyl group, sulfoalkoxyalkyl group (e.g. sulfoethoxyethyl group, sulfopropoxyethyl group), alkyl group having a carboxyl group (e.g. β-carboxylethyl group, γ-carboxypropyl group, γ-carboxybutyl group, δ- carboxybutyl group, etc.). R3 represents a methyl group, an ethyl group, or a propyl group. xl represents an anion commonly used in cyanine dyes (eg, halogen ion, benzenesulfonate ion, p-toluenesulfonate ion, etc.). m represents 1 or O,
When it is an inner salt, m=o.

Next, the configuration of the present invention will be explained in more detail.

First, specific examples of the compound represented by the above general formula [I] used in the present invention will be shown. However, in the present invention, the above general formula [+
Examples of compounds represented by 1 ■-11 ■-12 l-13 ■-15 ■-16 ■-21 ■-22 ■-23 ■-24 CH.

■-17 ■-18 ■-19 ■-25 ■-26 ■-27 ■-29 ! -33 ■-30 ■-34 ■-31 ■-35 ■-32 ■-36 The compound represented by the general formula [I] is preferably 1 mg to 2 g per mole of silver halide, more preferably 5 m
It is contained in the silver halide photographic emulsion in the range of 1 g to 1 g.

The compound represented by the general formula [I] can be directly dispersed into an emulsion. In addition, these can be prepared using a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

The compounds represented by the general formula [I] may be used alone or in combination of two or more. It can also be used in combination with sensitizing dyes other than those mentioned above. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The compound represented by the general formula [I] can be easily obtained by referring to U.S. Pat. can be synthesized into

The light-sensitive material of the present invention has at least one silver halide emulsion layer, and the emulsion layer contains silver halide grains having an average grain size of 0.33 μm or more.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
As the silver halide, it is preferable to use silver chlorobromide or silver chloroiodobromide having a silver chloride content of 50 mol % or more, more preferably silver chloride content of 60 mol % or more.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method, and the grain size is 0.33 μm.
0.3 μm or more, preferably 0.3 μm or less, and more preferably 0.3 μm or less.
It is 7 μm or more and 0.45 μm or less.

In the silver halide grains used in the above emulsion, water-soluble rhodium salts and water-soluble iridium salts are added during the grain formation process, and are included inside the grains and/or on the grain surfaces.

The amount added is 10-6 to 1 per mole of silver halide.
0-9 mol is preferred.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, US Patent No. 183,756, US Patent No. 4,225,66
No. 6, JP-A-55-26589, JP-A-55-427
Specifications such as No. 37, The Journal of Photographic Science (J, Photogr, 5c)
i) Particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can be prepared by the method described in the literature such as 21.39 (1973) and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodispersed emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size r is the frequency ni of particles having particle size ri.
The particle size r when the product n1Xri'' of and ri8 is maximum
Define as i.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when converted to a circular image with the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called unripened (Pr1m1t1ve) emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikman et al. or H. Fr1eser, ed.
Die
Grundlagen der Photography
ischen Prozesse mit Silbe
rhalogeniden, Akademicche
Verlaggesellschaft, 196
The method described in 8) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other heavy metal compounds can be used.

As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat. No. 1,574,944.
No. 2,410,689, No. 2,278,947, No. 2,728,668, and No. 3,656,955. As the reduction sensitizer, soot salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,419 ,97
No. 4, No. 2,518,698, No. 2,983,609
No. 2,983,610, and No. 2,694,637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, No. 399,083, No. 2.448,060, and US Pat. No. 618.061.

In addition, there are no particular restrictions on conditions such as pHlpAg and temperature during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is preferably maintained at 5 to 11, particularly 7 to 9. is preferred. Also, the temperature is 40 to 90°C, especially 4
5-75°C is preferred.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptopenzothiazole, and the like. Furthermore, if necessary, a silver halide solvent such as a thioether, or a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

Unnecessary soluble salts may be removed from the emulsion after the growth of silver halide grains is completed, or they may be left in the emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (especially nitro- or halogen-substituted), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1
-phenyl-5-mercaptotetrazole), mercaptopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially Many compounds known as stabilizers can be added, such as 4-hydroxy substituted (1,3,3a,7)tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, and the like.

An example of a compound that can be used is in The Theory of the Photographic Process, by K. Mees.
Theory of the Photography
ic Process, 3rd edition, 1966), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 2.947, No. 4,021,248 or Special Publication No. 1973
-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention contains U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Belgian Patent No. 762,833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, Various hardeners and ultraviolet absorbers such as ethyleneimine type, active halogen type, vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc., and ultraviolet absorbers include, for example, U.S. Patent No. 3,253, 92
No. 1, British Patent No. 1,309,349, etc., particularly 2-(2'hydroxy-5
-tertiary butylphenyl)penzotriazole, 2- (
2'-Hydroxy-3'5'-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3'
-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'
Examples include 5'-di-tertiary butylphenyl)-5-chlorobenzotriazole. Furthermore, coating aids,
British Patent No. 548,53 describes emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials.
No. 2, No. 1,216,389, U.S. Patent No. 2,026,
No. 202, No. 3,514,293, Special Publication No. 1977-26
No. 580, No. 43-179'22, No. 43-1792
No. 6, No. 43-3166, No. 48-20785, French Painting Patent No. 202,588, Belgian Patent No. 773,45
Anionic, cationic, nonionic or amphoteric compounds described in No. 9, JP-A-48-101118, etc. can be used, and among these, anionic surfactants having a sulfone group, For example, succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-241
No. 59, JP 4889979, U.S. Patent No. 2,882
, No. 157, No. 2,972,535, JP-A No. 1972-2
No. 0785, No. 48-43130, No. 4B-9039
No. 1, Special Publication No. 46-24159, No. 46-39312
There are compounds described in the following publications: No. 48-43809 and JP-A No. 47-33627.

In the manufacturing method according to the present invention, the pH of the coating liquid is 53 to
A range of 75 is preferred. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is in the above range of 53 to 7.5. If the pH is less than 5.3, the progress of hardening will be slow, which is undesirable, and if the pH is greater than 75, it will have an adverse effect on photographic performance, which is undesirable.

In the light-sensitive material of the present invention, the constituent layers include matting agents, such as silica described in Swiss Patent No. 330,158, glass powder described in French Painting Patent No. 1,296,995, and British Patent No. 1.
, 173,181; inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; starch as described in U.S. Pat. No. 2,322,037; Belgian Patent No. 62;
Starch derivatives described in No. 5,451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, and U.S. Patent No. 330,158. Organic particles such as polyacrylonitrile as described in US Pat. No. 3,022,169 and polycarbonate as described in US Pat.

In the photosensitive material of the present invention, the constituent layers include slipping agents, such as those described in US Pat. No. 2,588,756 and US Pat.
higher alcohol esters of higher aliphatics as described in US Pat. No. 3,295,979; higher aliphatic calcium salts as described in UK Patent No. 1,263.722; , U.S. Patent No. 3,042
, No. 522, and No. 3.489567. Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and Volume 187 I
tem18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type RD17643 RD187
161, chemical sensitizer page 23 6
Page 48, right column 2, Sensitivity enhancer
Same as above 4, Brightener Anti-stain agent Dye Image stabilizer Hardener Binder Plasticizer/Lubricant Coating aid/Surfactant Antistatic agent Page 24 Page 25 Right column Page 25 Page 26 Page 26 Page 27 Pages 26-27 Page 27, page 650, left to right column, page 651, left column, same as above, page 650, right column, same as above, same as above The photographic processing of the silver halide photographic material according to the present invention is as follows:
Various methods can be used without particular limitations.

The processing temperature is usually chosen between 18°C and 50°C,
The temperature may be lower than 18°C or higher than 50°C.

The developing agents used in the black and white developer used in the present invention are dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-
phenyl-3-pyrazolidone), aminophenols (
For example, N-methyl p-aminophenol) can be used alone or in combination.

The silver halide photographic material of the present invention may be photographically processed using a developer containing imidazoles as a silver halide solvent. It is also possible to process with a developer containing a silver halide solvent and an additive such as indazole or triazole. The developing solution generally contains various other preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and further contains dissolving aids, color toners, development accelerators, surfactants, antifoaming agents, etc. as necessary. , a water softener, a hardening agent, a viscosity imparting agent, and the like.

Furthermore, so-called "squirrel-type" development processing can be performed. As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed with an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones can be incorporated into the emulsion layer by the method described in Research Disclosure No. 169 and others.

Such development treatment may be combined with silver salt stabilization treatment using thiocyanate.

As the fixer, one having a commonly used composition can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The exposure for the photographic emulsion used in the present invention varies depending on the state of chemical sensitization, the purpose of use, etc.
Various light sources such as fluorescent lamps, arc lamps, mercury lamps, xenon sunlight, xenon flashes, cathode ray tube flying spots, laser beams, electron beams, X-rays, and fluorescent screens for X-ray photography can be used as appropriate.

In addition to normal exposure of 171,000 to 100 seconds, the exposure time for xenon flash, cathode ray tube, and laser light is 1.
Short exposure times of /10-' to 1/10-9 seconds can be applied.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example 1 <Preparation of coating solution for emulsion layer> (Preparation of emulsion A) Solution-1 Water 3
．． 4 Sodium chloride 7g Compound (a) 0.5g Gelatin 37g Solution-2 Water 0.
25.9 Compound (a) 0.
04g Sodium chloride 2.1g
Potassium Bromide Gelatin Solution-3 Water Compound (a) Sodium Chloride Potassium Bromide Potassium Hexachloroiridate Potassium Salt 001% Aqueous Solution 3.5m 0001% Aqueous Solution of Potassium Hexabromorodate Salt 6ml Solution-
4 Water nitrate Silver nitric acid solution-5 Water nitrate Silver nitric acid 2.7g 0.6 g 0.3 g 27g 56 g 13 to 90g 5cc 0.25fi 10g 0.4cc Note) Compound (a) HO (CH2C1 (20), ( CH2CH2CH20
) L7(CH2CH20)llHm+n=5.7 pH 3.0, pAg8 in solution-1 kept at 40°C
．． Solution-2 and solution-4 were added simultaneously over 10 minutes while maintaining the temperature at 0, then solution-3 and solution-5 were added simultaneously over a period of 50 minutes, and after the addition was completed, pl-15, Adjust to 9 and add 670nl of 20% magnesium sulfate aqueous solution! and 0.82 g of a 5% aqueous solution of polynaphthalene sulfonic acid, flocculated at 40° C., decanted and washed with water to remove excess salt from the aqueous solution. Then add 7 ounces of water to it.
20% magnesium sulfate aqueous solution 3
Add 30 mj2 and remove excess salt in the same way. Furthermore,
Add 7 liters of water to disperse the mixture, and add 230ml of a 20% aqueous magnesium sulfate solution to remove excess salt from the aqueous solution. Add 750m4 of water and 50g of gelatin to it,
Disperse for 30 minutes at 55°C. As a result, silver chlorobromide particles having a silver bromide content of 38 mop%, a silver chloride content of 62 mop%, an average particle size of 0.29 μm, and a monodispersity of 9 were obtained.

(Preparation of Emulsion B) Emulsion B was prepared in the same manner as in the preparation of Emulsion A, except that the mixing time of Solution-2 and Solution-4 was changed from 10 minutes to 20 minutes. This resulted in particles having an average particle size of 0.33 μm.

(Preparation of Emulsion C) Emulsion C was prepared in the same manner as Emulsion A except that the mixing time of Solution-2 and Solution-4 was changed to 30 minutes. This results in an average particle size of 041
Particles of μm were obtained.

Next, each of emulsions A, B, and C was heated to 60°C, 40 ml of 1% citric acid solution (16 ml of 1.5% potassium bromide solution) was added, and 38 ml of 0.1% chloroauric acid aqueous solution was added. Chemical ripening was achieved by adding 30 ml of 0.1% sodium thiosulfate solution to achieve the highest sensitivity.To this, 25 ml of 0.5% solution of 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1, 33a, 82 g of gelatin dissolved in 900 mQ of 1% solution of 7-chitrazaindene was added, and 40 ml (l) of 10% potassium bromide solution was added and divided into 10 equal parts.Then, the temperature was lowered to 50 ° C.
As shown in the figure, general formula [I] and compounds B, C, and D were added. At this time, Compound E was also added to each at the same time.

Each emulsion was divided into 10 equal parts, 6 m2 of a 20% Merck saponin solution, 10 ml of a 20% hydroquinone solution. 2.5 m/j of 2% phenidone solution, 4 g of polymer latex, 4 g of styrene-maleic acid copolymer as thickener.
% solution 18m, 9, 4-hydroxy-35 as hardener
13 m of a 25% sodium dichlorotriazine solution was added. Use 0.5N sodium hydroxide solution or 5% citric acid solution as a pH adjuster to adjust the pH as shown in Table 1.
It was added so that

Compound B Compound E (Preparation of coating solution for emulsion protective film layer) 60 g of gelatin was dissolved in 900 mj7 water, and 15 g of amorphous silica with an average particle size of 3.5 μm and bis-(2-ethylhexyl) as a surfactant were added. Sulfosuccinic acid ester 1
% solution 90r+3Q was added, and 50 mfl of 3.7% formalin aqueous solution was added as a hardening agent. As a pH adjuster, 0.5N sodium hydroxide solution or 5% citric acid solution was added to adjust the pH as shown in Table 1.

(Adjustment of backing opening coating solution) 70g of gelatin was dissolved in 13 minutes of water, and the following i
3 days Merck's 20% saponin solution 21ml 1.7% citric acid solution 7J, 4% styrene-maleic acid copolymer solution 50mj7 as a thickener and glyoxal 4% as a hardening agent.
1 ml of solution was added.

(Preparation of backing protective layer coating solution) Dissolve 60 g of gelatin in 1.0°C water, and prepare a solution with an average particle size of 4μ.
m of polymethyl methacrylate 2g1 1% solution of bis-(2-ethylhexyl)sulfosuccinate 60m
9. 50 ml of a 10% sodium chloride solution and 7 mfl of a 4% glyoxal aqueous solution as a hardening agent were added.

(Preparation of photosensitive material sample) On a subbed polyethylene terephthalate support, a backing layer of gelatin 412, 3 g 7' m, a backing layer protective film gelatin amount 1, 0 g/I'r?
The backing opening coating solution and the backing layer protective film coating solution were applied so that the following results were obtained.

Then on the side opposite the backing layer to the support,
Ag amount is 4.42g/mF, protective layer gelatin is 0.8g
A light-sensitive material sample was prepared by coating the emulsion layer coating solution and the emulsion protective film layer coating solution so that the coating solution was 0.25 mm/m.

The obtained sample was processed according to the processing conditions shown below. The compositions of the developer and fixer used are shown below. The automatic developing machine used was GR-26SR manufactured by Konica.

Permissible development time: 38°C, 12 seconds Fixing time
36°0 12 seconds Washing time Room temperature
10 seconds Drying time 50°0 10 seconds 800 ml of pure water (ion-exchanged water) 800 ml of disodium ethylenediaminetetraacetate 2 g of diethylene glycol 25 g of potassium sulfite (
55% W/V aqueous solution) 60mp potassium carbonate
15g hydroquinone
20g 5-methylbenzotriazole
300mg 1-phenyl-5-mercaptotetrazole 60mg Potassium hydroxide 10.5g Potassium bromide 3.5g 1-phenyl-4,4-dimethyl-3-pyrazolidone 300mgCH
,C112CH2NHCONHCH,CH,5C2H.

When using developer, add pure water and 1f! , and used it. pH was 10.8.

Fixed rattan tray (composition A) Ammonium thiosulfate (72 5% W/V aqueous solution) 40mQ 7g 6.5g 6g 6g 13 Sodium sulfite Sodium acetate trihydrate Nitric acid Sodium citrate dihydrate Acetic acid (90% W/W aqueous solution) (Composition) 17 ml of pure water (ion exchange water) 4.7 g of sulfuric acid (50% W/W aqueous solution)
26.5 g of aluminum sulfate (A (8.1% W/W in 120s equivalent unit) aqueous solution) When using a fixer, the above compositions were dissolved in 500 mQ of water in the order of the above composition A1, and used after finishing. fixer p
I-I was approximately 46.

(Sample evaluation) (Evaluation method) A facsimile machine manufactured by Matsushita Electric Transmission Co., Ltd. (P
T-503) was used. The latent image progression was evaluated using a high-intensity sensitometer manufactured by Yamashita Denso Co., Ltd.
Using a 60 nm interference filter, the densities of those developed at 30' and those developed at 5' after exposure were determined and expressed as the difference in density.

The storage stability was expressed as Δj2ogE, which is the difference in sensitivity between the samples left in a constant temperature bath at 55°C for 3 days and those left at 23°C for 3 days. The fog is DT-101 manufactured by Dainippon Screen Co., Ltd.
Measured with a dotmeter. However, the sensitivity is expressed as a relative value, with the value when Sample No. 7 was exposed to PT-503 being 100.

It was also found that the membrane surface pH can be adjusted in the emulsion layer, the protective layer, or in the emulsion layer and the protective layer.

[Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material that has high sensitivity, low fog, and has improved latent image progression and storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains silver halide grains having an average grain size of 0.33 μm or more. , the film surface pH on the side having the silver halide emulsion layer with respect to the support is 4.0 or more and 7.0 or less, and at least one of the compounds represented by the following general formula [I]
A silver halide photographic material characterized by containing seeds. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom. R_1 and R_2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R_3 represents a methyl group, an ethyl group, or a propyl group. X_1 represents an anion. n_1 and n_2 represent 1 or 2. m_1 represents 1 or 0, and when it is an inner salt, m_1=0. ]