JPS584335B2 - Photo-developable silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a print-out type silver halide photographic light-sensitive material, and more particularly to a photodevelopable silver halide photographic light-sensitive material suitable for oscillographic recording, which has improved and high spectral sensitivity. It is related to.

Print-out type silver halide photographic materials are already known, have been put to practical use, and various types are commercially available.

Such photographic light-sensitive materials are known to be produced using a dry photography technique in which light is used for development, unlike those produced by a wet photography technique using a conventional liquid developing method.

Therefore, such photographic materials are widely used, especially in oscillographic recording, since their processing is simplified and advantageous compared to wet methods.

In general, in photodevelopable silver halide photographic materials, a latent image is formed by short-time exposure to high-intensity light, and then the previously formed latent image is intensified by relatively long-time exposure to low-intensity light. It can be a visible image.

Conventional direct-writing electromagnetic oscillography devices have used ultra-high-pressure mercury lamps as light sources to form latent images, but since these ultra-high-pressure mercury lamps use high voltage in their lighting circuits, they are difficult to handle. It is dangerous, requires a relatively long time to obtain the amount of light necessary for exposure, and once the light is turned off, it also takes a long time to turn it on again.

Furthermore, the mercury vapor used in mercury lamps is extremely toxic, and it is necessary to consider the effects on the human body due to breakage.

Therefore, in recent years, high-intensity tungsten lamps, xenon lamps, and
Halogen lamps and the like are used, and a light source device is configured by a combination of these high-intensity light sources and a high-speed shutter.

These light sources generally have spectral characteristics on the longer wavelength side than the specific sensitivity wavelength range of silver halide, so in order to use this as a light source for exposure, silver halide photographic light-sensitive materials match the wavelength range of these light sources. It is necessary to have high spectral sensitivity.

Furthermore, the obtained image must be sufficiently suppressed from fogging and have sufficient contrast;
Moreover, it is necessary that there is no or little residual coloration due to the sensitizing dye.

Until now, photo-developable silver halide photographic materials to which a sensitizing dye has been applied and which have spectral sensitivity on the relatively long wavelength side have been disclosed in, for example, U.S. Pat. No. 3,287,136, U.S. Pat. It is stated in each publication.

．． However, these photographic light-sensitive materials have the disadvantage that they do not have sufficient spectral sensitivity for light sources that have spectral characteristics on the relatively long wavelength side, such as tungsten lamps, and they also suffer from a large amount of force blur. .

On the other hand, photodevelopable silver halide photographic materials generally contain certain compounds called "photodeveloper", such as thioureas (e.g. 1-isoben-2-thiourea, 1-phenyl-2-thiourea). , 1-ethyl-1-(α-naphthyl)-2-thiourea, etc.), metal salts of dithiocarbamic acid (for example, Japanese Patent Publication No. 15819/1983), etc., but these photodevelopers It is known that halogen acceptors (commonly referred to as "halogen acceptors") reduce the spectral sensitivity of photographic materials sensitized by the above-mentioned sensitizing dyes, especially merocyanine dyes, and further cause a decrease in maximum density. There is.

However, as described below, it was unexpected that by selecting a specific photodeveloper and a specific sensitizing dye, the spectral sensitivity could be improved and the occurrence of fogging could be suppressed.

Therefore, an object of the present invention is to provide a photodevelopable silver halide photographic material having improved spectral sensitivity.

Another object of the present invention is to provide a photodevelopable silver halide photographic material in which the occurrence of fog is suppressed without impairing the improved high spectral sensitivity.

Furthermore, another object of the present invention is to provide a photodevelopable silver halide photographic material in which the reduction in contrast due to residual coloring of sensitizing dyes is improved.

Another object of the present invention is to provide a photodevelopable silver halide photographic material with improved maximum density reduction.

The object of the present invention is to provide a photo-developable silver halide photosensitive material that forms a visible image through a latent image forming step by short-time high-intensity exposure and a subsequent photodevelopment step by low-intensity exposure. This is achieved by containing at least one compound represented by the following general formula (■) or a salt thereof and at least one sensitizing dye represented by the following general formula (formula) in its constituent elements.

General formula (I) In the formula, R1 has a hydrogen atom, a lower alkyl group (for example, a methyl group, an ethyl group, an n-amyl group, a t-amyl group, etc. having 1 to 5 carbon atoms), or a substituent. Indicates an aryl group (for example, phenyl group, tolyl group, etc.) which may be

Salts of the compound represented by the general formula (■) include alkali metal salts (e.g., sodium salts, potassium salts, etc.)
, ammonium salts or organic amine salts (e.g. 1,8
- salt of diazabicyclo[5,4,0]undecene-7,
lutidine salt, etc.).

Furthermore, in the compound represented by the above general formula, R1 represents a tautomer when it is a hydrogen atom.

Therefore, the salts of 2,5-dimercap I--1,3,4-thiadiazole include one salt and two salts.

2,5-dimercapto-1,3,4-thiadiazole is a known compound and is easy to synthesize.
Commercially available products also exist and can be obtained at low cost.

Compounds in which R1 is an alkyl group or an aryl group are also known compounds and can be easily synthesized.

Furthermore, since these compounds have considerable strength as acids, they can be easily synthesized as alkali metal salts, ammonium salts, or organic amine salts by conventional methods, and their purification is also relatively easy.

They are inherently intolerant to water and are used by dissolving them in organic solvents such as methanol, ethanol, and dimethylformamide2,5
-Dimercapto-1,3,4-thiadiazoles, these salts are 2,5-dimercapto-1,3,4
The solubility of monothiadiazole in water can be substantially increased, thus facilitating its addition into components and preventing precipitation, which is desirable in terms of convenience in use.

Further, when 2,5-dimercapto-1,3,4-thiadiazole is used as a salt, the photodevelopment effect becomes stronger and the sensitivity is also improved, which is preferable.

Next, typical examples of the photodeveloper used in the present invention are listed below, but the present invention is of course not limited to these.

Compound Example (1) 2,5-dimercapto-1,3,4-thiadiazole (2) 2,5-dimercapto-1,3,4-thiadiazole monosodium salt (3) 2,5-dimercapto-1,3, 4-thiadiazole dipotassium salt (4) 2,5-dimercapto-1,3,4-thiadiazole monoammonium salt (5) 2,5-dimercapto-1,3,4-thiadiazole mono(L8-diazabicyclo[ 5,4,0] undecene-7) salt (6) 2,5-dimercapto-1,3,4-thiadiazolebis(1,8-diazabicyclo[5,4,0] undecene-7) salt (7) 2 ,5-dimercapto-1,3,4-thiadiazole monolutidine salt (8) 2-mercapto-4-ethyl-1,3,4-thiadiazolin-5-thione (9) 2-mercapto-4-phenyl-1,3 , 4-thiadiazolin-5-thione potassium salt 00l 2-mercapto-4-methyl-1,3,4-thiadiazolin-5-
Potassium thione salt The compound represented by the general formula (■) or its salt used in the present invention can be contained in a wide range of concentrations, but generally a small amount is sufficient, and it is 0% relative to the silver halide contained.
．． A suitable amount is 1 to 10 mol%, preferably 0.3 to 2 mol%.

When the salt of the compound used in the present invention is incorporated into the constituent elements of the photographic light-sensitive material, it can be added dissolved in the form of an aqueous solution, and when the compound is not a salt, organic solvents such as methanol, ethanol, acetone, etc. It can be added after being dissolved in dimethylformamide or the like, or it can also be added after being dissolved in an alkaline aqueous solution, such as a potassium hydroxide solution or a sodium hydroxide solution.

The additive may be added at any step during the production of the photographic material, but is preferably added immediately before emulsion coating.

Alternatively, the coating material may be added by immersing it in a solution containing the compound used in the present invention or its salt after drying.

General formula (in the old formula, Z1 is a 5- or 6-membered heterocycle (e.g., penzoxazole ring, benzothiazole ring, penzoselenazole ring, naphthooxadur ring, naphthothiazole ring, naphthoselenazole ring) , oxazole ring, thiazole ring, indole term, etc.).

These heterocycles are those substituted with substituents (for example,
4-chlorobenzothiazole, 5-chloropenzothiazole, 6-chloropenzodiazole, 5-promobenzothiazole, 6-promobenzothiazole, 5-iodobenzothiazole, 6-io- Dobenzothiazole, 5-
Chloropenzoxazole, 5-bromobenzoxazole, 5-chloropenzoselenadur, 4-methylthiazole, 5-methylthiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole , 5-methylbenzoxazole, 6-methylbenzoxazole, 4-methyloxazole, 5
-methyloxazole, 3,3-dimethylindole,
4-methoxybenzothiazole, 5-methoxybenzothiazole, 4-ethoxybenzothiazole, 5,6-dimethoxybenzothiazole, naph+-[,2-a]thiazole, 5-methoxynaphtho(1,2-d)thiazole, 5-Ethoxynaphtho [1. , 2-dlthiazole, 8
-Methoxynaphtho[1,2-cl]thiazole, 7-methoxynaphtho[1,2-d]thiazole, Nat[1,
2d] Oxazole, 5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoselenazole, 5-hydroxybenzothiazole, 6
-Hydroxybenzothiazole, 5-hydroxybenzoxazole, 6-hydroxypenzoxazole, 5
-Hydroxybenzoselenazole, 5-phenylthiazole, 4,5-diphenylthiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 5-
phenylbenzoxazole, 5-phenylthiazole, 4-phenyloxazole, 4-(2-thynyl)thiazole, etc.).

Z2 represents a sulfur atom or >NR.

R is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, n-probyl group, iso-
7'lopyl group, t-amyl group, n-hexyl group, n-octyl group, carboxymethyl group, 2-carpoxyethyl group, 3-carpoxybrobyl group, 4-carpoxybutyl group, 3-carpoxybutyl group, 2-sulfoethyl group base, 3
-sulfopropyl group, 3-sulfobutyl group, 2-dimethylaminoethyl group, etc.) or an aryl group (eg, phenyl group, tolyl group, etc.).

R2 and R3 represent a substituted or unsubstituted alkyl group (specific examples include those similar to the alkyl group defined in R5 above), and R3 represents a hydrogen atom, an aryl group (e.g., phenyl group, naphthyl group), tolyl group, etc.) or an alkenyl group (eg, allyl group).

In addition, when R2 and/or R3 are a sulfoalkyl group or a carpoxyalkyl group, these are alkali metal salts (
For example, salts such as sodium salts, potassium salts, quaternary ammonium salts, and organic amine salts are also included.

R4 represents a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-probyl group, an iso-probyl group, etc.) or an aryl group (for example, a phenyl group, etc.).

n represents 0, 1 or 2. Representative examples of sensitizing dyes that can be used in the present invention are shown below, but the present invention is not limited thereto.

Representative example dye No. These sensitizing dyes and their manufacturing method are described by FrancesM.
．． Hamer, “-The Cyanine Dye
s and Related Compound3 (
The Cyanine Soybean and Related Campanuns) J (1964) Interscience
Published by Publishers, page 511', page 611, etc.

The sensitizing dye used in the present invention is generally used in an amount of from about 10 m9 to 1,000 mg per mole of silver halide in the silver halide emulsion, but preferably from 100 mg to 300 mg.

Further, a conventional method can be used to add such a sensitizing dye to the constituent elements of a photographic light-sensitive material, particularly to a silver halide emulsion.

For example, a method in which a sensitizing dye is dissolved in a water-compatible organic solvent such as acetone, methanol, ethanol, furopanol, methyl cellosolve, pyridine, dimethylformamide, etc. and added to an emulsion, or US Pat.
No. 469,987, a method in which a sensitizing dye is dissolved in a volatile organic solvent, this solution is dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion; Patent No. 2912345, Patent No. 299
No. 6287, No. 3342605, No. 342583
Examples include methods described in various specifications such as No. 5.

These sensitizing dyes may be added to the emulsion at any step prior to coating the support, and it is convenient to add them prior to coating the support.

Further, these sensitizing dyes can be dissolved in an organic solvent at the same time as the compound represented by the general formula (■) or its salt, and then added to the constituent elements of the photographic light-sensitive material.

As used herein, "components" refer to silver halide photographic emulsion layers and non-light sensitive layers (eg, top layers, filter layers, interlayers, etc.).

Therefore, in the present invention, the compound represented by the general formula (I) or a salt thereof and the sensitizing dye represented by the general formula (■) can be contained in at least one component, but preferably halogenated It is suitable to include it in a silver photographic emulsion.

In the photo-developable silver halide photographic material according to the present invention, a latent image is formed by short-time exposure to high-intensity light, and then the previously formed latent image is intensified by relatively long-time exposure to low-intensity light. can be made into a visible image.

The exposure to form the latent image is performed using a light source having a high intensity light energy key, such as a high intensity tungsten lamp,
Exposure is performed using a xenon flash, a halogen lamp, a laser beam, etc. for a short time of 1 second or less, preferably 10 -1 to 10 -6 seconds.

In addition, the exposure to intensify the latent image and make it a visible image is 25
Low intensity light energy of 0 to 1000 lux is utilized, with such light sources selected from the range of 250 to 1000 lux, such as fluorescent lamps, reflected natural light, tungsten lamps, black lights, etc. Exposure is performed for a long time, approximately 1 minute or more.

Such exposure is commonly referred to as "photodevelopment."

With such photo-developable silver halide photographic materials, almost no image is formed when the exposure to form a latent image is with low-intensity light; This is different from one that can form a visible image by continuous irradiation.

The silver halide emulsion used in the photo-developable silver halide photographic material of the present invention may be a silver bromide emulsion, a silver chlorobromide emulsion, a silver chloroiodobromide emulsion, or a silver iodobromide emulsion. However, emulsions containing 90 mol % or more of bromine in terms of halogen molar ratio are suitable, and in particular, latent type emulsions having high photosensitivity inside silver halide crystals are preferred.

A silver halide emulsion is prepared by combining a soluble silver salt solution, such as an aqueous silver nitrate solution, and a halide solution in the presence of a hydrophilic protective glue.
For example, it can be obtained by mixing a potassium bromide solution and physically ripening the mixture to an appropriate particle size.

Physical ripening is preferably carried out under acidic conditions, at least pH 5.0 or lower, preferably pH 3.
．． A value of 0 or less is suitable.

Hydrochloric acid, nitric acid, etc. are used as the acid for making it acidic.

The protective gelatin is gelatin, and other substances include gelatin derivatives (e.g., phthalated gelatin, succinated gelatin, etc.), albumin, collodion, gum arabic, agar, alginic acid, C/L'O-s derivatives (e.g., carpoxycellulose). alkyl esters, hydroxyethyl cellulose, carboxymethyl cellulose, etc.),
Synthetic resins (eg, polyvinyl alcohol, polyvinyl pyrrolidone, acrylic acid, ethyl acrylate copolymers, etc.) can be used, and these can be used alone or in combination.

In addition, when preparing an emulsion, a suitable silver halide solvent such as 1,8-dihydroxy-3,6-dithiaoctane described in U.S. Pat. The reaction can be carried out in the presence of an organic thioether compound, an alkali thiocyanate described in U.S. Pat.

Furthermore, by performing physical ripening in the presence of a water-soluble lead salt, the contrast of the resulting photographic material can be improved.

The photodevelopable silver halide photographic material of the present invention may contain suitable gelatin hardeners, gelatin plasticizers, coating aids, and other sensitizing dyes commonly used in photographic technology.

The photodevelopable silver halide photographic materials of the present invention can be coated on a wide variety of supports.

Suitable supports include paper, baryta paper, paper coated with polyethylene, polyethylene, polystyrene, polycarbonate, nitrocellulose, acetylcellulose, synthetic paper, glass, metal plates, and the like.

The photodevelopable silver halide photographic material of the present invention can be subjected to conventional wet development and fixing treatments, if necessary.

For example, after forming a latent image by short-time high-intensity exposure,
Alternatively, by performing normal development and fixing processing at some time after forming an image by low-light exposure following the above-mentioned exposure, it is possible to create a record that is stable against light and can be stored permanently.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 3 mol% of 1,8-cyhydroxy-3, based on silver nitrate
In the presence of 6-dithiaoctane and 0.5 mol% lead nitrate, a silver nitrate aqueous solution and an alkali halide aqueous solution consisting of potassium bromide and sodium chloride are simultaneously and gradually added to a dilute aqueous gelatin solution acidified with nitric acid (pH 3.0). This was added dropwise to prepare a silver chlorobromide (silver bromide 95 mol %, silver chloride 5 mol %) emulsion.

After cooling the resulting emulsion and removing water-soluble salts, an additional aqueous gelatin solution was added so that the weight ratio of gelatin to silver nitrate was 80%, and the sensitizing dyes listed in Table 1 below were added. 1707 per mole of silver halide
729 and was equally divided into 8 pieces.

For each of these, the exemplified 2,5-dimercapto-1,3,4-thiadiazole was added to silver halide at 0%
．． Samples of the present invention (sample Nos. 2 to 7) by adding 5 mol%
and comparison samples (sample Nos. 8 to 9) were created.

Furthermore, as a comparative sample (sample No. 10), the same amount of 2-thiouracil was used in place of the photodeveloper used in each of the above samples, and the same amount of the comparative dye C^* described below was used as a sensitizing dye. Samples prepared in exactly the same manner as each of the above samples were used, except for the following.

As a blank sample (sample No. 1), a sample of the present invention from which the sensitizing dye was removed was used.

Each of these samples was prepared by adjusting the gelatin concentration to 6% and then 110. It was coated on a non-baryta base paper of g/m2 so that the amount of silver at the time of coating was 3.0 g/m2, and dried.

For each of these, a wedge tablet with a density difference of 0.15 (Photograph Ink manufactured by Eastman Kodak) was used.
A high intensity exposure of 10-5 seconds was given by a xenon flash lamp through tablet A2), followed by 2
Photodevelopment was carried out for 5 minutes at a brightness of 500 lux using a 0 watt white fluorescent lamp, and the sensitivity, maximum density (Dmax), minimum density (Dmin), contrast (ID = Dmax - Dmin) and contrast of the obtained image were determined. Color staining was measured.

In addition, sensitivity is measured by total sensitivity and minus blue sensitivity, total sensitivity is measured by the number of visible steps for the entire wavelength range of xenon flash light using Kodak Photographic Step Tablet 42, and minus blue sensitivity is further measured by Kodak Photographic Step Tablet 42. Wratten filter no.
It was measured by the number of visible steps obtained when the blue light region of xenon flash light was cut using No. 16.

The density was measured using a reflection type densitometer, and the degree of colored contamination was visually observed and evaluated as large, medium, small, or none.

(“Large” indicates that the colored contamination is significant, “Medium” indicates that the colored contamination is relatively moderate, “Small” indicates that there is little colored contamination, and “No” indicates that the colored contamination is not visually observable. Each case is shown below.

) However, as comparative dyes A, B and C, the following sensitizing dyes were used.

Comparative dye A Comparative dye B Table 1 Minus total Blue feeling Colored sample waste Light Developer Sensitizing dye Sensitivity steps (degrees)
Number of stages) Dmax Dmin ΔD Contamination 1
2,5-dimerka (blank) puto 1,3,4-17.
5 0 0,49 0.34 0.
15 Non-thiadiazole 2 Dye A (1) 20.0
15.0 0.64 0.30 0.3
4 None 3 Dye 4 (8)
20.0 15.5 0.66 0.31
0.35 No 4 〃 Pigment (1
3) 21.0 16.0 0.63
0.31 0.32 None 5
Dye A (18) 20.5 16.0 0
．． 63 0.32 0.31 None 6
Dye A (28) 20.0 15.
0 0.61 0.30 0.31 No 7
〃 Dye A (29) 20.0
15.0 0.60 0.30 0.30
None 8 〃 Comparative dye A""
18.0 11.0 0.51 0.31
0.20 Medium 9 〃 Comparative dye B
”218.5 11.5 0.54 0.3
3 0.21 Large 10 2-Thioura"' Comparative dye C"3 18.0 10.0 0.
45 0.35 0.10 Large (for comparison) Comparative dye C''3 Example 2 The sensitizing dye of the above-mentioned dye No. (2) was added to the silver chlorobromide emulsion prepared in the same manner as in the above-mentioned Example 1 with silver nitrate. 20 per mole
This was divided into equal parts, and for each of them, the photodeveloper listed in Table 2 below was added at a ratio of 0.5 to silver halide.
A sample was prepared by containing mol %, and the same exposure and measurement as in Example 1 were performed.

These results are shown in Table 2 below.

Total sensitivity minus bull
Colored sample rot Light developer (number of stages) Sensitivity (number of stages) Dmax DITI i
n ΔD Contamination 11 Exemplary Compound (3)
20.5 16.0 0.6
6 0.30 0.36 None 12 // (
5) 21.0 16.0 0.66 0.3
1 0.35 no 13 tt (6) 20.5
16.0 0.69 0.31 0.38 No 14
// (7) 20.5 15.5 0
．． 68 0.30 0.38 no 15 tt (9)
20.0 15.0 0.67 0.30
0-37 no 16 p QO) 20.5 1
5.5 0.64 0.28 0. :36 no 17
1,3-diethylthiourea 18.5
11.0 0.50 0.32 0.18
Middle 7-7′″′″. :)t/. -5 one inch force 7°
19.0 13.0 0, 51
0.32 0.19 Large 18 Totetrazole 19 Ethylenethiourea 18.0
8.5 0.55 0.35 0
．． 20 Large 20 Di"di"dithioca"'dimic' acid
17.5 10.5 0.64 0
,39 0.25 Zinc 21 3,5-dithiourazole ]. 9
．． 0 13.0 0.59 0.38
0.24 Large 22 Rhodanine
18.5 12.5 0.53
0.36 0.17 Dog 23 Thiomalic acid
17.5 9.0
0.51 0.27 0.24 Medium 24 Stannous chloride 19.5 13.
5 0.65 0.4. O O. 25 Dog 4--71. :/Lz chime 'Mika'=” 18
．． 5 6.5 0.52 0.3
4 0.18 Dog 25 Example 3 The photo-developable silver halide photographic light-sensitive material used in Sample 11 of Example 2 was tested with an amplitude of 4 cr IL 1 frequency of 1 0 0 using a direct recording electromagnetic oscillograph using a xenon flash lamp. High intensity exposure was given under the conditions of C/S and feed rate of 1 m/sec, and then 20' knots of white fluorescent light 5
The trace was visualized by photodevelopment at 00lux for 5 minutes.

In each case, a dark blue trace appeared on the cream background within a few seconds after photodevelopment, and after 5 minutes, a clear recorded image with a high contrast of 1.0 was obtained.

Further, these recorded images were wet-developed according to the following recipe.

As a result, it was possible to obtain a black trace on a uncontaminated background even for the fallen one, whose Coin 1 helast was high and completely stable to the light beam.

Processing process. Processing temperature Processing time ■． Development 20°C 1 minute 30 seconds to 2 minutes 2. Establishment
[Rinse with water for at least 2 minutes]. The following developer was used for the development process for 0 minutes or more.

Developer Hydroquinone 6FI
P-methylaminophenol sulfate 6g 1-phenyl-3-virazolidone 0.2g anhydrous sodium sulfite 50g sodium carbonate monohydrate 50!91-phenyl-5-
Mercap 1 Tetrazole 0.5.9 Potassium Bromide
1g boric acid
10g potassium thiocyanate
2.9 Add water to make a total volume of 2 liters.

The following fixing solution was used for the fixing process.

Fixer Anhydrous sodium thiosulfate 3209 Anhydrous sodium sulfite 30.9 Acetic acid
60m/boric acid 15g potassium alum 4 (1) Add water to make a total volume of 2L.

Claims (1)

[Scope of Claims] 1. A photo-developable silver halide photographic light-sensitive material that forms a visible image through a latent image forming step by short-time high-intensity exposure and a subsequent photo-development step by low-intensity exposure. A photodevelopment product characterized in that the constituent elements contain at least one compound represented by the following general formula (■) or a salt thereof and at least one kind of sensitizing dye represented by the following general formula (■). type silver halide photographic material. General formula (■) (In the formula, R1 represents a hydrogen atom, a lower alkyl group, or an optionally substituted aryl group.) General formula (■) (In the formula, Z1 represents a 5- or 6-membered heterocycle. Indicates a nonmetallic atom group necessary for completion. Z2 represents a sulfur atom or >NR5. However, R5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R2 and R3 are substituted or unsubstituted. represents an alkyl group, and R3 may be a hydrogen atom, an aryl group or an alkenyl group. R4 represents a hydrogen atom, an alkyl group or an aryl group. n represents 0, 1 or 2.)2 Photodevelopment type silver halide photographic light-sensitive material contains at least 9 bromides in the yzO molar ratio of silver halide.
The photodevelopable silver halide photographic material according to claim 1, which contains 0 mol%. 3 The content of at least one compound represented by the general formula (■) or its salt is 0.3 to 0.3 to silver halide.
The photodevelopable silver halide photographic material according to claim 1, wherein the proportion is 2.0 mol%. 4 Photo-developable halogenation according to claim 1, 2 or 3, wherein the compound represented by the general formula (■) is 2,5-dimercapl--1,3,4-thiadiazole Silver photosensitive material. 5. Photodevelopment according to claim 1, 2 or 3, wherein the salt of the compound represented by formula (■) is a dialkali salt of 2,5-dimercapto-1,3,4-thiadiazole. type silver halide photographic material. 6 The salt of the compound represented by the general formula (■) is bis-(1,
The photodevelopable silver halide photographic material according to claim 1, 2 or 3, which is 8-diazabicyclo[5,4,0]undecene-7) salt. 7 In the sensitizing dye represented by the general formula (■), Z1 is a benzoxadur term, a benzothiazole ring, a benzoselenazole ring, a naphthoxazole term, a naphthothiazole ring, each of which may have a substituent, A photo-developable silver halide photograph according to claim 1, which is a group of nonmetallic atoms necessary to complete one heterocycle selected from a naphthoselenasol ring, an oxazole ring, a thiazole ring, and an indole ring. photosensitive material. 8. Claim 1 or 7, wherein the photo-developable silver halide photographic material is an oscillographic recording material.
A photodevelopable silver halide photographic material as described in 1.