JPH05696B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improvement in a negative image forming method for obtaining a negative image with high sensitivity, high contrast, and high maximum density through rapid phenomenon processing using physical phenomenon nuclei. The supply of metallurgical materials, which are essential as raw materials for silver halide photographic materials, is decreasing, while the demand in various industries is increasing, resulting in significant price fluctuations. Currently, attempts are being made to quantify silver. For example, one example is a silver salt diffusion transfer method that utilizes physical phenomenon nuclei. This method is extremely useful because the covering power (silver covering power) of the transferred image is very high, so a photographic image with higher density can be obtained with a small amount of silver halide, and the sensitivity and sharpness are also excellent. This is known as an image forming method. However, this method is a negative-positive diffusion transfer method, and the image finally obtained is a positive image, so it is not suitable for the purpose of forming a negative image. On the other hand, as a photosensitive material for the purpose of finally obtaining a negative image, (1) photosensitive silver halide (2) metal salt particles that are more easily soluble than photosensitive silver halide and have substantially no photosensitivity. A photographic material containing particles in which a refractory agent is adsorbed and (3) physical development nuclei has been proposed in JP-A-54-48544. This photographic material is processed with a physical developer containing a silver halide reducing agent and a substance that dissolves metal salt particles in order to obtain a negative image. In this method, silver ions are reduced and precipitated on physical development nuclei. The method requires time, lacks suitability for rapid processing, and also causes a decrease in sensitivity and maximum concentration, making it difficult to say that it is an adequate method. That is, further improvements have been desired from the viewpoint of speeding up the processing by shortening the development processing time. The object of the present invention is to improve the disadvantages of the negative image forming method using the silver-saving photographic materials mentioned above. SUMMARY OF THE INVENTION It is therefore a first object of the present invention to provide a method for forming negative images using photographic materials which provides improved sensitivity and contrast as well as high maximum density. A second object of the present invention is to provide a method for forming a negative image using a photographic material that has improved deterioration of photographic properties during raw storage. A third object of the present invention is to provide a negative image forming method that can quickly form a photographic image. The above object of the present invention is to contain at least one of the following compounds (1), (2) and (3) and the following general formula [] in a photographic constituent layer coated on a support. After image exposure, the photographic material is treated with a processing solution containing a reducing agent and a substance that dissolves the metal salt particles described in (2) below to selectively dissolve the metal salt particles in the exposed areas. ) is constituted by a negative image forming method characterized by having a step of depositing a metal image on the physical development nuclei of (a). (1) Photosensitive silver halide grains (2) Metal salt particles that are more easily soluble than the above (1) and whose surfaces have been made difficult to dissolve with a refractory agent (3) Physical development nucleus general formula [] Z ¹ and Z ² in the formula may be the same or different5
Represents the atomic group necessary to complete a nitrogen-containing or 6-membered heterocyclic nucleus, specifically an oxazoline nucleus,
Oxazole nuclei (e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 5-phenyloxazole, 4,5-
diphenyloxazole, etc.), benzoxazole nuclei (e.g., benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 5,6
-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-methoxybenzoxazole, 5-acetylbenzoxazole, 5-benzoylbenzoxazole, 5-chloro-6-methylbenzoxazole, 5-carboxybenzoxazole , 5-ethoxycarbonylbenzoxazole, 6-nitrobenzoxazole, 5-chloro-6-nitrobenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole core (e.g.
α-naphthoxazole, β-naphthoxazole, etc.), thiazophosphoric acid (e.g. thiazoline, 5
-methylthiazoline etc.), thiazole nucleus (e.g.
Thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,
4,5-diphenylthiazole, etc.), benzothiazole nuclei (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 5-methylbenzothiazole,
6-Methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole , 5-iodobenzothiazole, 6-iodobenzothiazole, 5-methoxycarbonylbenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole,
5-N,N-dimethylaminobenzothiazole,
5,6-dimethoxybenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 5-carboxybenzothiazole,
5-nitrobenzothiazole, 6-nitrobenzothiazole, 5-chloro-6-nitrobenzothiazole, 5,6-methylenedioxybenzothiazole, etc.), naphthothiazole nuclei (e.g., α-naphthothiazole, β-naphthothiazole, 5-methoxy-β-naphthothiazole, 5-ethoxy-
β-naphthothiazole, 8-methoxy-α-naphthothiazole, 7-methoxy-α-naphthothiazole, etc.), benzoselenazole core (e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazole nucleus (e.g., α-naphthoselenazole, β-naphthoselenazole, etc.), 2-pyridine nucleus (e.g., 2-pyridine, 3-methylpyridine) , 4-methylpyridine, 5-methylpyridine, 3,4-dimethylpyridine, 4-chloropyridine, 3-hydroxypyridine, 3-phenylpyridine, etc.), 4-pyridine nucleus (e.g., 4-pyridine, 2-methyl pyridine, 3-methylpyridine, 3-chloropyridine,
2,6-dimethylpyridine, 3-hydroxypyridine, etc.), 2-quinoline nuclei (e.g., 2-quinoline, 3-methylquinoline, 5-methylquinoline,
7-methylquinoline, 8-methylquinoline, 6-
chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.),
4-quinolinic acid (e.g., 4-quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinoline nucleus (e.g.,
1-isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinoline core (e.g., 3-isoquinoline, 5-methylisoquinoline, 1-methylisoquinoline, 6-chloroisoquinoline, 6-methoxyisoquinoline, 8-methoxyisoquinoline, etc.) represents. In addition, R ¹ and R ² in the above formula are lower alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, butyl, etc.), substituted alkyl groups (e.g., β-hydroxyethyl, γ-hydroxypropyl, etc.). hydroxyalkyl group, β-sulfoethyl,
a sulfoalkyl group such as γ-sulfopropyl or δ-sulfobutyl, or a carboxyalkyl group such as β-carboxyethyl or γ-carboxypropyl, and at least one of R ¹ and R ² is a sulfoalkyl group or a carboxyalkyl group. It is. Further, R ³ represents a lower alkyl group having 1 to 4 carbon atoms, X represents an anion (eg, halogen, etc.), l, m and n represent 0 or 1, and a represents 0 or 1. Next, the negative image forming method of the present invention will be explained in more detail. First, specific examples of the compound represented by the above general formula [] will be described below, but the present invention is not limited thereto. These compounds included in the above general formula [] are known, for example, Cyaninated Soy and Related Compound (Harmer, 1964).
and The Theory of the Photographic Process (by Mies James, 3rd edition,
(1966) and others.
In the negative image forming method of the present invention, the above-mentioned compound is added to the photographic constituent layer containing the metal salt particles or physical development nuclei, or is added to the photosensitive silver halide grains, metal salt particles and physical development nuclei. Although they may be added to a photographic constituent layer containing a mixture of development nuclei, it is most preferable to use them by adding and adsorbing them into a constituent layer containing photosensitive silver halide grains. The amount used is 10 ^-5 to 10 ^-2 mol, preferably 10 ^-4 to ^{10 -3} mol, per mol of silver halide. It may be added at any time during the manufacturing process, but in the case of a photosensitive silver halide emulsion, it may be added at any time during the early or late chemical ripening. Examples of the photosensitive silver halide used in the photographic image forming method of the present invention include silver chloride, silver bromide,
Silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or mixtures thereof are included, but it is preferable to use silver iodobromide, which has high sensitivity, especially when the Silver iodobromide containing silver iodide is preferred in the present invention. The above-mentioned photosensitive silver halide is applied to the present invention in the form of a silver halide emulsion, and the emulsion can be produced by various manufacturing methods including the usual manufacturing method, such as those described in Japanese Patent Publication No. 46-7772. Alternatively, the so-called conversion emulsion method described in US Pat. No. 2,592,250, such as the single-jet emulsion method and the double-jet emulsion method, can be used. Further, the photosensitive silver halide grains used in the present invention include those having various crystal habits.
Although the particle size varies depending on the intended use of the photographic material, it is usually within the range of 0.1 to 3.0 μm. These silver halide emulsions are then chemically sensitized using various chemical sensitizers. Chemical sensitizers include known sensitizers such as sulfur sensitizers, selenium sensitizers, and noble metal sensitizers, as well as reduction sensitizers,
Polyalkylene oxide-based sensitizers are also widely used. These silver halide emulsions can also be prevented from generating capri by using known stabilizers such as imidazoles, triazoles, and azaindenes. Next, in a state where the surface of the metal salt particles used in the present invention is not coated with the refractory agent, the dissolution rate in the substance that dissolves the metal salt particles described below is the same as that of the photosensitive silver halide. It is a salt of a metal that is larger than the above and has substantially no photosensitivity. More specifically, the conditions regarding the dissolution rate of both of these grains are as follows: The presence of at least one of the metal salt dissolving agents described below in the metal salt grain group (A) and the photosensitive silver halide grain group (B). The dissolution rate (mass of substance dissolved per unit time) (in the treatment liquid used in the present invention) shown below is (A) and (B) when the total mass of particles contained in both particle groups is equal. It is necessary that (A) is larger than the particle group (B). Measurement methods when such conditions are actually applied include the following methods. First, two types of emulsions each containing photosensitive silver halide particles and metal salt particles in a hydrophilic colloid were prepared, each emulsion was coated on a support and dried.
Create two types of samples. The amount of coating at this time is such that the amounts of photosensitive silver halide, metal salt, and hydrophilic colloid per unit area are equal between the two types of samples. The obtained sample is immersed in a 5% aqueous sodium thiosulfate solution (temperature 20°C) without stirring. The immersion time is several seconds, for example 2 seconds, 5 seconds and 8 seconds. Next, the sample is immediately transferred to a water tank, washed with water, and then dried. The amount of residual photosensitive silver halide and residual metal salt of the sample treated in this manner is analyzed and measured by a known method, and the residual percentage (%) is determined for each. Draw a graph of residual distillation rate and soaking time, and the residual distillation rate is 50%.
The immersion time t1 of the photosensitive silver halide sample corresponding to
and find the immersion time t2 of the metal salt particle sample, and calculate t2/t1
Find the value of. The value of t2/t1 determined in this way needs to be smaller than 1, and preferably smaller than 0.7. The metal salt particles used in the present invention may be appropriately selected from those having the above-mentioned properties, but in a preferred embodiment of the present invention, the metal salt particles are substantially photosensitive. Silver halide grains that do not have a silver halide grain and have a higher dissolution rate for a substance that dissolves silver halide grains than the photosensitive silver halide grains are selected. More specifically, the metal salt particles preferably applied to the present invention are pure silver bromide, pure silver chloride, or a mixed silver halide thereof that has not been subjected to chemical sensitization treatment, and is It is desirable that the crystals be finer than that of silver. In the method of the present invention, the term "substantially non-photosensitive" means "non-photosensitive" in relation to the photosensitive silver halide; Specifically, when the light-sensitive photographic element of the present invention is provided with the light energy necessary to sensitize the light-sensitive silver halide, it is to be understood that it is "substantially unsensitized" by the light energy. be. More specifically, the particles of the metal salt of the present invention are fine particles of the metal salt that generally have a photosensitivity that is at least 1/10 less than that of the photosensitive silver halide. The metal ions or metal complex ions produced as a result of the dissolution of the metal salt particles are reduced to metals on the physical development nuclei in the presence of a reducing agent. The metal salt particles used in the present invention are used in an amount of 0.1 to 100 mol per mol of photosensitive silver halide. The surface of the metal salt particles used in the present invention is coated with a refractory agent, and the refractory agent is adsorbed onto the surface of the metal salt particles, or a portion of the particle surface becomes an active site for a dissolution reaction. This is a compound that slows down the dissolution rate of particles in the presence of the metal salt dissolving agent by adsorbing to the metal salt dissolving agent, and this poorly soluble agent adsorbs to the surface of the easily soluble metal salt particles, dissolving the metal ions of the metal salt. It also includes compounds that form poorly soluble salts or complex salts with. According to one preferred embodiment of the present invention, the refractory agent is selected from compounds that adsorb to silver halide grains, which are easily soluble metal salt particles, and reduce the solubility thereof. These compounds are, for example, mercapto compounds, and more specifically cysteine, 1-phenyl-5-mercaptotetrazole, mercaptobenzthiazole, mercaptobenzselenazole, mercaptobenzoxazole, mercaptobenzimidazole, benzylmercaptan, 4- Ethyl-2-thio-oxazoline, 2-mercapto-6-azauracil, 4-hydroxy-2-mercapto-6-methyl-pyrimidine, 3-mercapto-4-phenyl-5-methyl-1,2,4-triazole, etc. are included as representative examples. Further, thiourea, indazoles, triazoles, imidazoles and the like are also preferred compounds that can be used in the present invention. Among these, mercaptotetrazole compounds are preferred. The substance that dissolves the metal salt particles used in the present invention (hereinafter referred to as metal salt dissolving agent) is a substance that acts on the metal salt particles used in the present invention to generate metal ions or soluble metal complex ions. This may be the solvent of the treatment liquid used in the present invention, such as water. According to a preferred embodiment of the present invention, the dissolving agent is a substance that does not substantially dissolve the photosensitive silver halide used in the present invention, or is a metal in an amount that does not substantially dissolve the photosensitive silver halide. The photosensitive silver halide, which is a salt particle, is a substance that dissolves fine particles of silver halide that have different solubility, and typical examples include sulfites such as sodium sulfite,
Thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; cyanates such as potassium cyanide and sodium cyanide; thiocyanates such as sodium thiocyanide and potassium rhodan; amino acid compounds such as cystine and cysteine; thiourea; Phenylthiourea, 3,6-di-
Examples include thiourea compounds such as thia-1,8-octadiol, thioether compounds, and the like. In the present invention, the most preferred embodiment is that the metal salt dissolving agent is present in the processing solution, while the refractory agent is present in the photographic constituent layer containing the metal salt particles. Moreover, methanol is suitable as a solvent when adding the refractory agent. Regarding the addition amount, when it is included in the photographic constituent layer, the refractory agent is added per mole of metal salt of the metal salt particles used in the present invention.
The range is preferably 0.01g to 7.0g, and more preferably 0.1g to 5.0g. Among the metal salt dissolving agents, sodium sulfite in particular is generally used as a preservative for developing solutions, so the amount of the above dissolving agents used per processing solution excluding sodium sulfite is preferably 0.001 to 50 g. The amount ranges from 0.01 to 30 g, but by using the compound of the general formula [] according to the present invention, the amount of the metal salt dissolving agent used can be reduced.As a result, the generation of sludge in the developer and the storage stability are improved. was successful. Furthermore, physical development nuclei used in the present invention include colloids of precious metals such as gold, silver, and platinum;
Metal sulfides such as palladium and zinc, metal selenides, and the like can be used. Among these, metal silver particles obtained by reducing silver compounds (for example, silver nitrate, silver halide, etc.) and palladium sulfide are particularly preferred. These physical development nuclei are substances that have the function of catalytically promoting the process in which the metal ions or metal complex ions produced by dissolving the metal salt are reduced to metal by a reducing agent, or such a function. It does not necessarily have to be a physical particle. The content of the above-mentioned physical development nuclei in the photographic constituent layer varies depending on the type thereof, but for example, in the case of silver sulfide, it is 0.001 g/m ² to 1.0 g/m 2 as metallic silver, and metallic silver (reducing fine particles of silver chloride) (manufactured by)
A range of 0.01 g to 3.0 g/m ² is suitable. The photographic light-sensitive material according to the present invention can have various configurations of constituent layers depending on its purpose or use. That is, the photographic light-sensitive material according to the present invention comprises, on a support, (1) photosensitive silver halide grains, (2) metal salt particles that are more easily soluble than the silver halide and have substantially no photosensitivity, and ( 3) Although it is a photographic light-sensitive material containing physical development nuclei, the above (1) to (3) may be contained in separate layers, or any two or more of the above (1) to (3) may be contained. They may be contained in the same layer. For example, a layer containing physical development nuclei, a layer containing metal salt particles, a layer containing photosensitive silver halide particles, and a layer containing a silver halide developer are laminated on a support in this order from the support side. Starting with the layer structure, the order of lamination may be reversed, or for example, a layer containing physical development nuclei and a silver halide developer is coated from the support side, and a layer containing a photosensitive halogen It is possible to have a two-layer structure in which silver halide grains and metal salt particles are mixed in the same layer, and photosensitive silver halide grains, metal salt particles, and physical development nuclei are present in the same layer. It is also possible to form a single layer structure by coating a mixture of layers on a support. Still another method is to prepare two supports and perform the layer construction separately for each support, or even prepare three supports and coat each layer one layer at a time. may be set. A preferred layer structure of the silver halide photographic light-sensitive material according to the present invention is a single layer in which photosensitive silver halide grains, metal salt particles, and physical development nuclei are mixed and present on the same support. Either a layer structure coated on top or a layer containing a mixture of metal salt particles and physical development nuclei is coated from the support side,
Preferably, a layer containing only photosensitive silver halide grains is coated thereon to form a two-layer structure. The layer structure of the photographic light-sensitive material according to the present invention has already been described above, but if necessary, for example, a protective layer, an anti-halation layer, a non-diffusible dye layer in which a dye is fixed with a mordant, etc. are added at appropriate positions. Auxiliary layers may be provided and photographic additives other than those mentioned above may be added to these layers. Further, the photosensitive silver halide, metal salt particles, and physical development nuclei described above are present individually or in a mixture of two or more thereof, dispersed in a suitable binder. Various hydrophilic colloids can be used as the binder, and gelatin is typically preferably used. Furthermore, for the purpose of improving the physical properties of a coating film containing the above-mentioned hydrophilic colloid as a binder, it is preferable to use various film property improving agents, such as a hardening agent, as necessary. The coating composition containing hydrophilic colloid as a binder used in the present invention may contain photographic additives other than the above-mentioned hardeners, such as gelatin plasticizers, surfactants, ultraviolet absorbers, and antistain agents, if necessary. , PH regulator, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener,
Development speed regulators, matting agents, silver halide developers, etc. can be used within the range that does not impair the effects of the present invention. Supports used in the photographic material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, Typical examples include polypropylene film, polycarbonate film, polystyrene film, etc., and these supports are appropriately selected depending on the intended use of the photographic material. After exposure, the silver halide photographic material used in the present invention is processed with a processing solution containing a reducing agent. A developing agent is advantageously used as the reducing agent in the processing solution used in the present invention. As a developing agent,
For example, hydroquinone, which is well known in the art,
Polyhydroxybenzenes represented by toluhydroquinone, 2,5-dimethylhydroquinone, etc., such as 1-phenyl-3-virazolidone,
3-virazolidones represented by 1-phenyl-4-methyl-3-virazolidone, such as ο-
Aminophenols represented by aminophenol, p-aminophenol, etc., such as 1-(p
-hydroxyphenyl)-3-aminovirazolidone, 1-aryl-3-aminovirazolines such as 1-(p-methylaminophenyl)-3-virazoline, ascorbic acid, and others, C.
EKMees and THJames, “The Theory of
the Photographic Process” 3rd edition (1966,
Maemillan Co, NY), Chapter 13, LPA
Photographic Processing by Mason
"Chemistry" (1966, The Focal Press,
Compounds described as developing agents on pages 16 to 30 (London) can be used alone or in combination. The PH of the treatment liquid is 5 or more, preferably PH5.5 to 13.2
degree is optimal. The processing solution may contain various additives such as an alkaline agent, a PH buffer, a development accelerator, and an antifoggant, if necessary. The processing temperature using the above-mentioned processing liquid is suitably in the range of 20°C to 50°C. As mentioned above, the silver halide photographic material which has been reduced in silver by the method of the present invention can be used not only as a general-purpose black-and-white photographic material, but also as a highly sensitive radiation-sensitive material or a high-contrast photographic material for printing. It can be applied to a wide range of materials, including photosensitive materials for lithographic printing. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 [Preparation of photosensitive silver halide emulsion] Gold sensitized and sulfur sensitized by a conventional method.
A high-sensitivity silver iodobromide gelatin emulsion containing 4.0 mol% of silver iodide that has been aged to the highest sensitivity is added with 4-hydroxy-6-methyl-1,3,3a, as a stabilizer.
A photosensitive silver halide grain emulsion was prepared by adding 1.5 g of 7-tetrazaindene per mole of silver halide. The average grain size of this emulsion was approximately 1.3μ. [Preparation of metal salt grains (substantially non-photosensitive silver halide grains)] A pure silver chloride gelatin emulsion consisting of nitrate and sodium chloride was prepared by a neutral method. The average grain size of this emulsion was easily soluble silver chloride grains of about 0.1 μm. [Preparation of physical development angle] 1% polyvinyl alcohol (saponification degree 99)
%, polymer with a degree of polymerization of 1000) in 10 ml of an aqueous solution of
50 ml of 0.2% chloroauric acid was added and stirred at room temperature, and 10 ml of 1% sodium borate hydride was added to form physical development nuclei of gold colloid. First, a silver chloride emulsion with virtually no photosensitivity was taken from among the three types prepared as described above, and 1.2 g of 1-phenyl-5-mercaptotetrazole was added per mole of silver halide as a refractory agent. ,
Subsequently, 120 mg of the above-mentioned physical development nucleus was added as chloroauric acid per mole of silver chloride emulsion, and then an appropriate amount of saponin was added as a coating aid to prepare a coating solution. At the time of application, it was applied uniformly to both sides of a polyethylene terephthalate base that had been subjected to undercoat processing. Subsequently, the photosensitive emulsion prepared as described above was collected, divided into equal parts, and the compound represented by the general formula [] according to the present invention was added as shown in Table 1 below. For comparison, a sample without the addition of the dye and a sample with the following comparative dye [R] added thereto were prepared. Next, an appropriate amount of saponin was added as a coating aid to each layer, and then coated uniformly on both sides of the silver chloride emulsion layer. Furthermore, on top of this layer, a suitable amount of a hardening agent (formalin) and a coating aid (succinic acid-2-
A 2.5% aqueous gelatin solution containing ethylhexyl-ester monosulfonate (sodium ethylhexyl ester monosulfonate) was coated in multiple layers to prepare various negative-working silver halide photographic materials. The amount of coating on both sides of the obtained sample was as follows: the amount of silver in the silver chloride layer as a non-photosensitive silver halide emulsion layer was 1.0 g/m ² , and the amount of gold as physical development nuclei was 1.0 mg/m ²
The silver content of the silver iodobromide layer as a photosensitive silver halide emulsion layer was 3.0 g/m ² . Each of the obtained samples was subjected to a raw storage test treatment under the conditions shown in Table 1, and then each sample film piece was wedge-exposed to 3.2 CMS light, and then incubated at 35°C using a developer with the following formulation. The film was developed for 30 seconds, then fixed, washed with water, and dried before sensitometry. [Developer formulation] Add hydroquine anhydrous sodium sulfite phenidone sodium hydroxide 5-methylbenzotriazole potassium bromide water to make 1. 12.0g 65.0g 1.0g 15.0g 0.5g 2.0g The results obtained are shown in Table 1 below. Note that the sensitivity values in the table are expressed as relative sensitivities, with the sensitivity of sample No. 1 being 100.

[Table] As is clear from Table 1, samples Nos. 2 to 13 obtained by the method of the present invention have high sensitivity, contrast, and maximum density, and are free from fog due to storage at high temperature and low humidity and high temperature and high humidity. It can be seen that the increase can be significantly reduced. Example 2 The following Example 2 was prepared in exactly the same manner as in Example 1, except that the above-mentioned exemplary compounds and the following comparative dyes were added to the photosensitive silver halide emulsion.
Samples were prepared as shown in the table. comparison dye These samples were treated in the same manner as in Example 1, and the results obtained are shown in Table 2 below.

[Table] Samples No. 15, 16 and 17 are comparative dyes - [A]
Samples Nos. 18 and 20 were compared with comparative dye-[B] in green light sensitivity in terms of relative sensitivity. Samples No. 22 and 24 are comparative dyes, respectively.
This is a value obtained by comparing the red light sensitivities of [C] and [D] in terms of relative sensitivity. As is clear from these results, it can be seen that the sample containing the dye of the present invention maintains high sensitivity and high gamma even if it is left under severe film storage conditions for a long period of time. Example 3 This example shows that the present invention has advantages in terms of rapid processability as well.
This shows that high-sensitivity, high-gamma silver images with little fog can be obtained in a short time. Among the samples prepared in Examples 1 and 2, those shown in Table 3 below were subjected to rapid development processing. The same developer as in Example 1 was used.

【table】

[Table] As is clear from Tables 3 (1) and (2), it can be seen that the samples according to the present invention have excellent rapid development processability.

Claims (1)

[Scope of Claims] 1 A photographic constituent layer coated on a support contains at least one of the following compounds (1), (2) and (3) and the following general formula [] After image exposure, the photographic material is treated with a processing solution containing a reducing agent and a substance that dissolves the metal salt particles described in (2) below to selectively dissolve the metal salt particles in the exposed areas. 1.) A method for forming a negative image, comprising the step of depositing a metal image on the physical development nuclei of .). (1) Photosensitive silver halide grains (2) Metal salt particles that are themselves more easily soluble than the above (1) and whose surfaces have been made refractory with a refractory agent (3) Physical development nucleus general formula [] [In the formula, Z ¹ and Z ² each represent a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic nucleus, and R ¹ and R ² are each a lower alkyl group or a substituted alkyl group. At least one of R ¹ and R ² is a sulfoalkyl group or a carboxyalkyl group. R ³ is a lower alkyl group,
is an anion, l, m and n are 0 or 1, a is 0
Or represents 1. ]