JPS5948371B2 - Photographic material for forming negative images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic light-sensitive material for forming negative images, and more specifically, it provides negative images with high sensitivity, high contrast, and high maximum density, and also allows the use of a developing solution with improved storage stability. The present invention relates to a photographic material for forming negative images.

In general, the silver salt diffusion transfer method that uses physical development nuclei has a very high covering power (silver covering power) of the resulting transferred image, so it is possible to obtain a high-density photographic image with the use of a small amount of silver halide. It is also widely known as an extremely useful photographic image forming method because it is excellent in sensitivity and graininess.

However, the above method is usually a negative or positive type diffusion transfer method, and the final image obtained is a positive image, so it is not suitable for the purpose of the present invention of forming a negative image.

JP-A No. 54-48544 discloses that a photosensitive material for obtaining a negative image includes (1) a layer containing photosensitive silver halide (more easily soluble than photosensitive silver halide and substantially A photographic light-sensitive material has been proposed that has a combination layer consisting of a layer in which a refractory agent is adsorbed to metal salt particles that do not have photosensitivity, and a layer containing three-process development nuclei. Silver halide reducing agent (
(e.g. developer) and silver halide solvent (e.g. sulfite)
This method concerns a photographic light-sensitive material processed with a physical developer containing This may lead to a decrease in the maximum concentration, etc.
In addition, the color tone of the dark image is difficult to become neutral gray, and as a result, it is difficult to say that this is an appropriate method for silver saving.

Moreover, in these methods, in order to speed up the processing, it is necessary to use a developer with a high ability to dissolve the metal salts mentioned above, which results in the production of sludge and narrow processing applicability. For these reasons, it is difficult to say that this method is necessarily satisfactory. Therefore, an object of the present invention is to form a negative image with high sensitivity, high contrast, and high maximum density in a relatively short development time without requiring the use of a developer having a high solubility for metal salts. The object of the present invention is to provide a method, and further, to provide a photographic material capable of obtaining a negative image with high sensitivity, high contrast, and high maximum density, and in which a developing solution with improved storage stability can be used. be. As a result of intensive research to achieve the above object, the present inventors found that (1) photosensitive silver halide, (2) the surface of the silver halide was made difficult to solubilize by an agent that made it difficult to dissolve; Contains particles of a metal salt that is more easily soluble than silver halide and has substantially no photosensitivity, (3) physical development nuclei, and (4) at least one compound represented by the following general formula. It has been found that the above object can be achieved by means of a photographic material for forming negative images.

(In the formula, Q represents an atomic group necessary to form a heterocycle which may have a substituent, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) More details Examples of the heterocycle represented in the above general formula include a thiazoline-2-thione ring, a benzthiazoline-2-thione ring, a thiazolidine-2-thione ring, an imidazolidine-2-thione ring, and a selenazolidine-2-thione ring. , 1, 3, 4, thiadiazoline
2-thione ring, 1,3,4-zelenadiazoline-2
-thione ring, 4-zelenazoline-2-thione ring,
1,2-dihydrobiridine-2-thione ring, benzoxazoline-2-thione ring, benzimidazoline-2
-thione ring, benzzelenazoline-2-thione ring, 1,
Examples include a 2-dihydroquinoline-2-thione ring and a rhodanine ring.

Among these, thiazoline-2-thione ring, benzthiazoline-2-thione ring, thiazolidine-2-thione ring, 1,3,4-thiadiazolin-2-thione ring and rhodanine ring are preferred. R is an alkyl group having 1 to 10 carbon atoms, which is unsubstituted or substituted with a hydroxyl group, an aryl group, a morpholino group, etc., such as a methyl group, an ethyl group, a probyl group, a hexyl group, a decyl group,
Examples include hydroxyethyl group, benzyl group, morpholinoethyl group, unsubstituted or substituted aryl group with alkyl group, alkoxy group, halogen atom, etc., 4-methoxyphenyl group, 4-chlorophenyl group, and the like. Next, specific examples of the compound represented by the above general formula that can be used in the present invention are described below, but the present invention is not limited thereto.

′0!5 ″0 ″5 That is, in the present invention, the suitability for rapid processing and the image characteristics are improved in the conventional negative image type method. The solvent for the metal salt particles as shown above, which had been added in large amounts to the developing solution for the purpose of It has been possible to provide a method for forming a negative image and a photographic material A for forming a negative image, which has improved characteristics and image characteristics, and has a four-function developer that has excellent storage stability.

The photographic material for forming negative images of the present invention will be explained in detail below.

Examples of the photosensitive silver nogenide in the photographic material according to the present invention include silver chloride, silver bromide, silver iodide, silver bromide, silver iodobromide,
Silver chloroiodobromide or a mixture thereof is included, but preferably a high-sensitivity 02{:±:[MeF9-[Me=F. be.

Photographic milk A containing the above-mentioned photosensitive silver halide can be manufactured by various manufacturing methods including the conventional manufacturing method, the method described in Niba Special Publication No. 1983-J Kamo V2, or the method described in U.S. Patent No. 2,592. , 25 (can be prepared by the so-called conversion method described in the specification, such as the single jet emulsion method and the dinit emulsion method).

The photosensitive silver halide grains mentioned above include grains having various types of A.

The particle size varies depending on the purpose of use of the photosensitive book, but is usually 0.
．． F5V#4 of 1μ~3〃: Quotient? Chemically sensitized using a chemical sensitizer.

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. Furthermore, the above silver halide emulsion can also be spectrally sensitized using various sensitizing dyes.

These emulsions can also be prevented from fogging by using known stabilizers. Next, as the physical development nuclei used in the present invention, for example, noble metal colloids such as gold, silver, platinum, etc., metal sulfides such as silver, palladium, zinc, etc. 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 amount of the above-mentioned physical development nuclei in a photographic element varies depending on the type thereof, but for example, in the case of silver sulfide, it is 0.001θ to 1.0θ/Trl in terms of metallic silver) metallic silver (
0.
A range of 0.019 to 3.09/wl is appropriate.

Next, when the surface of the metal salt particles used in the present invention is not coated with the refractory agent, the dissolution rate in the solution of the compound that dissolves the metal salt particles is lower than that of the photosensitive halogen. It is a salt of a metal that is larger than silver and has virtually no photosensitivity. More specifically, the conditions for the dissolution rate of these two grains are as follows: The metal salt grain group (A) and the photosensitive silver halide grain group (self) contain at least one of the metal salt dissolving agents described below. Dissolution rate (for example, in the processing liquid used in the present invention) in the presence of
The mass of the substance dissolved per unit time) is (A), [F])
Under the condition that the total mass of particles included in both particle groups is equal, it is necessary that the particle group ^ is larger than the particle group (self). 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 are prepared, each emulsion is coated onto a support and dried to prepare 2IV 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 set at several levels, 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 percentage vs. immersion time, determine the immersion time tl of the photosensitive silver halide sample and the immersion time T2 of the metal salt particle sample corresponding to a residual percentage of 50%, and determine the value of T2/tl.

The value of T2/tl determined in this way needs to be smaller than 1, and preferably smaller than 0.7. Next, 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 energy necessary to sensitize the light-sensitive silver halide is applied to the light-sensitive photographic element according to the present invention, the light-sensitive silver halide is "substantially not sensitized" depending on the light energy.
This should be understood as such.

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 most 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 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 Crystals of these metal salts are preferably finer than silver, and the amount of particles of these metal salts ranges from 20 mol to 1000 mol per 100 mol of photosensitive silver halide. Furthermore, the surface of the metal salt particles used in the present invention is coated with a refractory agent, which is adsorbed onto the surface of the metal salt particles or acts as an active site for dissolution reaction. It is a compound that slows down the dissolution rate of the particles in the presence of the metal salt dissolving agent by adsorbing to a part of the particle surface of the readily soluble metal salt. , also includes compounds that form poorly soluble salts or complex salts with the metal ions of the metal salts.
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-based compounds, 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-
Typical examples include phenyl-5-methyl-1,2,4-triazole. Further, thiourea, imidazoles, triazoles, imidazoles, etc. are also preferred compounds that can be used in the present invention. Among these, mercaptotetrazole compounds are particularly preferred. The photographic light-sensitive material according to the present invention is characterized in that, in addition to the above-mentioned various elements, one or more compounds represented by the above general formula are contained in any of the constituent layers described below. .
The above compounds can be used alone or in combination of two or more, and the amount added is 1 x 10 - per mole of photosensitive silver halide in the emulsion layer or adjacent layer.
It can be used in a range of 5 to 1 x 10-1 mol, preferably 1 x 10-4 to 1 x 10-2 mol. As for the addition method, it may be directly dispersed in a photographic emulsion, or it may be added after being dissolved in an organic solvent such as methanol or ethylene glycol. Regarding the layer structure of the photosensitive material in the present invention, several embodiments are possible, including particles of photosensitive silver halide, for example, a metal salt having substantially no photosensitivity such as silver chloride, physical development nuclei and Either the four compounds represented by the above general formula are contained in the same coating composition (emulsion) and this is coated on a support, or the support is first coated with a substantially photosensitive material. A layer containing metal salt particles, physical development nuclei, and a compound represented by the above general formula in the same layer (
It is possible to arbitrarily select a structure in which an emulsion layer (emulsion layer) is coated, and an emulsion layer containing photosensitive silver halide is further coated on top of this layer.

In addition to these constituent layers, auxiliary layers such as a protective layer and an antihalation layer may be provided at appropriate positions as necessary, and photographic additives other than those mentioned above may be added to these layers. can. The photosensitive silver halide, metal salt particles, and physical development nuclei each independently include:
Alternatively, two or more types may be mixed and 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. Furthermore, the support used in the present invention includes, for example, baryta paper, polyethylene-coated paper, polyester film, cellulose acetate film, etc., and is appropriately selected depending on the intended use of the photographic material. After exposure, the photographic material according to the present invention is processed with a processing solution (developer) containing a reducing agent.

A developing agent is advantageously used as the reducing agent. As the developing agent used as a reducing agent in the processing agent of the present invention, any developer can be used.

For example, hydroquinone, 4-N-methylaminophenol (methol), ascorbic acid, isoascorbic acid, 2,6-dimethyl-4-aminophenol, toluhydroquinone, 2,6-dimethylhydroquinone, 2
-Methyl-4-amino-6-methoxyphenol, 2
, 6-dimethoxy-4-aminophenol, 2,5-dimethylhydroquinone, 2,4,6-triaminophenol, 2,4-diaminophenol (amidol), N
, N-diethyl-hydroxylamine, 4,6-diamino-ortho-cresol, and 1-phenyl-3-virazolidone. Further, as alkaline agents, for example, inorganic alkaline agents such as caustic soda and soda carbonate, as well as organic alkaline agents such as diethylamine, are also added to this treatment liquid.

In addition, development inhibitors such as those commonly used in developing solutions for silver halide photographic light-sensitive materials! Various additives such as color toning agents, curing agents, and development accelerators may be added as necessary. In particular, as the development inhibitor, derivatives such as imidazole, intazole, and triazole are preferably used. In the present invention, it is not necessary to add and contain a substance that dissolves the metal salt in the processing solution, for example, a dissolving agent, but as long as the amount does not adversely affect the storage stability of the developer. Substances that dissolve metal salts, such as sulfites such as sodium sulfite, thiosulfates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, cyanates such as potassium cyanide, sodium cyanide, thiocyanates such as sodium thiocyanide, potassium thiosulfate, etc. acid salts, cystine, amino acid compounds such as cysteine, thiourea, phenylthiourea, 3,6-dithia-1,8-
A thiourea compound such as octadiol, a thioether compound, etc. (preferably sodium sulfite and a combination thereof with potassium chloride or a thioether compound) may be contained in the treatment liquid. As for the conditions for development using such a processing solution, if rapid processing is required, processing can be performed at 30°C to 50°C for 10 to 50 seconds, but the temperature and time may be adjusted as necessary. can be selected.

As described in detail above, according to the present invention, the general formula By containing at least one of the compounds shown above, the photographic light-sensitive material for negative image formation of the present invention does not require the use of a special developer containing a large amount of silver halide solvent as in the past. , it is possible to use a general-purpose developer, and the development induction time is shortened during development, resulting in higher sensitivity and higher sensitivity than the above-mentioned conventional photosensitive materials.
It has become possible to form negative images with high contrast and maximum density, and therefore it has become more suitable for rapid processing. Hereinafter, the photographic material for forming negative images of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of photosensitive silver halide emulsion Silver nitrate, sodium chloride, potassium bromide and potassium iodide were prepared by a conventional neutral method to give a halogen composition of 74 mol% chlorine, 25 mol% bromine, respectively. A silver chloroiodobromide emulsion containing 1 mol% of iodine was prepared, and after second ripening was performed by sulfur sensitization, 4-hydroxy-bromide was added as a stabilizer.
A photosensitive emulsion was prepared by adding 0.39 6-methyl-1,3,3a,7-tetrazaindene per mole of silver halide.

(2) Preparation of silver halide grains with virtually no photosensitivity After washing a pure silver chloride emulsion consisting of silver nitrate and sodium chloride by a precipitation method using a normal neutral method, 1-phenyl 5-Mercaptotetrazole to silver chloride 1
850 per mole was added immediately.

(3) Preparation of physical development nuclei Silver nitrate was reduced with dextrin in an alkaline aqueous solution by a conventional method to produce ultrafine silver colloid particles, which were used as physical development nuclei.

High-sensitivity silver chloroiodobromide emulsion prepared by the method described above,
A fine-grained silver chloride emulsion and physical development nuclei were mixed, an appropriate amount of saponin was added as a coating aid, and the compounds according to the present invention as shown in Table 1 were added, and the mixture was coated uniformly on a subbed polyester base. .

At this time, the amount of coated silver per square meter was 2.09 for the high-speed emulsion, 20 m for the silver chloride fine grain emulsion) and 20 m for the physical development nucleus, and the amount of gelatin was 3.59.
It was hot. This layer is then overlaid with an appropriate amount of formalin hardener as a protective layer and succinic acid-2,- as a coating aid.
A sample was prepared by coating a 2.5% aqueous gelatin solution containing an appropriate amount of sodium ethylhexyl ester monosulfonate in multiple layers.

This sample was wedge-exposed to 320 CMS light, then developed for 30 seconds at 38°C using a developer with the following formulation, then fixed, washed with water, dried, and then the density was measured. The results are shown in Table 1. .

As is clear from Table 1 above, the photographic light-sensitive material containing the compound of the present invention in its constituent layers can obtain images with high sensitivity, high gamma, and high density even during high-temperature rapid processing compared to the comparative sample without the compound. can. Example 2 Using the sample prepared in Example 1, the processing solution was prepared by adding a compound (4) having the following structural formula to the developer 11 described in Example 1 according to the amount shown in Table 2 at 38° C. for 30 seconds. The results of the development are shown in Table 2.

As is clear from Table 2, when the photographic material according to the present invention is processed with a developer containing a silver halide solvent,
Images with high maximum density can be obtained by adding a very small amount of silver halide solvent, but in photographic materials not according to the present invention, images with high maximum density cannot be obtained unless a large amount of silver halide solvent is added to the developer. It is understood that high-quality images cannot be obtained. Example 3 A silver chloride emulsion prepared by the method described in Example 1 and a metallic silver colloid were mixed, an appropriate amount of saponin was added as a coating aid, the mixture was coated on a subbed polyester base, and the layer was further coated. A silver iodobromide emulsion (6 moles of iodine) prepared by a conventional neutral method, sensitized with gold and sulfur, and stabilized with 4-hydroxy-6-methyl-1,3,3a,7-tetrazyindene. #)) is mixed with an appropriate amount of sodium succinic acid mono-2-ethylhexyl ester monosulfonate as a coating aid and coated.

Claims (1)

[Scope of Claims] 1 (1) photosensitive silver halide, (2) the surface of which has been made difficult to solubilize by an agent that makes it difficult to dissolve; itself is more easily soluble than the photosensitive silver halide, and substantially 1. A photographic light-sensitive material for forming negative images, which contains particles of a metal salt that is not photosensitive, (3) physical development nuclei, and (4) at least one compound represented by the following general formula. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Q represents the atomic group necessary to form a heterocycle that may have a substituent, and R represents a substituted or unsubstituted alkyl group, a substituted or represents an unsubstituted aryl group.)