JPS5946378B2 - Method of forming dye images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which provides an excellent neutral black dye image.

In a typical black-and-white photographic system, a latent image is created in a silver halide photographic light-sensitive material by light, and this is processed using a common black-and-white developing agent (e.g., metol, phenidone, pyrogallol, hydroquinone, etc., which are well known in the art). The metallic silver produced in the exposed area by developing with a developer containing 2 is used as an image.

The oxidized developing agent is then promptly removed from the system. If the oxidized developing agent can be used as a substantially black dye image, further improvements in density and sensitivity can be expected. Various force methods have been proposed for this purpose.

For example, in West German Patent Nos. 492,518 and 537,923, black pigments are developed by mixing couplers such as yellow, magenta, and cyan, which are currently commonly used in color photography, and performing color development. A method of forming an image is described. However, in this method, coupling speeds between these three color couplers and a color developing agent such as a paraphenylene diamine color developing agent or a p-aminophenol color developing agent are different. Therefore, it is difficult to obtain a neutral black image. Further, West German Patent No. 1158836 and other documents describe a method of producing a black color image by condensing the oxidation product with an active methylene compound using a 4-aminopyrazolinobenzimidazole developing agent. . However, even with this method, it is practically difficult to obtain a substantially neutral black dye image of sufficient density. For example, British Patent No. 1,210,417 and US Pat. No. 3,615,509 describe methods using developer per couplers.

This involves developing a silver halide emulsion using a developing agent that has a p-aminophenol developing agent moiety and a coupler moiety composed of phenol, etc. in the same molecule to produce a polymerized dye in the exposed area. The dye is chelated by copper chelate bath treatment to obtain a substantially black dye image with sufficiently high density. However, since this method uses a so-called developer's per coupler, it is naturally an external process, and there remain problems with the stability of the processing bath, processing problems due to the use of copper chelate, and image stability. has been done.

Furthermore, in U.S. Pat. No. 3,674,490, etc., a silver image obtained by current black and white photographic processing is oxidized and coupled with an aromatic hydroxyamino compound in the silver image area using hydrogen peroxide as a reaction catalyst. A method for forming a quinone-based black pigment is described.

However, this method requires a large number of processing baths and it is difficult to obtain a sufficient concentration under normal conditions. Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a black image-forming coupler which has excellent photographic properties without such conventional drawbacks, and more specifically, it is an object of the present invention to provide a silver halide photographic material containing a black image-forming coupler that has excellent photographic properties without such conventional drawbacks. An object of the present invention is to provide a silver halide photographic light-sensitive material containing a coupler which forms a substantially black dye image by coupling with an oxidation product of an aromatic primary amine color developing agent used as a color developing agent.

The object of the present invention is to provide at least one 3-amylamino-5-pyrazolones and at least one ortho-position of the hydroxy group with a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a substituted oxy group or The present invention achieves this by processing a silver halide photographic emulsion with an aromatic primary amine color developer in the presence of at least one parahydroxybenzaldehyde substituted with an amide group. found out.

In the present invention, any 5-pyrazolones in which the 3-position of the pyrazolone ring is substituted with an acylamino group can be effectively used.

Representative examples of these compounds include those represented by the following general formula (1). General formula (1) 1X1 In the formula, R1 is a hydrogen atom or a chain or cyclic alkyl group (e.g. methyl, ethyl, isopropyl, t-butyl, t-octyl, allyl, cyclohexyl, norbornyl, etc.); or a substituted chain or cyclic alkyl group (substituents include halogen atom, nitro, cyanoaryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acyl, aminoureido, heterocycle, arylsulfonyl) Those selected from oxy and oxo groups, such as β-cyanoethyl, β-chloroethyl, benzyl, nitrobenzyl, dichlorobenzyl, γ-(2,4-di-t-pentylphenoxy)-propyl, β-phenoxyethyl, etc. ).

Furthermore, R1 is an aryl group (e.g. phenyl, α or β
-naphthyl group, etc.) or an aryl group having one or more substituents (substituents include, for example, alkyl, alkoxy,
aryloxy, halogen atom, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamide, arylsulfonamide, cyano, and nitro group).

In particular, phenyl groups in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. (e.g., 2,4,6-trichlorophenyl group, 2,
(6-dichloro4-methoxyphenyl group, etc.) are useful. R1 can also be a heterocyclic group (a 5- or 6-membered heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom, etc. as a heteroatom, a fused heterocycle, such as pyrrolyl, pyridylquinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, naphthoxazolyl) ) or a heterocyclic group further substituted with the substituents listed for the aryl group above. R2 represents an alkyl group, a substituted anolekyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group, each having the same meaning as R1 described above.

R2 can also be substituted oxy groups (e.g. methoxy, ethoxy, phenoxy, tolyloxy groups, etc.) or amino groups (e.g. substituted or unsubstituted N-alkylamino, cycloalkylamino, N,N dialkylamino,
N-alkyl-N-arylamino, N-arylamino group, etc.). In the formula, R3 represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group, each having the same meaning as R1, and a substituted oxy group having the same meaning as R2. or amino group. R3 can also be a halogen atom (e.g. fluorine, chlorine, bromine, iodine atom) or an amide group (
For example, it represents an acetamide group, a benzamide group, etc.). R
4, R5 and R6 each represent a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a substituted oxy group, an amide group or an amino group, each having the same meaning as R described above. R4, R5 and R6 also each represent a hydrogen atom or a substituted thio group (eg, ethylthio, propylthio, phenylthio, tolylthio group, etc.). Next, specific examples of 3-acylamino-5-pyrazolones (hereinafter referred to as pyrazolones of the present invention) used in the present invention are shown below, but the pyrazolones of the present invention are not limited thereto.

Compound Examples Next, specific examples of parahydroxybenzaldehydes (hereinafter referred to as the aldehydes of the present invention) used in the present invention are shown below, but the aldehydes of the present invention are not limited to these.

Compound Examples The pyrazolones and aldehydes of the present invention can be easily synthesized according to known methods, and commercially available aldehydes are available.

To form a dye image by processing a silver halide photographic emulsion with an aromatic primary amine color developer in the presence of the pyrazolones and aldehydes of the present invention (hereinafter referred to as compounds of the present invention), The compound of the present invention may be present in a position where a dye is formed by a color development reaction during color development, but in a preferred embodiment, the compound of the present invention is present in a silver halide emulsion layer or its silver halide emulsion layer. It is contained in an adjacent layer or in a color developing solution.

The reason why the silver halide photographic material of the present invention provides excellent black images is not clear in detail.

The dye image obtained by the force method of the present invention consists of three types of dyes: yellow, magenta, and cyan.
A black color is obtained by appropriate production ratios of the species pigments. The amount ratio of the three types of dyes to be produced depends on the type of pyrazolones of the present invention, the type of aldehydes of the present invention, and the amounts used thereof, as well as the composition of the silver halide emulsion used, the type of high-boiling solvent, and the development process. It is affected by the type of active ingredient, the pH and temperature of the developer, etc. Therefore, by changing these factors, a neutral black color can be easily obtained. The pyrazolones of the present invention can be used alone or in combination of two or more.

Furthermore, the aldehydes of the present invention can be used alone or in combination of two or more. This aldehyde is about 0.05% per mole of the pyrazolone of the present invention.
It is used in amounts of mol to 5 mol, preferably 0.1 mol to 1 mol. The pyrazolones and aldehydes of the present invention can be incorporated into silver halide emulsions according to techniques commonly used in conventional internal color photography. For example, the pyrazolones of the present invention and aldehydes are simultaneously added to a high boiling point organic solvent with a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl fucrate, or a low boiling point organic solvent such as ethyl acetate or butyl propionate, alone or in combination. After dissolving, it is mixed with an aqueous gelatin solution containing a surfactant, emulsified and dispersed in a high-speed rotating mixer or colloid mill, and then added to a silver halide emulsion, or after the emulsified dispersion is set, it is shredded and washed with water. After removing the low boiling point organic solvent by means such as the above, it may be added to the silver halide emulsion. Further, those having alkali solubility can also be added by the so-called Fischer dispersion method. The silver halide photographic light-sensitive material containing the compound of the present invention (hereinafter referred to as the silver halide photographic light-sensitive material of the present invention) can simultaneously contain ordinary yellow, magenta, and cyan couplers and the coupler described in JP-A-53-46029. May contain. When the silver halide photographic material of the present invention is developed with a conventional aromatic primary amine color developing agent, the exposed silver halide grains are reduced by the color developing agent. A silver image is formed while the oxidized color developing agent couples with the compound of this invention to provide a black dye.

Therefore, the silver halide photographic light-sensitive material of the present invention provides a substantially black dye image through a processing system of color development, fixation, and water washing, and uses the currently available aromatic primary amine as a developing agent. All color developing agents can be used, and particularly preferred color developing agents include p-aminophenol and p-phenylenediamine type developing agents, such as p-aminophenol, N,N-
Diethyl-p-phenylenediamine, N-ethyl-N-
ω-Sulfobutyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, p-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl N~(β -Hydroxyethino(c)aniline, 4-amino-3-methyl-N-ethyl-N-(β-methoxyethyl)aniline, 4-amino-
Examples include 3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)aniline and p-aminophenols. Furthermore, the present invention includes, for example, 2
, 2'-methylenebis(p-aminophenol), N,
It is also possible to use so-called De-Dev compounds such as N'-ethylenebis(4-amino-3-methyl-N-ethylaniline).

Also, U.S. Patent No. 2507114, U.S. Patent No. 3342599
It can also be used together with the developer precursor described in the above. In the silver halide photographic light-sensitive material of the present invention, known hydrophilic colloids such as gelatin and gelatin derivatives can be used to advantageously be used to prepare the light-sensitive emulsion.

The silver halide used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halide photographic emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Whatever is used applies. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can be prepared by various methods including commonly used methods, such as the method described in Japanese Patent Publication No. 46-J Kamo V2, or U.S. Pat. No. 2,592,250. The silver halide emulsion can be prepared by any method described in the specifications, ie, the production method of a so-called conversion emulsion or a so-called Lippmann emulsion, and this silver halide emulsion can be chemically sensitized by a known method. and further stabilization with triazoles, imidazoles, azaindenes, benzothiazolium compounds, mercaptans, or mixtures thereof, and thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitization. It is also possible to contain a compound.

Furthermore, in this silver halide emulsion, for example, glycerin, dihydroxy alkanes such as 1,5-pentanediol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, water-dispersible compounds obtained by emulsion polymerization, etc. It can contain a wetting agent such as a fine particle polymer compound, a plasticizer, a film property improver, etc.
In addition, hardeners such as ethyleneimine compounds, dioxane derivatives, dicarboxylic acid chlorides, diesters of methanesulfonic acid, coating aids such as saponin, sulfosuccinates, etc.
Various photographic additives such as fluorescent brighteners, antistatic agents, and antistain agents can be contained. Each of the silver halide photographic emulsions used in the present invention may be optically sensitized with a suitable sensitizing dye to impart photosensitivity in a desired wavelength range.

Various sensitizing dyes can be used, and one type or a combination of two or more types of sensitizing dyes can be used. The silver halide photographic material of the present invention may further contain various photographic additives in addition to the above-mentioned compounds, if necessary.

For example, in the photosensitive emulsion layer or its adjacent layer, there may be a compound that releases a development inhibitor in accordance with the density of the image during development, such as a development inhibitor-releasing compound as described in Japanese Patent Publication No. 46-22514. Alternatively, for example, a tetrazolium compound or the like may also be included depending on the purpose.
The silver halide photographic light-sensitive material of the present invention is prepared by applying the silver halide photographic emulsion layer according to the present invention containing various photographic additives to a support which has been subjected to corona discharge treatment, flame treatment or ultraviolet irradiation treatment. It is manufactured by coating on top or via a subbing layer, intermediate layer, etc.

Advantageously used supports include, for example, baryta paper,
In addition to polyethylene-coated paper, glass plates, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyamides, polycarbonates, polystyrene films, etc. can be mentioned, and each is selected depending on the intended use of the silver halide photographic light-sensitive material.

In applying the method of the present invention, preferably the compound of the present invention is contained in a silver halide photographic emulsion and color development is carried out by a color development method used for conventional so-called internal silver halide color photographic light-sensitive materials. Advantageously, so-called external color processing methods may also be applied.

Examples of internal color developing solutions include those having the following composition.

These developers may contain one or more black and white developing agents such as metol, phenidone, hydroquinone, etc., depending on the purpose.

After development, the silver halide photographic material of the present invention which has been color-developed using such a developer may be subjected to conventional photographic processing such as a stop solution containing an organic acid, an organic acid and hybo, or ammonium thiosulfate. A stop fixer containing a fixing component such as Hybo or ammonium thiosulfate, a fixer containing a fixing component such as Hybo or ammonium thiosulfate,
In addition, treatments selected from treatment with a treatment liquid such as a stabilizing liquid, washing with water, drying, etc. may be performed in an appropriate combination.

The silver halide photographic material of the present invention can be advantageously applied to all black and white photosensitive materials, such as general black and white negative photosensitive materials, general black and white paper or X-ray photosensitive materials, printing photosensitive materials, and general microphotographic photosensitive materials. This method is particularly effective in high-silver-content black-and-white photosensitive materials such as X-ray photosensitive materials and printing photosensitive materials, and the silver content can be greatly reduced without increasing the sensitivity. Further, the method of the present invention is described in, for example, Japanese Patent Publication No. 49-46419, Japanese Patent Application Publication No. 51
It can also be advantageously applied to the image enhancement processing methods described in Japanese Patent Application Laid-open No. 51-16029, Japanese Patent Application Laid-open No. 51-36136, and by applying this force method, even wider silver The amount can be reduced.

Furthermore, the method of the present invention can also be applied to color photographic materials described in, for example, Japanese Patent Application Laid-Open No. 53-13432 and Japanese Patent Application No. 131803-1983.

That is, a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler and a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler used in silver halide color photography based on ordinary subtractive color mixing color photography. The compound of the present invention can be incorporated into a silver halide photographic material having a combination of a red-sensitive silver halide emulsion layer containing a dye-forming coupler and a cyan dye-forming coupler.

In one embodiment, the compound of the present invention is contained in at least one silver halide emulsion layer containing a cyan coupler, magenta coupler or yellow coupler.

In another embodiment, the compounds of the invention are contained in at least one silver halide emulsion layer that is separate from the silver halide emulsion layer containing cyan coupler, magenta coupler or yellow coupler. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited by these.

Example (1) Each of the couplers 209 listed in Table 1 below was added to a mixture of 20 ml of dibutyl phthalate and 40 ml of ethyl acetate, and the mixture was heated to 60° C. to completely dissolve.

This solution was mixed with 10,711 liters of a 6% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, and emulsified and dispersed in a colloid mill. The resulting dispersion of each coupler was 1
kg of high-sensitivity silver iodobromide emulsion (containing 3.0 mol% A9), and 3% methanol of 1,3,5-triachlorohexahydro-S-triazine as a hardening agent. After adding 35 ml of hardener solution (hereinafter referred to as hardener solution), the mixture was coated on a triacetate base and dried to obtain a color photographic material having a stable coating film. Separately, a color photographic material was obtained in the same manner using a mixture of coupler 209 and aldehyde shown in Table 1 below. These light-sensitive materials were exposed to light in a conventional manner and then subjected to the following development treatments. The composition of the treatment liquid used in each treatment step was as follows. The density of the obtained image was set to 436 nm.
Concentrations were measured using buffered light at 1546 nm and 644 nm, and Table 1 shows the relative concentrations for each wavelength, assuming that the density for 546 nm light is 100 for a stage where the concentration for 546 nm light is approximately 1.0.

As is clear from Table 1, even if a coupler belonging to the present invention is combined with an aldehyde other than the present invention, a black image cannot be obtained by combining a coupler other than the present invention with an aldehyde of the present invention, but a black image cannot be obtained when the coupler belonging to the present invention is combined with an aldehyde other than the present invention. When the aldehydes of the present invention are combined, a black image is obtained, and the comparative compound (3) is
Although the coupler is known as a coupler that gives a black image described in No. 3-45029, the image obtained by the combination of the coupler of the present invention and an aldehyde is visually closer to a neutral black color than the image obtained from the comparative compound (3). .

Similarly, Exemplified Compound (1) and Exemplified Compound (114), Exemplified Compound (5) and Exemplified Compound (105), Exemplified Compound (1)
A combination of 1) and exemplified compound (108) also provides a nearly neutral black color. Example (2) Exemplified compound (101) 109 and Exemplified compound (3) 2.6
9 was added to a mixture of 10 d of dibutyl phthalate and 30 ml of ethyl acetate and completely dissolved at 40°C.

This solution was mixed with 5rn1 of a 10 (fl) aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
The mixture was mixed with 200 d of a 5% gelatin aqueous solution and emulsified and dispersed using a colloid mill to prepare a mixed dispersion of coupler and aldehyde. This dispersion was added to 5009 general black and white negative silver iodobromide emulsion (containing 5 mol% silver iodide) and 20 ml of hardener solution was added, resulting in an amount of coated silver of approximately 20 mg per 100 Cf. (Sample A). On the other hand, as a comparison, the same emulsion containing no mixed dispersion of Exemplified Compound (101) and Exemplified Compound Makisho) was coated on a triacetate base so that the silver amount was approximately 40 to 100 d (Sample B-Control). Samples A and B were exposed to normal wedge light and then developed for 6 minutes at 20° C. with a developer having the following composition.

After development, stopping, fixing, and washing were carried out in the usual manner, and the obtained samples were designated as A-1 and B-1, respectively.

On the other hand, after exposing sample A, color development was performed at 20° C. for 6 minutes using the following developer. After development, the sample was stopped, fixed, and washed with water in the usual manner, and the resulting sample was designated as A-2.

A-2 gave a blue-black color tone.

The results of the sensitometry are summarized in Table 2. As is clear from Table 2, sample A-2 according to the present invention is:
Although the amount of silver is half, control sample B-1
It was observed that the maximum concentration (Dmax) and the maximum concentration (Dmax) were at almost the same level.

Also, in place of exemplified compound (3), exemplified compound (2), (
Similar results were obtained when using 4), (8), and (self). Note) Specific sensitivity indicates the relative sensitivity when the sensitivity of sample B-1 is set as 100.

Example (3) The mixed dispersion of the coupler and aldehyde prepared in Example 11 (2) was added to a low-sensitivity silver chlorobromide emulsion for printing 5009 photosensitive material, and 20 ml of hardener solution was added. After that, the amount of silver is about 20/100? (Sample C).

For comparison, the same emulsion without dispersion was prepared with a silver content of approximately 50
It was coated on a triacetate base to give an instant/100 cIL (Sample D). Sample D has almost the same amount of silver as current printing photosensitive material products, but sample C is a low silver amount photosensitive material containing only 2/5 of silver halide. Samples C and D
A screen negative was brought into close contact with the film, and after exposure using a printer, the film was developed with a developer having the following composition at 20°C for 2 minutes and 30 seconds.

After development, a normal fixing wash was carried out, and the obtained samples were designated as C-1 and D-1, respectively.

On the other hand, Sample C, which had been exposed in the same manner, was subjected to color development using the following developer at 20° C. for 2 minutes and 30 seconds. After development, the sample was washed with normal fixing water and designated as C-2.

The results showed that sample C-1 had a lower halftone dot density than the control sample D-1, and the properties of the halftone dots themselves were also poor. However, in sample C-2, which was subjected to color development as described above using the same sample C, the blue-black color increases due to the color reaction, so the density and properties of the halftone dots change even though the amount of silver is 2/5. It became equivalent to the control sample D-1. Example (4) Exemplified compound (111) 109 and Exemplified compound (3) 3.4
The mixture of 9 was added to a mixture of 10 ml of tricresyl phosphate and 30 ml of ethyl acetate and completely dissolved at 50°C.

This solution was mixed with 5 ml of a 10% aqueous solution of Alkanol B and 200 ml of a 5% aqueous solution and emulsified using a colloid mill to prepare a mixed dispersion of coupler and aldehyde.
This dispersion was added to 5009 X-ray grade silver iodobromide (containing 5 mol% silver iodide) emulsion, and after adding 20 ml of hardener solution, the silver amount was adjusted to about 40 mg/100 CI1. was applied to one side of a polyester base (sample E). On the other hand, a control sample F was prepared by coating the same emulsion containing the coupler and aldehyde on one side of a polyester base so that the silver amount was 40η/100d.
After exposing sample F to the wedge, it was exposed to a developer with the following composition at 20°C for 50 minutes.
Separate development was performed, followed by normal fixing and water washing.

On the other hand, Sample E, which had been exposed in the same manner, was subjected to color development using a developer having the following composition at 20° C. for 5 minutes, followed by ordinary fixing washing.

As a result of processing, Sample E consisted of a dye image with black edges and a silver image as compared to Control Sample E as shown in Table 3.

However, the specific sensitivity in the table is a relative value when the sensitivity of sample B is set as 100. Example (6) A mixed dispersion of Exemplified Compound (101) and Exemplified Compound (2) was added to a silver chlorobromide emulsion for general black and white photographic paper, and a hardening agent solution was further added thereto. It was coated as shown in Table 5, and a protective film made of gelatin, a hardening agent, and a spreading agent was provided thereon.

Samples G and H were exposed to wedge light and then developed with a developer having the following composition at 20° C. for 1 minute.

After development, the sample was subjected to the usual stopping, fixing, and water washing. /F6. 1, 2 and 3.

On the other hand, for Samples H and I, different samples were subjected to color development at 20° C. for 1 minute with a developer having the following composition after wedge exposure. Next, the samples were subjected to the usual stopping, fixing, and water washing, and were designated as Samples 4 and 5.

Furthermore, regarding Sample 1, a sample that had been exposed to light using a wedge was placed in the above color developing solution at a concentration of 2.09 cobalt (m) per 11.
1 at 20°C with a solution containing hexaammine chloride.
After processing for a minute, stop, fix, and wash the sample in the same manner as below. It was set at 716.6.

The maximum concentration was determined for each sample. The results are summarized in Table 6. In this way, when the method of the present invention is used (A6.4), the amount of silver can be reduced to about half even in the normal case, and when cobalt hexaammine chloride is used (waste 6), the amount of silver is even more significant. The amount of silver can be reduced.

Example (7) A silver halide photographic emulsion was coated on a polyester base under the conditions shown in Table 7 below.

Further, a gelatin protective film containing a hardening agent, a spreading agent, etc. was coated on the silver halide photographic emulsion layer. In addition, a silver iodobromide emulsion for X-rays was used as the silver halide emulsion, and samples L and M
A mixture of Exemplified Compound (113) and Exemplified Compound (2) was protected and dispersed using tricresyl phosphate in the same manner as in Example-1. After exposing sample J to the wedge, it was developed with the monochrome developer used in Example 4 for 2'C5 minutes.
After that, it was fixed as usual and washed with water.

This was designated as sample plate 7 (control). Sample K was also treated in the same way. /F68. For samples L and M, the color developing solution used in Example-4 was used at 20°C for 5.
Color development was carried out for a minute, followed by fixing and washing with water in the same manner. This was designated as sample washing 9 and 10. Samples L and M were further treated with a developer having the following composition at 20° C. for 5 minutes. Next, the sample was fixed in the usual manner and washed with water.
And so.

After development, Sample M was further treated in a hydrogen peroxide bath having the composition shown below at 20° C. for 6 minutes, then fixed and washed in the same manner as described above, and the resulting sample was designated as Taki 13. Fog of the samples obtained by the above processing and maximum samples 0, P, Q, R
, S and T were subjected to normal halftone exposure and processed as follows.

Table 8 summarizes the results of measuring the density for Samples 0 and P at 20° C. for 2 minutes and 30 minutes using a developer having the following composition.
Table 8 shows that by combining the compound of the present invention and hydrogen peroxide reinforcing bath treatment, an even greater reduction in the amount of silver in the monochrome sensitive material can be achieved. Example (8) Using a low-sensitivity silver chlorobromide emulsion for printing and an alkaline dispersion of a mixture of Exemplified Compound (103) and Exemplified Compound (2),
Samples were prepared under the conditions shown in the table.

Separately, 5% DES [di-(ethylhexyl succinate)]
- Sodium sulfonate] aqueous solution 15 ml 10% gelatin aqueous solution 60 d 1,3,5-triphenyltetrazolium chloride (hereinafter abbreviated as T-Salt) 200 Tf 19
The solution obtained by ultrasonic dispersion using 35 ml of water was added to the mixture of the above emulsion and dispersion, and coated on a triacetate film base under the conditions shown in Table 10. Samples P and S were developed with the following developer at 20°C for 2 minutes and 30 seconds, fixed, and washed with water.The resulting product was used as sample 7f.
6.15 and 18.

Samples Q and T were developed in the same manner as Samples 15 and 18 using the above developer, then treated in a hydrogen peroxide amplification bath with the following composition at 20°C for 5 minutes, then fixed and washed with water. 16 and 19.

The results are summarized in Table 11.

Judging from the results in Table 11, samples containing T-Salt can produce halftone dots with good image quality even when processed with a general developer rather than a special developer for printing sensitive materials, and the combination with the coupler of the present invention It can be seen that halftone dots with sufficient density and image quality can be obtained with approximately half the amount of silver and with a greatly reduced amount of silver by using a hydrogen peroxide reinforcement bath.

Example (9) A silver halide emulsion layer and a protective layer were coated on a polyethylene terephthalate base according to Example (4) under the following conditions.

(1) Silver iodobromide emulsion for high-sensitivity X-ray Next, this sample was exposed with a wedge and developed with the following developer at 20°C for 3 minutes, then stopped and fixed as usual, washed with water, and dried to form a black color image. A negative result was obtained.

Adjust the pH to 11.0 with caustic soda.

The fog and maximum density (Dmax) of the obtained sample were as follows.

The above results show that the amount of silver can be significantly reduced (to 1/3 or less) compared to conventional X-ray films.

Example (Own) A green-sensitive silver iodobromide emulsion for X-ray containing Exemplified Compound (110) and Exemplified Compound (2) was coated on a polyethylene terephthalate base according to Example 8f1X4), and the coating amount was as follows. A sample consisting of a silver halide emulsion layer and a protective layer was prepared.

This sample was passed through an aluminum wedge using a Toshiba GTH orthotype intensifying screen (70KUP1100MA11).
X-ray exposure was performed at a distance of m.

This sample was color developed with the developer of Example (9) at 20° C. for 3 minutes, followed by usual fixing, washing with water, and drying.

Claims (1)

[Scope of Claims] 1. At least one of the 3-acylamino-5-pyrazolones and at least one of the ortho positions of the hydroxy group are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, or a substituted oxy group. or a method for forming a dye image, comprising processing a silver halide photographic emulsion with an aromatic primary amine color developer in the presence of at least one parahydroxybenzaldehyde substituted with an amide group. . 2. The method for forming a dye image according to claim 1, wherein the 3-acylamino-5-pyrazolones are represented by the following general formula (I) and the parahydroxybenzaldehydes are represented by the general formula (II). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group or an amino group. ] General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available. , R_5 and R_6 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Represents a multi-ring group, substituted oxy group, substituted thio group, amino group or amide group. ]