JP3248350B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for forming an ultra-high contrast negative image using the same. In particular, the present invention relates to a silver halide photographic light-sensitive material used in a photomechanical process. The present invention relates to a super-high contrast negative type photographic light-sensitive material suitable for a room light-sensitive material.

[0002]

2. Description of the Related Art In the field of graphic arts, in order to improve the reproduction of continuous tone images or the reproduction of line images by halftone images, a super-high contrast (particularly, a gamma of 1) is required.
(0 or more) is required. U.S. Pat. Nos. 4,224,401, 4,168,977, and 4,166,742 disclose methods for obtaining high-contrast photographic characteristics using a stable developer.
Nos. 4,311,781, 4,272,606
No. 4,221,857 and No. 4,332,87
No. 8, No. 4,634,661, No. 4,681,5
No. 74, No. 4,269,922, No. 4,650,
No. 746, No. 4,681,836 and the like using a hydrazine derivative are known. According to this method, high-sensitivity photographic characteristics can be obtained,
Further, since the addition of a high concentration of sulfite to the developer is allowed, the stability of the developer to air oxidation is dramatically improved as compared with the lith developer.

[0003] The light-sensitive material for a bright room used in the plate collecting and reversing processes is prepared by using a developed film on which a character or a halftone dot image is formed as an original and exposing the original and the reversal photosensitive material in close contact with each other. This is a photosensitive material used for performing negative image / positive image conversion or positive image / positive image conversion. A halftone image, a line image, and a character image are each converted into a negative image according to its halftone dot area, line width, and character image width. It is required to have the performance of image / positive image conversion. It is required to have the ability to adjust the tone of the halftone dot image and the line width of the character line image. Have been. However, in the advanced image conversion work of forming a blank character image by overlapping, in the conventional method using the bright room reversing process using a light room photosensitive material, the conventional bright room reversing process using the bright room reversing photosensitive material is performed. There is a disadvantage that the quality of the blank character image is deteriorated as compared with the method based on the process.

The method of forming a blank character image by overlapping is described in more detail. A transparent or translucent laminated base (usually a polyethylene terephthalate film having a thickness of about 100 μm is used), a character or line image Film (line drawing manuscript) and a film with a halftone image formed on a transparent or translucent pasting base (halftone manuscript)
The original is superimposed on the halftone original, and the exposure is performed by bringing the emulsion surface of the return photosensitive material into close contact with the halftone original. A post-exposure development process is performed to form a white part of a line image in a halftone dot image. An important point in such a method of forming a blank character image is that a negative image / positive image conversion is ideally performed according to a halftone dot area and a line width of a halftone dot document and a line drawing document. However, while a halftone original is exposed in direct contact with the emulsion surface of the return photosensitive material, a line drawing original is attached and the return photosensitive material is exposed via the base and the halftone original in the middle. become.
For this reason, if an exposure amount that faithfully converts a halftone dot document into a negative image / positive image is given, the line image document becomes out-of-focus exposure through the spacer by the sticking base and the halftone dot document. The line width becomes narrow. This is the reason why the quality of the blank character image is degraded.

To solve the above problems, systems using a hydrazine compound are disclosed in JP-A-62-80640, JP-A-62-235938, JP-A-62-235939, and JP-A-62-235939.
No. 3-104046, No. 63-103235, No. 63
-296031, 63-314541 and 64-
No. 13545. However, in this method, although the image quality is remarkably improved, air oxidation is remarkable due to the high pH of the developer, and the dot% fluctuation or Dmax
Therefore, there is a demand for a super-high contrast image forming system in which performance fluctuation is small.

[0006] The light-sensitive material for a light room is designed to have low sensitivity to visible light and can be handled in a light room. As a method for producing such a light-sensitive material, a silver halide mainly composed of silver chloride is used. A well-known method is to use an emulsion obtained by adding an inorganic or organic desensitizer such as a rhodium salt, an iridium salt, pinacritol yellow, or phenosafranine to the emulsion. In particular, a method of using a rhodium salt and / or an organic desensitizer in a fine grain silver chloride or a fine grain silver chlorobromide emulsion of 0.05 to 0.5 μm which is not subjected to chemical sensitization is preferably used. Further, in combination with these emulsions, a method of incorporating a yellow dye or an ultraviolet absorbing dye into a light-sensitive material is used for the purpose of adjusting sensitivity and imparting safelight safety. As a method of imparting ultra-high contrast photographic characteristics to a photosensitive material, a method of including a hydrazine derivative in the photosensitive material is known, but the method of including the above-described yellow dye or ultraviolet absorbing dye in the photosensitive material is known. When combined, it inhibits the high contrast effect of the hydrazine derivative,
In some cases, a problem that good line drawing reproduction performance is lost occurs.

[0007] WO 88/04794 discloses that the inclusion of a solid crystalline dye in the form of microcrystals makes the dye impossible to diffuse between layers. However, if these dyes are added so as to obtain safelight safety and target sensitivity, the amount becomes extremely large, and problems such as residual color or recoloration after the development process occur. A method of processing a photographic material containing a hydrazine compound in the presence of an ascorbic acid developing agent is already known.
Nos. 233734 and 63-47755, WO93 / 1
1456, WO 93/12463.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to firstly provide a method for forming an image of a silver halide photographic light-sensitive material for a bright room, which can obtain extremely hard photographic properties using a stable developer. To provide. A second object of the present invention is to provide a method for forming an image of a silver halide photographic light-sensitive material for a light room with a high practical skill Dm and a small variation in practical skill even with a developer that has been processed and run. Thirdly, it is an object of the present invention to provide a method for forming an image of a silver halide photographic light-sensitive material for a bright room, which has a high contrast and good image quality. Fourthly, it is an object of the present invention to provide a method for forming an image of a silver halide photographic light-sensitive material for a bright room, which has good safelight safety and little recoloring (coloring over time) after development processing.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide silver halide grains having a silver chloride content of at least 90 mol% and at least 1 × 10 ^-6 mol of rhodium and ruthenium per mol of silver; After imagewise exposing a silver halide photographic material having a silver halide emulsion layer containing a rhenium or osmium compound and containing a hydrazine compound in the emulsion layer or another hydrophilic colloid layer, (1)
(2) 1-phenyl-3-pyrazolidone-based or p-aminophenol-based auxiliary developing agent of 0.001 to 0.06 mol / L, (3) 0.3 to 1.2 mol / l of free sulfite ions, (4) a compound containing a compound represented by the following general formula (I), and a dihydroxybenzene-based compound The concentration ratio of the main drug is 0.03 to 0.12, and the pH is 9.0 to 12.0.
The image forming method is characterized in that development processing is performed with a developing solution. General formula (I)

[0010]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q represent It represents an atomic group which forms a 5- to 8-membered ring together with the two vinyl carbon atoms substituted by R ₁ and R ₂ and the carbon atom substituted by Y when bonded to each other. Y represents = 0 or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group.

The compound of the formula (I) of the present invention will be described in detail. In the general formula (I), R ₁ and R ₂ each represent a hydroxy group or an amino group (substituents include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group,
-Including those having a butyl group, a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-
A toluenesulfonylamino group, an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, and an alkylthio group (a methylthio group, an ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy, hydroxyalkyl, carboxyl, carboxyalkyl, sulfo, sulfoalkyl, amino, aminoalkyl,
Represents an alkyl group, an alkoxy group, a mercapto group, or P and Q are bonded to form 5 to 5 carbon atoms together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y; Represents the group of atoms necessary to form an 8-membered ring. Specific examples of the ring structure, -O -, - C (R 4) (R 5) -, -
_{C (R 6) =, -} C (= O) -, - N (R 7) -, - N =,
Are configured in combination. Where R ₄ , R ₅ , R ₆ ,
R ₇ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group or a sulfo group may be mentioned as a substituent), or an aryl group having 6 to 15 carbon atoms which may be substituted. Represents a group (an alkyl group, a halogen atom, a hydroxy group, a carboxy group, or a sulfo group can be given as a substituent), a hydroxy group, or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. And as an example of a preferred 5- to 6-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ＯO or ＮN—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxy group. Represents an alkyl group (for example, carboxymethyl, carboxyethyl). Hereinafter, specific examples of the compound of the general formula (I) are shown, but the present invention is not limited thereto.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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Among them, preferred is ascorbic acid or erythorbic acid (stereoisomer) (I-1). The amount of the compound represented by the general formula (I)
(The value obtained by dividing the concentration of the compound represented by formula (I) by the concentration of the dihydroxybenzene-based developing agent) is 0.03 to
It is in the range of 0.12. The preferred concentration ratio is 0.03 to
0.10, and a particularly preferable concentration ratio is 0.05 to 0.1.
09.

Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone,
Examples thereof include 2,5-dimethylhydroquinone, and particularly preferred is hydroquinone. The concentration of the hydroquinone derivative in the developer is from 0.2 to 0.75 mol / l, preferably from 0.2 to 0.5 mol / l, particularly preferably from 0.2 to 0.4 mol / l. is there.

The 1-phenyl-3-pyrazolidone derivative developing agents used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Tolyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like, preferably 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like.

The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol and p-aminophenol.
-Aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol and N- (4-hydroxyphenyl) glycine, among which N-methyl-p-aminophenol is preferable. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
Mol / l to 0.5 mol / l, the latter being 0.0
Preferably, it is used in an amount of 6 mol / l or less.

The preservative used in the developing solution of the developing agent of the present invention is a free sulfite ion, and as a form added to the developing solution, there are sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and the like. . The concentration of free sulfite ions is from 0.3 to 1.2 mol / l, preferably from 0.4 to 1.0 mol / l, particularly preferably from 0.5 to 0.8 mol / l. The pH of the developer used in the development processing of the present invention is in the range of 9.0 to 12.0, preferably 9.5 to 12.0. The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, sodium carbonate, sodium tertiary phosphate, potassium hydroxide, and potassium carbonate. Usually, the borate used as a buffering agent forms a complex with the ascorbic acid derivative compound of the compound of the general formula (I), so that it is preferably not present in the developer.

The developer used in the method of the present invention may contain a dialdehyde hardener or a bisulfite adduct thereof. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleic dialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α -N-butoxyglutaraldehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, or bisulfite adduct thereof. Among them, glutaraldehyde or its bisulfite adduct is most commonly used. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time does not significantly increase. Specifically, the amount is 1 to 50 g, preferably 3 to 10 g per liter of the developer.

The developer used in the method of the present invention contains an antifoggant, and examples thereof include indazole, benzimidazole and benztriazole. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-
5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-thiadiazol-2-yl) thio] butane Sodium sulfonate, 5-amino-1,
3,4-thiadiazole-2-thiol and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer. In addition to these organic antifoggants, for example, halides such as potassium bromide and sodium bromide can be used.

Further, various organic and inorganic chelating agents can be used in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, acyelinic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartar and the like, but are not limited thereto.

Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitriloacetic acid, nitrilic acid propionic acid, ethylenediaminomonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriamine Pentaacetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diaminotetraacetic acid, and others as described in JP-A-52-25632 and 55-67.
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
No. 2,276,39, etc., hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research Disclosure).
Disclosure) Volume 181, Item 18170 (1979
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminotetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. Other examples include Research Disclosure No. 18170, JP-A-57-208554, and JP-A-57-208554. -61125, 5
Compounds described in JP-A-5-29883 and JP-A-56-97347 can be exemplified.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65555
And the compounds described in Research Disclosure No. 55-65556 and Research Disclosure No. 18170 described above. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

In the developer used in the method of the present invention, in addition to the above-mentioned composition, a buffer (eg, carbonate, alkanolamine), an alkali (eg, hydroxide, carbonate), a solubilizing agent, if necessary. (For example, polyethylene glycols,
These esters), pH adjusters (eg, organic acids such as acetic acid), development accelerators (eg, US Pat. No. 2,648,604).
No., JP-B-44-9503, U.S. Pat. No. 3,171,247.
And various cationic compounds described above, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304, U.S. Pat.
No. 31832, No. 2950970, No. 2577127
Nonionic compounds such as polyethylene glycols and derivatives thereof, polythioethers described in JP-B-44-9
No. 509, Belgian Patent No. 682,862, thioether compounds described in U.S. Pat. No. 3,212,242, particularly preferably thioether compounds), and surfactants.

The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the processing temperature is about 20 ° C. to about 50 ° C. and the processing time is 10 seconds to 2 minutes. When processing 1 square meter of a silver halide black-and-white photographic material, the replenisher of the developing solution is 700 ml or less, preferably 500 ml or less.

After the development step, a fixing step is performed.
The fixing solution used in the fixing step of the present invention is an aqueous solution containing sodium thiosulfate, ammonium thiosulfate, and, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, and salts thereof. Usually, the pH is about 3.8 to about 7.0, preferably, pH 5.0 to 7.0, and particularly preferably, p.
H5.2 to 6.0. Among these components, the fixing agent is sodium thiosulfate or ammonium thiosulfate. The amount of thiosulfate used is 0.5 to 2.0 mol /
Liter, preferably 0.7 to 1.6 mol / l, particularly preferably 1.0 to 1.5 mol / l. The fixing solution may contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, boric acid), p
H regulator (eg, ammonia, sulfuric acid), chelating agent,
Surfactants, wetting agents and fixing accelerators can be included.
Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyester surfactants, and amphoteric surfactants described in JP-A-57-6840. In addition, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkyl glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122.
Nos. 535 and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459, and mesoionic compounds described in JP-A-4-229860. . Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, and citric acid; and inorganic buffers such as boric acid, phosphate, and sulfite. It is preferable to use an inorganic buffer from the viewpoint of suppressing odor and rust generation of equipment materials. Here, the pH buffer is used for the purpose of preventing the pH of the fixing solution from rising due to the carry-in of the developing solution, and is used in an amount of about 0.1 to 1.0 mol / l, more preferably about 0.2 to 0.6 mol / l. .

The hardener in the fixing solution of the present invention includes a water-soluble aluminum salt and a chromium salt. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. The fixing temperature and time are preferably from about 20 ° C. to about 50 ° C. for 5 seconds to 1 minute. The replenishment rate of the fixing solution is 700 ml / m ² or less, particularly preferably 500 ml / m ² or less.

The photosensitive material which has been developed and fixed is then washed or stabilized. The washing or stabilizing treatment can be carried out with a replenishment amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. In other words, not only water saving processing becomes possible,
It is possible to eliminate the need for piping for installing the automatic processing machine. When washing with a small amount of water, JP-A-63-18350, 6
It is more preferable to provide a septic tank for a squeeze roller described in 2-287252 and the like. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the anti-bubbling means to the washing or stabilizing bath by the method of the present invention in accordance with the treatment is disclosed in
As described in JP-A-235133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. In addition, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness which is easily generated in a small amount of aqueous solution and / or to prevent a processing agent component attached to a squeeze roller from being transferred to a processed film. Good. Further, in order to prevent contamination by dyes eluted from the photosensitive material, JP-A-63-16
The dye adsorbent described in No. 3456 may be installed in a washing tank.

In some cases, a stabilization treatment may be performed after the water washing treatment.
Baths containing the compounds described in JP-A Nos. 2-132435 and 1-125553 and JP-A-46-44446 may be used as the final bath of the photosensitive material. If necessary, metal compounds such as ammonium compounds, Bi and Al, fluorescent brighteners, various chelating agents, membrane pH buffers, hardeners, bactericides, fungicides, alkanolamines and surfactants Water used for the agent is tap water, deionized water, halogen, ultraviolet germicidal lamps and various oxidizing agents (ozone,
It is preferable to use water sterilized by hydrogen peroxide, chlorate, or the like.

The hydrazine derivative of the present invention will be described. Hydrazine derivatives are used as nucleating agents and RESEAR
CH DISCLOSURE Item 23516 (November 1983,
p. 346) and references cited therein, as well as U.S. Pat. Nos. 4,080,207, 4,269,929, 4,276,364, 4,278,748, and 4; No. 4,385,347, No. 4,560,638, No. 4,478,928, British Patent No. 2,011,391B, JP-A-60-1797.
No. 34, No. 62-270948, No. 63-29751
No. 61-170733, No. 61-270744
Nos., European Patent Nos. 217,310 and 356,898.
No. 4,686,167, JP-A-62-1
No. 78246, No. 63-32538, No. 63-104
Nos. 047, 63-121838 and 63-1293
No. 37, No. 63-223744, No. 63-23424
No. 4, No. 234245, No. 63-234246, No. 63-294552, No. 63-306438, No. 6
4-1233, JP-A-1-90439, 1-1
No. 00530, No. 1-105941, No. 1-1059
No. 43, No. 1-276128, No. 1-280747
Nos. 1-285548, 1-283549, 1-285940, 2-2541, 2-770
No. 57, No. 2-139538, No. 2-196234
Nos. 2-196235, 2-198440, 2-198441, 2-198442, and 2-2
No. 20042, No. 2-21953, No. 2-2219
No. 54, No. 2-302750, No. 2-304550
And the known compounds described in Japanese Patent Application No. 5-94925 can be used.

As the hydrazine derivative of the present invention, those represented by the general formula (II) are particularly preferred. General formula (I
I)

[0041]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, Represents a carbamoyl group or an oxycarbonyl group, and G ₁ represents a —CO— group, a —SO ₂ — group,
SO- group

[0043]

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A represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group; A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Or an unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group. The R ₃ is selected from the same range as radical as defined R _2, may be different from R _2.

The hydrazine compound represented by the general formula (II) will be described in detail. In the general formula (II), R
_The aliphatic group represented by ₁ preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have a substituent. In the general formula (II), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group. Preferred as R ₁ is an aryl group, particularly preferably a group containing a benzene ring. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido. Group,
Urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, Alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide group, R ₄ —NH
A CON (R ₅ ) —CO— group (R ₄ and R ₅ are selected from the same groups as defined for R ₂ and may be different from each other), and a preferred substituent is an alkyl group (preferably Represents an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably having 1 to 20 carbon atoms). An amino group substituted with an alkyl group), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 3 carbon atoms)
0), a ureido group (preferably having 1 to 3 carbon atoms)
0), a phosphoric amide group (preferably having 1 carbon atom)
To 30). These groups may be further substituted.

In formula (II), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene Containing a ring). G
If ₁ is a -CO- group, preferred among the groups represented by R ₂ is a hydrogen atom, an alkyl group (e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamide propyl Phenylsulfonylmethyl group), an aralkyl group (eg, o-
A hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, a 2-hydroxymethylphenyl group), and particularly hydrogen. Atoms are preferred. R ₂ may be substituted, and the substituents listed for R ₁ can be applied.

G _{1 in the} general formula (II) is most preferably a —CO— group. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. Examples thereof include those described in JP-A-63-29751. A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (II) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy group, alkylphenoxy group and the like. Further, as a polymer, for example,
No. 100530.

R ₁ or R _{2 in} the general formula (II) may have a group in which a group which enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorptive group include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups such as U.S. Pat.
No. 4,459,347, JP-A-59-195233.
Nos. 59-200231 and 59-201045
Nos. 59-201046 and 59-201047
Nos. 59-201048 and 59-201049
No. 61-170733, No. 61-270744
Nos. 62-270948 and 63-234244
And groups described in JP-A-63-234245 and JP-A-63-234246.

In the general formula (II), at least one of R _{1 and} R ₂ has a ballast group or R ₁ or R ₂
It is preferable that at least one of these has a group that enhances adsorption to the surface of the silver halide grains. Further, R ₁ has a trialkylammonium group, R ₁ has an alkylthio group (including a cycloalkylthio group) or an arylthio group, and R ₂ is other than a hydrogen atom, particularly a carbon atom bonded to G _{1 in} R _2. Is particularly preferably substituted by an electron-withdrawing group (eg, a halogen atom, a cyano group, a nitro group, a sulfonyl group, etc.).

Specific examples of the compound represented by formula (II) are listed below, but the present invention is not limited thereto.

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The hydrazine derivatives used in the present invention include, in addition to the above, RESEARCHDISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent No. 2,011,
No. 391B, JP-A-60-179834 and JP-A-62-2
No. 70948, No. 63-29751, No. 61-170
Nos. 733 and 61-270744, European Patent No. 21
7,310, 356,898, U.S. Pat.
86,167, JP-A-62-178246, 63
No. 32538, No. 63-104047, No. 63-1
Nos. 21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
No. 245, No. 63-234246, No. 63-2945
No. 52, No. 63-306438, No. 64-10233
No., JP-A-1-90439, JP-A-1-100530,
No. 1-1055941, No. 1-105943, No. 1-
No. 276128, No. 1-280747, No. 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962
No. 35, No. 2-198440, No. 2-198441,
2-198442, 2-2-20042, 2-
Nos. 221953, 2-221954 and 2-302
Nos. 750 and 2-304550 can be used.

In the present invention, the hydrazine derivative is preferably added in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and more preferably 1 × 1 ^-2 mol, per mol of silver halide.
The range of 0 ^-5 mol to 2 × 10 ^-2 mol is a preferable addition amount.

The hydrazine derivative of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcell It can be used by dissolving it in Solve or the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved and mechanically emulsified. A dispersion can also be prepared and used. Alternatively, the hydrazine derivative powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

Particularly, when a rhodium or ruthenium complex is contained in an amount of 1 × 10 ⁻⁵ mol or more per mol of silver, or when processed with the developing solution of the present invention having a pH of less than 11, a silver halide photographic light-sensitive material contains halogen. It is preferable to add a nucleation accelerator such as an amine derivative, an onium salt, a disulfide derivative, and a hydroxylamine derivative to the silver halide emulsion layer or another hydrophilic colloid layer.

As the amine derivative, for example, JP-A-60
-140,340, 62-50,829, 62
-222,241, 62-250,439, 6
Compounds described in 2-280,733, 63-124,045, 63-133,145, 63-286,840 and the like can be mentioned. More preferably as an amine derivative, JP-A-63-124,045, 63-133,1
Nos. 45 and 63-286,840, etc., compounds having a group adsorbing to silver halide, or JP-A-62-22
Compounds having a sum of 20 or more carbon atoms described in US Pat. No. 2,241 or the like, US Pat. No. 4,975,354, EP458P70
Examples thereof include amine compounds having an ethylene group described in No. 6A and the like, and compounds described in JP-A-62-50829. As the onium salt, a pyridinium salt, an ammonium salt or a phosphonium salt is preferable. Preferred examples of the pyridinium salt include the compounds described in Japanese Patent Application No. 5-97866. Also,
Preferred examples of the ammonium salt are described in JP-A-62-2.
Compounds described in JP-A Nos. 50,439 and 62-280,733 can be exemplified. Examples of preferred phosphonium salts are described in JP-A-61-16793.
No. 9, 62-280, 733 and the like. Examples of the disulfide derivative include compounds described in JP-A-61-198,147. Examples of the hydroxymethyl derivative include, for example, U.S. Patent Nos. 4,698,956 and 4,777,118, EP23
No. 1,850, JP-A-62-50,829 and the like, and more preferred are diaryl methacrylol derivatives. Examples of the acetylene derivative include, for example, JP-A-3-168735 and JP-A-2-27.
1351 and the like. Examples of the urea derivative include compounds described in JP-A-3-168736.

Next, specific examples of the nucleation accelerator will be shown. However, the present invention is not limited to the following compounds.

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The optimum addition amount of these compounds differs depending on the kind thereof, but 1.0 × 1 per mol of the hydrazine compound.
0 ^-2 mol to 1.0 × 10 ² mol, preferably 1.0 × 10 ² mol
It is desirable to use in the range of 10 ^-1 mol to 5.0 × 10 mol. These compounds are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. Objects can also be created and used. Alternatively, powders of these compounds can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

Examples of useful nucleation development accelerators contained in the developing solution used in the present invention include, for example, JP-A-56-106244 and JP-A-61-267759.
No. 61-230145, No. 62-21647
And benzyl alcohol derivatives described in JP-A-60-200250. In particular, the general formula (I
Compounds represented by II) are preferred. General formula (III) R ₁₁ -N (R ₂₂ ) -R _{23 In the} formula, R ₂₁ , R ₂₂ and R ₂₃ are each HR ₂₁ , H-
R _22, as H-R ₂₃ of n- octanol / water partition log
(log P) represents a substituted or unsubstituted alkyl group having a sum of values of 2.6 or more and less than 10.0. And lo
Compounds in which the sum of the values of g P falls within the range of 3.0 or more and less than 8.0 are particularly preferred.

Next, the general formula (III) will be described in detail. Examples of the substituent of the substituted alkyl group represented by R _{21 to} R ₂₃ include a hydroxyl group, an alkoxy group, a carboxy group,
Examples include a sulfo group, an aryloxy group, and an amino group. The value of the logarithm (log P) of the n-octanol / water partition coefficient is calculated by the method of Substituent Constints-Hofo Correlation Analysis in Chemistry and Biology (Substituent Constants). For Correlation Analy
sis in Chemistry and Biology) Handbook of
Handbook of Chemical Property Estimation Metho
ds) and defined in the present invention. log P
Is also obtained in this way. Typical H
It indicates the value of log P of -R ₂₁ and H-R ₂₂ and H-R _23.
The value of logarithm (log P) of n-octanol / water partition coefficient of HR ₂₁ , HR ₂₂ , and HR ₂₃

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Specific examples of the amino compound represented by the general formula (III) are shown below.

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The amino compound represented by the general formula (III), unlike other amino compounds, remarkably promotes high contrast in a small amount, but has a weak effect of silver halide as a solvent, and thus has a low silver stain. It has excellent performance that it does not cause. The amino compound represented by the general formula (III) is preferably contained in an amount of 0.1 to 1 liter per developer.
It is used in the range of 01 to 0.30 mol / liter,
Particularly, it is preferably used in the range of 0.01 to 0.2 mol / liter. The amino compound represented by the general formula (III) has a relatively low solubility in a developing solution (water). For the sake of convenience of storage and transportation, when the developing solution is concentrated to reduce its volume, it is generally used. The amino compound of the formula (III) may precipitate and precipitate. However, the following general formula
When the compound represented by (IV) or (V) is used, even if the liquid is concentrated, such generation of precipitation / precipitation can be prevented. General formula (IV)

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Formula (V)

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Here, M represents hydrogen atoms Na, K, and NH ₄ . R ₂₄ and R ₂₅ represent an alkyl group having 3 or more carbon atoms, an alkylbenzene group, or a benzene group.

Specific examples of the compound of the general formula (IV) include p
-Sodium toluenesulfonate, sodium benzenesulfonate, sodium 1-hexanesulfonate and the like. Specific examples of the compound of the general formula (V) include sodium benzoate, sodium p-toluate, potassium isobutyrate, sodium n-caproate, sodium n-caprylate, sodium n-caprate and the like. The amount of the compound represented by the general formula (IV) or (V) varies depending on the amount of the amino compound represented by the general formula (III), but is usually 0.005 mol / L or more, particularly 0.1 mol / L or more.
A suitable range is from 03 mol / l to 0.1 mol / l. The range is suitably 0.5 to 20 mol per 1 mol of the amino compound of the general formula (III).

When a dye is added to at least one of the hydrophilic colloid layers of the light-sensitive material of the present invention for the purpose of a filter function, an antihalation function, and other purposes, it is preferable to use a fine crystal dispersion dye. The dye of the microcrystal dispersion used in the present invention will be described. These dyes are represented by the following general formulas (KI), (K-II), (K-III), (K-III)
-IV) and (KV) are contained in the silver halide emulsion layer or the hydrophilic colloid layer as a microcrystal dispersion of at least one compound selected from the group consisting of (KV). General formula (K
-I)

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Formula (K-II)

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General formula (K-III)

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General formula (K-IV)

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General formula (KV)

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(Wherein A ₃ and A ₃ ′ may be the same or different and each represents a substituted or unsubstituted group having a carboxyphenyl group, a sulfamoylphenyl group, a sulfonamidophenyl group, a carboxyalkyl group, or a hydroxyphenyl group. Wherein the acid nucleus includes 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine and B ₃ represents a substituted or unsubstituted basic nucleus having a carboxyl group, a sulfamoyl group or a sulfonamide group, and examples of the basic nucleus include pyridine, quinoline, indolenine, oxazole, and benzo. Oxazole, naphtho .R ₃₀ selected from the group consisting of Kisazoru and pyrrole represents a hydrogen atom or an alkyl group, R _31, R ₃₂ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group R ₃₁ and R ₃₂ may be linked to form a 5- or 5-membered ring, R ₃₃ and R ₃₆ represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a halogen atom; ₃₄ and R ₃₅ are each a hydrogen atom or R
₃₁ and R ₃₄ or R ₃₂ and R ₃₅ represents a non-metallic atomic group necessary for forming a 5 or 6-membered ring. However, the compounds represented by the general formulas (KI), (K-II), (K-III), (K-IV) and (KV) have a volume ratio of water to ethanol in one molecule. Has at least one dissociative group having a pKa in the range of 4 to 11 in a 1: 1 mixed solution. )

Formulas (KI), (K-II) and (K-II)
I), (K-IV) and (KV) will be described in detail. Acidic nucleus represented by A _3, or A ₃ 'is preferably 2-pyrazoline-5-one, rhodanine, hydantoin,
Represents thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine or hydroxypyridone. Basic nucleus represented by B ₃ preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, the naphthoxazole or pyrrole. The group having a dissociable proton having a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution in which the volume ratio of water and ethanol is 1 to 1 is pH 6 or pH
The type and substitution position of the dye molecule are not particularly limited as long as the dye molecule is substantially water-insoluble at pH 6 or less and the dye molecule is substantially water-soluble at pH 8 or pH 8 or higher, but is preferably not limited. A carboxyl group, a sulfamoyl group, a sulfonamide group, and a hydroxy group are more preferable, and a carboxyl group is more preferable. The dissociable group may be substituted not only directly on the dye molecule but also via a divalent linking group (for example, an alkylene group or a phenylene group). Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl,
3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl,
2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl, 4- (p-cyamibenzenesulfonamido) phenyl, 3-hydroxyphenyl, 2-
Hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4
-Carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-
Sulfamoylphenyl, 2,5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3
-Carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl and the like. R ₃₀ , R ₃₃
Or an alkyl group represented by R ₃₆ is preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n- propyl, isoamyl, there can be mentioned groups of the n- octyl. The alkyl group represented by R ₃₁ and R ₃₂ has 1 carbon atom.
To 20 alkyl groups (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl), and a substituent [e.g., a halogen atom such as chlorine or bromine, a nitro group , Cyano group, hydroxy group, carboxy group, alkoxy group (eg, methoxy, ethoxy), alkoxycarbonyl group (eg, methoxycarbonyl, i-propoxycarbonyl), aryloxy group (eg, phenoxy group), phenyl group, amide group (Eg, acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), and a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)]. R ₃₁ or R ₃₂
The aryl group represented by is preferably a phenyl group or a naphthyl group, and is a substituent (substituents include the above-mentioned groups represented by the alkyl group represented by R ₃₁ and R ₃₂ and alkyl groups (eg, methyl and ethyl) Is included. ]
May be provided. The acyl group represented by R ₃₁ or R ₃₂ is preferably an acyl group having 2 to 10 carbon atoms, and examples thereof include groups such as acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, and benzoyl. Examples of the alkylsulfonyl group or arylsulfonyl group represented by R ₃₁ or R ₃₂ include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl,
Groups such as n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, o-carboxybenzenesulfonyl and the like can be mentioned. The alkoxy group represented by R ₃₃ or R ₃₆ is preferably an alkoxy group having 1 to 10 carbon atoms, for example, methoxy, ethoxy, n-butoxy, n-
Groups such as offoxy, 2-ethylhexyloxy, isobutoxy, isopropoxy and the like can be mentioned. R ₃₃
Alternatively, examples of the halogen atom represented by R ₃₆ include chlorine, bromine, and fluorine. R ₃₁ and R ₃₄ or R ₃₂
And the ring formed by linking R ₃₅ include, for example, a julolidine ring. Examples of the 5- or 6-membered ring formed by linking R ₃₁ and R ₃₂ include a piperidine ring, a morpholine ring, and a pyrrolidine ring. The methine group represented by L ₃₁ , L ₃₂ or L ₃₃ may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl). The electron-withdrawing groups represented by X ₃ or Y ₃ may be the same or different and include a cyano group, a carboxy group, an alkylcarbonyl group (optionally substituted alkylcarbonyl group, for example, acetyl, propionyl, heptanoyl, dodecanoyl , Hexadecanoyl, 1-oxo-7-chloroheptyl group, etc.), arylcarbonyl group (optionally substituted arylcarbonyl group, for example, benzoyl,
4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl group and the like, alkoxycarbonyl group (optionally substituted alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl,
t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2
-Cyanoethoxycarbonyl, 2- (2-chloroethoxy) ethoxycarbonyl, 2- [2- (2-chloroethoxy) ethoxy] ethoxycarbonyl group, etc.), aryloxycarbonylcarbamoyl group, etc.), sulfonyl group (for example, methylsulfonyl) , Phenylsulfonyl group, etc.) and sulfamoyl group (optionally substituted sulfamoyl group, for example, sulfamoyl, methylsulfamoyl group, etc.). Next, specific examples of the dye used in the present invention will be described, but the present invention is not limited thereto.

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The dye used in the present invention is described in International Patent WO8.
8/04794, European Patent EP 0274723
Nos. A1, 276,566, 299,435, JP-A-52-92716, 55-155350, 55-155351, 61-205934, and 4
8-68623, U.S. Pat. No. 2,527,583,
No. 3,486,897, No. 3,746,539, No. 3,933,798, No. 4,130,429, No. 4,040,841, etc. And can be easily synthesized.

The method for dispersing the dye of the present invention is described in International Application Publication (WO) 88/04794, European Patent (EP) 0276566A1, and JP-A-63-1979.
43, etc., a method of mechanically pulverizing with a ball mill or a sand mill, a colloid mill, etc., stabilizing with a surfactant and gelatin, dissolving a dye in an alkaline solution, lowering the pH, and precipitating. A method is used. However, the invention is not limited to these methods. The dye of the present invention in the dispersion has an average particle size of 10 μm or less, more preferably 2 μm or less, and particularly preferably 0.5 μm or less. The dye is used in an amount of 1 to 1000 mg per 1 m ² of the photosensitive material, preferably 1 to 800 mg per 1 m ² .

The organic desensitizer used in the present invention is generally known to be used directly in a positive silver halide emulsion. That is, the organic desensitizer used in the present invention is characterized by its polarographic half-solution potential, that is, its redox potential determined by polarography. Organic desensitizers useful in the present invention are those in which the sum of the polarographic anode potential and the polarographic cathode potential is positive. Methods for measuring these oxidation-reduction potentials are described in, for example, US Pat. No. 3,501,307. Specific examples of such organic desensitizers are described in a large number of patent specifications and literatures, all of which have the same action in the present invention. For example, Japanese Patent Publication No. 36-17595, 3-764
50, Dojo 39-20261, Dojo 40-26751,
43-1167, 45-8833, 47
-8746, 47-10197, 50-375
30, JP-A-48-24734 and JP-A-49-8463.
9, No. 56-142525, U.S. Pat. No. 2,271,
No. 229, No. 2,541,472, No. 3,03
No. 5,917, No. 3,062,651, No. 3,1
No. 24,458, No. 3,326,687, No. 3,
Compounds described in the specification such as 671,254 can be used.

The organic desensitizer used in the present invention preferably has at least one water-soluble group or alkali-dissociable group. When these organic desensitizers are used in a high-contrast material containing a hydrazine compound, the sensitivity can be effectively lowered without hindering high-contrast. The phenomena occurring in this system are extremely complicated, and the mechanism is unclear, but the present inventors speculate as follows. That is, as described above, at the time of image exposure, these organic desensitizers accept photoelectrons and lower the sensitivity to prevent the formation of a latent image, but at the time of development processing,
The hydrazine compound dissolves in the processing solution or separates from the silver halide grains, and does not effectively act as an acceptor for electrons donated by the hydrazine compound. It is thought to occur. Specific examples of the water-soluble group present in at least one organic desensitizer include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and the like. These groups include organic bases (eg, ammonia, pyridine, triethylamine). , Piperidine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.) and the like. Alkali dissociable group is the pH of the developing solution
(It is usually in the range of pH 9 to pH 13, but other p
There may be processing solutions that exhibit H. ) Or an anionic substituent which causes a deprotonation reaction at other pH. Specifically, at least one hydrogen atom bonded to a nitrogen atom by a substituent such as a substituted / unsubstituted sulfamoyl group, a substituted / unsubstituted carbamoyl group, a sulfonamide group, an acylamino group, and a substituted / unsubstituted ureido group. Refers to the substituents and hydroxy groups that are present. Further, a heterocyclic group having a hydrogen atom on a nitrogen atom constituting the hetero ring of the nitrogen-containing hetero ring is also included in the alkali-dissociable group.

These water-soluble groups and alkali-dissociable groups may be connected to any part of the organic desensitizer.
It may have more than one species at the same time. Preferred examples of the organic desensitizer used in the present invention include the following general formula (D-
1) to those represented by the general formula (D-3).
However, the substituents Z ₁ , Z ₂ , T, P and Q represented by the general formulas (D-1) to (D-3) have at least 1
It has two water-soluble groups or alkali-dissociable groups.

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In the formula, Z ₁ represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and this ring may further have a substituent. T is an alkyl group, cycloalkyl group, alkenyl group, halogen atom, cyano group, trifluoromethyl group, alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, carboxyl group, carbamoyl group, sulfamoyl group, malyl group, acylamino A sulfonamide group, a sulfo group, or a benzo-fused ring, which may further have a substituent. q represents 1, 2, or 3 r represents 0, 1, or 2. In the general formula (D-1), specific examples of the nitrogen-containing heterocycle completed by Z ₁ include, for example, a 1,2,4-triazole ring, 1,3,4
-Oxadiazole ring, 1,3,4-thiadiazole ring, tetraazaindene ring, pentaazaindene ring, triazaindene ring, benzothiazole ring, benzimidazole ring, benzoxazole ring, pyrimidine ring, triazine ring, pyridine ring , Quinoline ring, quinazoline ring, phthalazine ring, quinoxaline ring, imidazo [4,5-b]
Examples thereof include a quinoxaline ring, a tetrazole ring and a 1,3-diazaazulene ring, and these rings may further have a substituent or may have a condensed ring.

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In the formula, P and Q may be the same or different from each other, and may be a cyano group, an acyl group, a thioacyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted group. Represents a substituted carbamoyl group, a nitro group, or a substituted or unsubstituted aryl group. n represents 1, 2, or 3. T,
r and q have the same meanings as described in formula (D-1).

[0150]

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In the formula, Z ₂ is a ketomethylene ring, for example, a pyrazolone ring, an isoxazolone ring, an oxindole ring,
Barbitur ring, thiobarbitur ring, rhodanine ring,
Imidazo [1,2-a] pyridone ring, 2-thio-2,4
-Oxazolidinedione ring, 2-thio-2,5-thiazolidinedione ring, thiazolidone ring, 4-thiazolone ring,
A non-metal atom group necessary for completing a 2-imino-2,4-oxazolinone ring, a 2,4-imidazolinedione ring (hydantoin ring), a 2-thiohydantoin ring, a 5-imidazolone ring, and the like. m represents 1, 2, and 3. T,
r and q have the same meanings as described in formula (D-1).

Next, specific examples of the compounds represented by formulas (D-1) to (D-3) are described below. However, the present invention is not limited only to these.

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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Further, in the present invention, the following organic desensitizers can also be used. 1) Pinacritol yellow 2) 1,1'-Dibutyl-4,4'-bipyridium dibromide 3) 1,1'-Ethylene-2,2'-bipyridinium
Dibromide 4) phenosafuranine

The organic desensitizer in the present invention may be contained in the silver halide emulsion layer in an amount of 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / m ² ,
In particular, it is preferable that 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ^{2 be} present.

The average grain size of the silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is not particularly limited, but is preferably 0.30 μm or less. Especially 0.
It is preferably from 08 to 0.16 µm. In the present invention, the silver halide grains are prepared by mixing at a reaction temperature of 50 ° C. or lower, preferably 40 ° C. or lower, and a silver potential of 70 m under a sufficiently high stirring speed for uniform mixing.
V or more, preferably 300 mV to 500 mV, or
5,6-cyclopentane-4-hydroxy-1,3,3
Good results can be obtained by adjusting the voltage at 80 mV to 120 mV in the presence of a stabilizer such as a, 7-tetrazaindene. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size, and more preferably within ± 20%. The silver halide grains of the present invention preferably have regular crystals such as cubes and octahedrons, and particularly preferably cubes. The silver halide grains preferably contain a transition metal.

Preferred as the transition metal compound selected from Rh, Ru, Re or Os used in the present invention is a transition metal coordination complex, which is a hexacoordinate complex represented by the following general formula. [M (NY) _m L _6-m ] ⁿ , wherein M is Rh, Ru, Re or Os; L is a bridging ligand; Y is oxygen or sulfur;
1, 2 and n = 0, -1, -2, -3. Preferable examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyanate Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. In the present invention, an iridium compound may be further used in combination. As the iridium compound, a hexacoordinate complex represented by the above formula is preferable.

Specific examples of the transition metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl _5] ^-2 2. [RuCl ₆ ] ^-3 3. [Ru (NO) Cl _5] ^-2 4. [RhCl ₆ ] ^-3 5. [Ru (H ₂ O) Cl _5] ^-2 6. _{[Ru (NO) (H 2 O} ) Cl 4 ] ^-1 7. [Re (NO) Cl ₅ ] ^-2 . [Os (NO) Cl ₅ ] ^-2 9. [Ir (NO) Cl ₅ ] ^-2 10. [Ir (H ₂ O) Cl ₅ ] ^-2 11. [Re (H ₂ O) Cl ₅ ] ^-2 12. [RhBr ₆ ] ^-2 13. [Os (NS) Cl (SCN) ₄ ] ^-2 . [ReCl ₆ ] ^-3 15. [IrCl ₆ ] ^-3 16. [Re (NS) Cl ₄ (SeCN)] ^-2

In order to incorporate the above metal complex into silver halide, it can be added during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 1.times.10.sup.- ⁶ mol, preferably 1.times.10.sup.- ^{6 to} 5.times.10.sup.- ⁴ mol, and more preferably.times.1 mol per mol of silver halide. 10 ^-6 to 2
× 10 ^-4 mol. The above transition metals may be used in combination. There is no particular limitation on the distribution of the transition metal in the silver halide grains, but it is preferable that the transition metal be present more outside the grains.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is silver chlorobromide or silver chloroiodobromide comprising at least 90 mol% of silver chloride. An increase in the ratio of silver bromide or silver iodide is not preferable because the safelight safety in a bright room deteriorates or γ decreases.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. A specific example is U.S. Pat.
8,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a first tin salt, an amine salt, formamidinesulfinic acid, a silane compound and the like can be used.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the region of 380 nm to 600 nm may be used. These dyes are added to the emulsion layer depending on the purpose, or added to the upper part of the silver halide emulsion layer, that is, the specific photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support, and fixed. It is preferable to use them. Examples of the ultraviolet absorber include a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound,
Benzoxazole compounds and UV absorbing polymers can be used. Specific examples of the ultraviolet absorbent include U.S. Pat. Nos. 3,533,794, 3,314,794, 3,352,681, JP-A-46-2784, and U.S. Pat. 3,707,375,
No. 4,045,229, No. 3,700,455, No. 3,499,762, West German Patent Application Advertising 1,547,
No. 863 and the like. Different by the molar extinction coefficient of the UV absorber, but is added in an amount of usually ^{10 -2 g / m 2 ~1g /} m 2. Preferably it is 20 mg to 500 mg / m ² .

The safelight dye preferably reduces the sensitivity in the photosensitive region of 400 nm or more in the inherent photosensitive wavelength region of the silver halide emulsion.
Dyes having an absorption maximum at 0 nm are preferably used. There is no special limitation on the chemical structure of the dye, oxonol dye,
Although hemioxonol dyes, merocyanine dyes, cyanine dyes, azo dyes, arylidene dyes and the like can be used,
Water-soluble dyes are useful in terms of eliminating residual color after treatment. Specifically, for example, US Pat. No. 2,274,782
Pyrazolone oxonol dyes described in US Pat. No. 2,956,879, diarylazo dyes described in US Pat. Nos. 2,956,879, and US Pat. Nos. 3,423,207 and 3,384,48.
No. 7, styryl dyes and butadienyl dyes, US Pat. No. 2,527,583, merocyanine dyes,
U.S. Pat. Nos. 3,486,897 and 3,652,2
No. 84, No. 3,718,472, merocyanine dyes and oxonol dyes described in U.S. Pat.
No. 61, enamihemiooxonol dyes described in
No. 1-3623, arylidene dyes described in JP-A-52-20822, Japanese Patent Application Nos. 60-54383 and 60-5883.
No. 21306, No. 60-117456, No. 60-17
No. 8324, bis-type dyes and British Patent 584;
No. 609, No. 1,177,429, JP-A-48-8
No. 5130, No. 49-99620, No. 49-1144
20, U.S. Pat. Nos. 2,533,472 and 3,1
No. 48,187, No. 3,177,078, No. 3,
No. 247,127, 3,540,887, 3,575,704, and 3,653,905. The dye is preferably added in an amount of 10 mg to 400 mg per 1 m ² of the light-sensitive material, and particularly preferably in the range of 20 mg to 300 mg.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the corresponding places shown below can be preferably used. Item 1) Nuclear nucleation accelerators From page 13, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536, the general formulas (II-m) to (II-p) ) And compounds II-1 to II-22, and compounds described in JP-A-1-179939. 2) Surfactant, antistatic Japanese Patent Application Laid-Open No. 2-1236, page 9, upper right column, line 7 or the lower agent, right lower column, line 7, and JP 2-185542, page 2 lower left column, line 13 From the eye, on page 4, lower right column, line 18; 3) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, furthermore, JP-A-1-237538. Thiosulfinic acid compounds described in the official bulletin. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 6) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, line 15; 7) Hardener JP-A-2-103536, page 18, upper right column, 5th line to 17th line. 8) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 9) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-18832. Hereinafter, the present invention will be described in detail with reference to Examples.

[0170]

【Example】

Example 1 (Emulsion A) In a gelatin aqueous solution containing 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (5 × 10 ⁻³ mol per mol of silver) kept at 40 ° C. 4 × 10 ^-5 mol of (NH ₄ ) ₂ Rh (H ₂ O) C per mol of silver nitrate aqueous solution and silver
l Sodium chloride aqueous solution containing ₅ is added simultaneously in 7 minutes,
By controlling the potential during this time to 95 mV, 0.12 μm of core particles was prepared. Thereafter, 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh per mol of silver nitrate aqueous solution and silver
Cubic silver chloride grains having an average grain size of 0.15 μm were prepared by simultaneously adding an aqueous sodium chloride solution containing (H ₂ O) Cl ₅ for 14 minutes and controlling the potential during the addition to 95 mV. (Emulsion B) 4-hydroxy-6-methyl-1,3,3
Using 5,6-cyclopentane-4-hydroxy-1,3,3a, 7-tetrazaindene instead of a, 7-tetrazaindene, containing (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ Emulsion A was prepared in the same manner as for emulsion A except that the amount (both core and shell) was 6.5 × 10 ⁻⁵ mol per mol of silver.

(Preparation of Coated Sample) First Photosensitive Emulsion Layer The following additives were added to Emulsion A described above and coated so that the silver amount was 1.7 g / m ² (gelatin was 0.9 g / m ² ). . The hydrazine compound was added as shown in Table 2. Polyethyl acrylate latex (average particle size 0.05 μm) 0.6 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 30 mg / m ² Compound A 40 mg / m ² Compound B 10 mg / M ² Hardener (Compound C) 98mg / m ²

Second photosensitive emulsion layer On the first photosensitive emulsion layer, an emulsion layer similar to the first photosensitive emulsion layer except that the above-mentioned emulsion B was used, a silver amount of 1.3 g / m ² , gelatin 0 0.7 g / m ² . However, no hydrazine compound is contained.

Protective lower layer A protective lower layer having the following composition was further formed on gelatin at 0.55 g / m ^2.
It applied so that it might become. 1-hydroxy-2-benzaldoxime 15 mg / m ² Compound D 80 mg / m ² Compound E 10 mg / m ² Polyethyl acrylate latex (average particle size 0.05 μm) 0.28 g / m ²

Protective Upper Layer Further, a protective upper layer having the following composition was further coated with gelatin 0.95
g / m ² . Amorphous matting agent (silicon dioxide, average particle size 3.0 μm) 30 mg / m ² Spherical matting agent (PMMA, average particle size 2.7 μm) 30 mg / m ² Liquid paraffin gelatin dispersion 50 mg / m ² N-perfluorooctane Sulfonyl-N-propyl glycine potadium 5 mg / m ² Sodium dodecylbenzenesulfonate 10 mg / m ^{2 To} this protective upper layer, the solid disperse dye of the present invention and a comparative water-soluble dye were added as shown in Table 2.

[0175]

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Comparative water-soluble dye

[0177]

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Support A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was used as the support and the first and second subbing layers having the following composition were applied to both surfaces. <First layer of undercoat layer> Core-shell type vinylidene chloride copolymer- 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25〃 Polystyrene fine particles (average particle size 3μ) 0.05〃 Compound- 1 0.20〃 Colloidal silica (Sonotex ZL: particle size 70-100 mμ, manufactured by Nissan Chemical Co., Ltd.) 0.12〃 Add water 100〃 Add 10% by weight of KOH to adjust pH = 6. The coating solution was dried at a drying temperature of 180 ° C. for 2 minutes and the dried film thickness was 0.1 mm.
It was applied to 9 μm.

<Second layer of undercoat layer> Gelatin 1 g Methylcellulose 0.05−２ Compound-2 0.02〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03〃 Compound-3 3.5 × 10 ⁻³ {acetic acid 0.2} water was added and 100 μl This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes to a dry film thickness of 0.1 μm.

[0180]

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Then, the following conductive layer and back layer were simultaneously coated on the opposite side of the support. Conductive layer SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 77 {compound-67} sodium dodecylbenzenesulfonate 10 {dihexyl-α -Sodium sulfosuccinate 40 {sodium polystyrene sulfonate 9}

Back layer Gelatin (Ca ⁺⁺ content: 30 ppm) 2.82 g / m ² Fine particles of polymethyl methacrylate (average particle size: 3.4 μ) 54 mg / m ² Compound-6 33 {Compound-740} Compound-840 〃 Compound-980 化合物 Compound-10 120 ナ ト リ ウ ム Sodium dodisylbenzenesulfonate 75 ナ ト リ ウ ム Sodium dihexyl-α-sulfosuccinate 20 〃 Compound-II 5 ナ ト リ ウ ム Sodium sulfate 50 ナ ト リ ウ ム Sodium acetate 85 〃 1,2-bis (vinylsulfonyl Acetamide) ethane 150

[0183]

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[0184]

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The evaluation was performed by the following test methods. (Photo characteristics 1) Photo characteristics 1 is Dainippon Screen Co., Ltd.
After exposing through an optical wedge with a light-making room printer P-627FM, use a FG-680A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) at 38 [deg.] C.
0 "processing. The fixing solution used was GR-F1. The practical sensitivity was 50% halftone dot area by the above printer using a manuscript as shown in FIG. 1 of JP-A-58-190943. The value of Sample 1 was defined as 100 as the relative value of the reciprocal of the appropriate exposure amount so as to provide a halftone dot area of 50% on the sample, and the practical skill Dm is the maximum blackening density when the above appropriate exposure amount was given. The processing is the same as described above.

(Photo Characteristics 2) A running experiment was performed using the sample prepared above. Running conditions are 2 per day
30 sheets of each film of large paper size (50.8 × 61.0 cm), which has been blackened to 0% (2 out of 10 exposed), are run for 6 days and then run for 1 day. I went there. Replenishment amount is 75ml for development and 100ml for fixing
Met. Using each developer after the running, evaluation was made under the same conditions as in photographic characteristics 1.

(Image quality of extracted characters) The image quality of extracted characters was tested by using the above-mentioned printer using an original as shown in FIG. 1 of JP-A-58-190943. (The processing is the same as that of the photographic characteristic 1.) Here, the blank character image quality 5 means that a halftone dot area of 50% is obtained by using a document as shown in FIG. This is an image quality in which a character having a width of 30 μm is reproduced when a proper exposure is performed, which is a very good quality of a blank character. On the other hand, when the same proper exposure as that of the blank character quality 1 is given, 150
It is a poor character quality that cannot be said to be an image quality that can only reproduce characters having a width of μm or more, and ranks 4 and 2 are provided between 5 and 1 in sensory evaluation. Three or more is a practical level.

(Safelight Safety) In order to evaluate the safelight safety of each sample, a UV cut fluorescent lamp (FLIR-40SW-DLX-NU / M, Toshiba Corporation) was used.
After being left under Lux for 2 to 60 minutes, it is developed with running developers 1 to 4 in the same manner as in the photographic characteristics 2 described above,
The limit irradiation time at which the fog value starts to increase was determined.

(Color reversibility) The term "color reversibility" means that when the processed film is stored (colorless and transparent), the actual (unexposed) portion is colored. Developers 1-4 after running as in the above-mentioned photographic characteristics 2 without exposure as a forced test of recoloring
, And then subjected to a heat treatment at 50 ° C. and 80% RH 3d. Five levels were evaluated, 5 was the best level without any recoloring, 1 was the worst level with remarkable recoloring, and was assigned a rank of 4-2 in sensory (visual) evaluation. Three or more is a practical level.

Next, the composition of the developer is shown below. Potassium hydroxide 90.0 g Sodium hydroxide 8.0 g Disodium ethylenediaminetetraacetate 1.0 g Sodium metabisulfite 65.0 g Potassium bromide 10.0 g Hydroquinone 55.0 g 5-Methylbenzotriazole 0.40 g N-methyl-p -Aminophenol 0.50 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium 0.30 g 3- (5-Mercaptotetrazole) benzenesulfonic acid sodium 0.20 g N-n-butyl-diethanol-amine 14.0 g N, N -Dimethylamino-6-hexanol 0.20 g Sodium toluenesulfonate 8.0 g 5-Sulfosalicylic acid 45.0 g Potassium hydroxide is added, and water is added to make 1 liter, and the pH is adjusted to 11.9. 1 liter Based on this developing solution formulation, as shown in Table 1, developing solutions 1 to 4 to which the compound of the general formula (I) of the present invention was added were prepared.

[0191]

[Table 1]

[0192]

[Table 2]

As is clear from Table 2, the developer (N
o. 2-4), the actual skill Dm in photographic characteristic 2
, The increase in practical skill sensitivity is small, and the processing running property is greatly improved. Further, fog with respect to the safelight light hardly occurs, and the safelight safety is improved.
When the solid disperse dye of the present invention is used, the quality of a blank character is remarkably improved.

Example 2 A nucleation promoting agent was added as shown in Table 4 in place of compound D of the protective lower layer of Example 1, and a hydrazine compound added to the first photosensitive emulsion layer and added to the protective upper layer Samples were prepared in the same manner as in Example 1 except that the dye of the present invention or a comparative dye was added as shown in Table 4. This sample was subjected to the same test as in Example 1. However, the developing solution was developed using the following formulas 5 to 8, and the replenishment amounts of the photographic characteristics 2 were 50 ml for development and 75 ml for fixing per the whole.

Next, the composition of the developer is shown below. Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sulfonic acid 0.15 g sodium hydroxide Add potassium hydroxide, add water to make 1 liter, and adjust the pH to 10.5. 1 liter Based on the formulation of the developing solution, developing solutions 5 to 8 to which the compound of the general formula (I) of the present invention was added as shown in Table 3 were prepared.

[0196]

[Table 3]

[0197]

[Table 4]

Table 4 also shows that the developer of the present invention (No.
When 8) is used, the fluctuation of the practical skill Dm and the practical sensitivity of the photographic characteristics 1 and 2 is small, and the processing running performance is greatly improved. Also, safelight security is improved. When the solid disperse dye and the developing solution of the present invention are used, the image quality of blank characters is excellent, and the color reproducibility is also good.

Example 3 Example 2 was changed with the following changes.
A sample was prepared in the same manner as described above. Changes: Emulsion A (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added in an amount of 4 × 10 ⁻⁶ mol per mol of silver in both the core and the shell. Emulsion B (NH ₄ ) ₂ Rh (H ₂ core the amount of O) Cl _5, per mol of silver 7 × 10 ^-6 mol hydrazine compound shell both nucleation accelerator and, the dyes of the present invention or the comparative was added as shown in Table 5.

[0200]

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This sample was subjected to the same test as in Example 2. However, between the light source at the time of exposure and the sample, Mitsubishi Rayon Co., Ltd. Dialite P-1003 mm thickness (393 mm)
Exposure was performed by inserting a filter having a transmittance of 50% in nm and absorbing light on the shorter wavelength side and transmitting light on the longer wavelength side. (This means that the exposure was performed with light having a wavelength of 370 nm or more.) In addition, for a safelight safety evaluation, instead of a UV cut fluorescent lamp, Toshiba Corporation's white fluorescent lamp (FL40SW) was used instead of Fuji. The test was carried out under 400 Lux using a film covered with a sharp cut filter SC-42 manufactured by Photo Film Co., Ltd.

[0202]

[Table 5]

As is clear from Table 5, when the developing solution of the present invention (Nos. 6 to 8) is used, the fluctuation of the practical skill Dm is small, and the processing running property is good. Safelight safety is also improved. When the solid disperse dye and the developing solution of the present invention are used, the quality of blank characters and the reproducibility are good.

Example 4 In Example 3, (NH ₄ ) ₂ R contained in emulsions A and B
Instead of h (H ₂ O) Cl ₅ , K ₂ Ru (NO) Cl ₅ was added to Emulsion A for each of silver 1
5 × 10 ^-6 mol per mol, 9 × 1 per mol silver in emulsion B
0 ^-6 mol is contained, otherwise it creates a similarly samples as in Example 3, was subjected to similar evaluation. Even when the heavy metal compound contained in the emulsion was changed, the same effect as in Example 3 was obtained.

Example 5 In place of compound D of the protective lower layer of Example 1, compound (A-54) as a nucleation promoting agent was added at 3 × 10 ^-4 mol / m ² ,
1 × 10 ⁻⁴ mol / m ² of the compound (II-73) was added as a hydrazine compound to be added to the first photosensitive emulsion layer, and the solid disperse dye of the present invention, an organic desensitizer, and a comparative compound were added to the protective upper layer. Was added as shown in Table 5 except that a sample was prepared in the same manner as in Example 1. This sample was subjected to the same test as in Example 1. Furthermore, the following tests of safelight safety before and after exposure were also performed. However, the developing process was carried out using the developing solutions 5 to 8 shown in Example 2, and the replenishment amounts of the photographic characteristics 2 were 50 ml for development and 75 ml for fixing. Safelight safety test after exposure After exposing through an optical wedge with the printer used for photographic characteristics 1, 400 Lu of safelight UV cut fluorescent lamp (Toshiba Corporation FLR-40SW-DLX-NU / M)
After exposure for 1 hour under x, the same treatment was performed. Safelight safety test before exposure The unexposed sample was exposed to the same safelight for 1 hour, then exposed similarly, and immediately developed.

[0206]

[Table 6]

As is clear from Table 6, the developer (N
o. Using 6 to 8), the practical skill Dm in photographic characteristics 2
, High performance, little increase in sensitivity, and greatly improved processing running performance. Further, fogging to safelight light hardly occurs. When the organic desensitizer of the present invention is used, fogging hardly occurs and safelight safety is improved. When the solid disperse dye of the present invention is used alone or in combination with an organic desensitizer having a water-soluble group (D-1- (9)),
The image quality of a blank character is remarkably improved, and the color reproducibility is also improved when processed with the developing solution of the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI G03C 1/83 G03C 1/83 5/30 5/30 (56) References JP-A-63-47755 (JP, A) JP-A-63-47755 JP-A-4-333384 (JP, A) JP-A-2-300747 (JP, A) JP-A-5-165149 (JP, A) JP-A-63-103235 (JP, A) JP-A-6-508226 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 5/29 G03C 1/06

Claims (3)

(57) [Claims] 1. A silver halide emulsion comprising silver halide grains having a silver chloride content of 90 mol% or more and containing at least 1 × 10 ^-6 mol of a rhodium, ruthenium, rhenium or osmium compound per mol of silver. After a silver halide photographic material comprising a hydrazine compound in the emulsion layer or another hydrophilic colloid layer is image-exposed, (1) 0.2 to 0.75 mol / l (2) 0.001-0.06 mol / liter of 1-phenyl-3-pyrazolidone or p-aminophenol auxiliary developing agent, (3) 0.3-1.2 mol (4) containing a compound represented by the following general formula (I), wherein the concentration ratio of the compound represented by the general formula (I) to the dihydroxybenzene-based developing agent is 0.03 to A .12, an image forming method characterized in that pH is developed with a developing solution is 9.0 to 12.0. General formula (I) In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Is a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group,
Sulfoalkyl group, an amino group, an aminoalkyl group, or represents an alkyl group or an aryl group, or, by combining P and Q together, R _1, two vinyl carbon atom to which R ₂ is substituted with Y is substituted Represents a group of atoms forming a 5- to 8-membered ring together with the carbon atoms. Y is = 0 or = NR ₃
Represents R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. 2. The image forming method according to claim 1, wherein the hydrophilic colloid layer other than the photosensitive silver halide emulsion layer contains at least one dye solid-dispersed in fine particles. 3. A hydrophilic colloid layer other than the photosensitive silver halide emulsion layer contains at least one dye dispersed in fine particles in a solid state, and the emulsion layer or the other hydrophilic colloid layer contains an organic dye. The image forming method according to claim 1, wherein at least one kind of a sensitizer is contained.