JPH0777783A - Image forming method - Google Patents

Abstract

PURPOSE:To provide an image forming method capable of obtaining a high contrast photographic image by using a developer high in environmental safety. CONSTITUTION:A silver halide photosensitive material containing a hydrazine derivative and a redox compound releasing a development suppressing agent by oxidation is treated with a developer containing a compound expressed by a formula as a developing main chemical after exposure. In the formula, each of R1 and R2 isohydroxyl group or the, like, each of P and Q is hydroxyl group or the like or a group which can form a ring by bonding, Y is oxygen or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly to an image forming method for developing an ultrahigh contrast image with a developing solution containing no dihydroxybenzene type developing agent. Is.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting super-high gradation (especially γ of 10 or more) is provided in order to improve reproduction of continuous tone images or line images by halftone dot images. is necessary. As a method for obtaining high-contrast photographic characteristics, a lithographic development method utilizing a so-called "infectious development effect" has been used for a long time, but it has a drawback that the developer is unstable and difficult to use. There is a demand for an image forming system which can be developed with a processing liquid having good storage stability to obtain photographic characteristics of ultra-high contrast, and one of them is US Pat. No. 4,166,74.
No. 2, No. 4,168,977, No. 4,221,8
No. 57, No. 4,224,401, No. 4,243,
No. 739, No. 4,269, 922, No. 4,27.
No. 2,606, No. 4,311,781, No. 4,3
No. 32, 878, No. 4,618,574, No. 4,634,661, No. 4,681,836, No. 5,650,746 and the like are disclosed. These are surface latent image type silver halide photographic light-sensitive materials to which a hydrazine derivative is added, and stable MQ having a pH of 11.0 to 12.3.
Alternatively, the system is a system for obtaining a super-high contrast negative image in which γ exceeds 10 by processing with a PQ developer. According to this method, super-high contrast and high-sensitivity photographic characteristics are obtained, and a high concentration of sulfite in the developer is obtained. Can be added, the stability of the developer against air oxidation is dramatically improved as compared with the conventional lith developer.

Also in the light-sensitive material for a bright room used in the plate collecting and returning process, for example, if the halftone dot original and the line drawing original are faithfully overlapped on the original, an ultrahigh contrast image forming method is required. A system using hydrazine is also necessary for this purpose.
-235938, 62-235939, 63-
104046, 63-103235, 63-2
No. 96031, No. 63-314541, No. 64-13
No. 545, etc. are disclosed. However, these developing systems are systems using a dihydroxybenzene-based developing agent as a developing agent, and have some disadvantages from the ecological and toxicological points of view. For example, hydroquinone is an undesired component due to its allergic effect, and 1-phenyl-3-pyrazolidones are poor biodegradable components. In addition, high concentration of sulfite has high COD
(Chemical oxygen demand) is shown.

On the other hand, it is well known that enediols such as ascorbic acid function as a developing agent, and is attracting attention as a developing agent free from the above ecological or toxicological problems. For example, U.S. Pat. No. 2,668,54
9 and 3,826,654 at least pH 1
It is said that image formation is possible under a highly alkaline condition of 2 or more. However, it is impossible to obtain a high-contrast image by these image forming methods. Some attempts have been made to increase the contrast in a developing system using ascorbic acid. For example, Zwicky says that a type of squirrel effect appears when ascorbic acid is used as the only developing agent (J.Phot.Sci. 27, 185 (1
979)), and the contrast was considerably lower than that of the hydroquinone developing system. Also, US Patent No. 8
Nos. 96,022 and JP-B-49-46939 disclose a system in which a diquaternary ammonium salt and ascorbic acid are used in combination, but there is almost no contrast enhancing effect even though there is a development accelerating effect. In addition, JP-A-3-2497
No. 56 and No. 4-32838 describe the combined effect of ascorbic acid and a quaternary salt, but the contrast of the obtained image is not sufficient. Furthermore, JP-A-5-88306
No. 1 ascorbic acid as the sole developing agent, pH 1
Although it is said that a high contrast can be obtained by keeping it at 2.0 or more, there is a problem in the stability of the developing solution. An example in which a special developer containing ascorbic acid and a specific hydrazine derivative as a main component can be used to form a developer with high sensitivity and low stain and fog (US Pat. No. 3,730,
No. 727), but no mention is made of improvement in contrast. WO93 / 11456, US5
No. 236816 discloses an example of processing a light-sensitive material containing a hydrazine derivative with a developer using ascorbic acid as a main agent. However, this method is related to original reproducibility which is important in a light-sensitive material for graphic arts. It wasn't enough and needed further improvement.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to use a developer which has a high contrast image which can realize excellent original reproducibility, which is required in the field of graphic arts, and which does not pose a problem to the ecosystem and working environment. It is to provide a novel image forming method obtained by the above.

[0006]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least the emulsion layer or another hydrophilic colloid layer. One layer contains at least one hydrazine derivative, and at least one layer of the emulsion layer or other hydrophilic colloid layer contains at least one redox compound capable of releasing a development inhibitor by being oxidized. The characteristic silver halide photographic light-sensitive material is developed with a developer containing substantially no dihydroxybenzene-based developing agent as a developing agent and containing a developing agent represented by the following general formula (I). Was achieved by the following image forming method. General formula (I)

[0007]

[Chemical 6]

In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an 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 are mutually It represents an atomic group forming a 5- to 7-membered ring together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = O 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.

Next, the developing solution used in the present invention will be described. The developer of the present invention contains substantially no dihydroxybenzene-based developing agent as described above, and the main developing agent is the compound represented by the general formula (I). The developer of the present invention preferably contains a 1-phenyl-3-pyrazolidone type auxiliary developing agent and / or a p-aminophenol type auxiliary developing agent as an auxiliary developing agent.

The compound of formula (I) which is the developing agent of the present invention will be described in detail. In the general formula (I),
R ₁ and R ₂ each include a hydroxy group, an amino group (having a substituent having an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-butyl group, or a hydroxyethyl group as a substituent). ), An acylamino group (acetylamino group, benzoylamino group, etc.), an alkylsulfonylamino group (methanesulfonylamino group, etc.), an arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.),
It represents an alkoxycarbonylamino group (such as a methoxycarbonylamino group), a mercapto group, and an alkylthio group (such as a methylthio group and an ethylthio group). 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 represent a hydroxy group, a carboxy 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 an atomic group which is bonded to each other to form a 5- to 7-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y.

Examples of the 5- to 7-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 preferred examples of the 5- or 6-membered ring include
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is a group composed of ═O or ═N—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), carboxy. Represents an alkyl group (eg carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11]

[0019]

[Chemical 12]

Of these, ascorbic acid and erythorbic acid (stereoisomers) are preferred. As a general range of the amount of the compound of the general formula (I) used,
The amount is 5 × 10 ⁻³ mol to 1 mol, and particularly preferably 10 ⁻² mol to 0.5 mol, per liter of the developer.

1-Phenyl-3 as an auxiliary developing agent
Examples of pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxylmethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-p
-Aminophenyl-4,4 dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based auxiliary developing agent, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2- There are methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.
When the combination of the compound represented by the general formula (I) of the present invention and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the latter is usually added in an amount of 10 ⁻³ mol / liter to 0.1. It is preferably used in an amount of mol / liter, more preferably 10 ⁻³ mol / liter to 0.06 mol / liter.

In the present invention, the term "substantially free of dihydroxybenzenes" means that the concentration of the dihydroxybenzenes in the developing solution is taken relative to the amount of the compound of the general formula (I) or the auxiliary developing agent. Not enough (eg 5 × 1
^0-4 mol / liter or less). The developer of the present invention preferably contains no dihydroxybenzenes.

Sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite and sodium formaldehyde bisulfite may be added to the developer of the present invention as preservatives.
The sulfite is used at 0.01 mol / l or more. If used in a large amount, it will dissolve silver halide emulsion grains and cause silver stains. Moreover, since it also causes an increase in COD (chemical oxygen demand), the amount added should be minimized.

The pH of the developer used in the development processing of the present invention is preferably in the range of 10.0 to 12.0. pH is 1
When it is 2.0 or more, stains and black spots in the non-image area increase rapidly, which is not preferable. Further, if the pH is 10.0 or less, sufficient contrast cannot be obtained. Alkali agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. The developer of the present invention includes saccharides (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid) described in JP-A-60-93433.
A pH buffering agent such as silicate, sodium triphosphate, potassium triphosphate can be used. The concentration of the buffer is preferably 0.3 mol / liter or more. Boron compounds such as boric acid and sodium metaborate may react with the compound of the present invention represented by the general formula (I) to be inactivated, which is not preferable.

Development inhibitors such as potassium bromide and potassium iodide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, and indazoles such as 5-nitroindazole. Compounds, benzimidazole compounds such as sodium 2-mercaptobenzimidazole-5-sulfonate, and antifoggants such as benztriazole compounds such as 5-methylbenztriazole, Research Disclosure Volume 176. No. 17643, Item XXI (December issue, 1978). It may also contain amine compounds described in U.S. Pat. No. 4,269,929, JP-A-61-267759 and Japanese Patent Application No. 1-291818. Further, a color tone agent, a surface active agent, a hardener, etc. may be contained if necessary. The developer of the present invention includes European Patent Publication 13
6582, British Patent No. 958678, US Patent No. 3
Amino compounds such as alkanolamines described in JP-A No. 232761 and JP-A No. 56-106244 can be used for the purpose of promoting development and increasing contrast.

The fixer used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 4.2.
Has 7.0. Sodium thiosulfate as a fixing agent,
There are ammonium thiosulfate and the like, but ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / liter. The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum. Tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more in the fixing solution. It is effective that these compounds contain 0.005 mol / liter or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid) pH adjusters (eg, sulfuric acid, ammonia), chelating agents having a water softening ability may be included in the fixer, if desired. Surfactants, wetting agents, fixing accelerators, and compounds described in JP-A-62-78551 may be included. Examples of the fixing accelerator include thiourea derivatives described in JP-A Nos. 45-35754, 58-122535, and 58-122536, alcohols having a triple bond in the molecule, and U.S. Pat.
Examples thereof include thioether compounds described in JP-A No. 59, and compounds described in JP-A-2-44355 may be used.
Further, as the dye elution accelerator, the compounds described in JP-A 64-4739 can be used.

In the development processing method of the present invention, development,
After the fixing step, it is treated with washing water or a stabilizing solution and then dried. 3 per 1 m ^{2 of} silver halide light-sensitive material
It is also possible to treat with a replenishing amount of less than or equal to 1 liter (zero, that is, including a washing with water) of washing water or a stabilizing solution.
That is, not only water saving processing becomes possible, but also piping for installing the automatic processing machine can be eliminated. As a method of reducing the replenishment amount of flush water, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known. When this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is processed in a gradually cleaning direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water. When washing with a small amount of water, the method described in JP-A-63-1 is used.
It is preferable to provide a washing tank for a squeeze roller and a cross over roller as described in Nos. 8350 and 62-287252. Further, various oxidizers may be added or filter-filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. In the above water-saving treatment or pipe-less treatment, it is preferable to apply antifouling means to the washing water or the stabilizing solution.

As an anti-fungus means, Japanese Patent Laid-Open No. 60-263
UV irradiation method described in No. 939, 60-26394
Method using magnetic field described in No. 0, Ibid.
A method for producing pure water using the ion exchange resin described in JP-A No. 62-115154 and JP-A No. 62-15395.
No. 2, No. 62-220951, No. 62-209532
It is possible to use the method using the antibacterial agent described in No.
Furthermore, LFWest, "Water Quality Criteria" Photo.
Sci. & Eng., Vol.9 No.6 (1965), MWReach, "Microbi
ological Growths in Motion- picture Processing ", SM
PTE Jounal Vol.85 (1976), RODeegan, "Photo Proces
sing Wash Water Biocides ", J. Imaging Tech., Vol.10,
No. 6 (1984), and JP-A-57-8542 and 57-
56143, 58-105145, 57-13.
No. 2146, No. 58-18631, No. 57-9753
No. 0, No. 57-157244 and the like can be used in combination with antibacterial agents, antifungal agents, surfactants and the like. In addition, RTKreiman can be used as a washing bath or stabilizing bath.
Research Disclosure No. 2, isothiazolidine compounds described in J. Imaging Tech., 10 (6) p.242 (1984).
The compounds described in Vol. 05, No. 20526 (1981, No. 4) and the like can be used together as a bacteriostatic agent (Microbiocide).
In addition, compounds such as those described in "The Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) May be included.

When rinsing with a small amount of rinsing water in the method of the present invention, it is also preferable to adopt a rinsing step configuration as described in JP-A-63-143548. Furthermore, some or all of the overflow from the washing or stabilizing bath caused by supplementing the washing or stabilizing bath with antifungal means by the method of the present invention depending on the treatment is disclosed in JP-A-60-
As described in No. 235133, it can also be used for a processing liquid having a fixing ability which is a processing step before that. In the development processing of the present invention, the development time is 5 seconds to 3 seconds.
Min, preferably 8 seconds to 2 minutes, the development temperature is 18 ° C
-50 degreeC is preferable, and 24 degreeC-40 degreeC is more preferable.

The fixing temperature and time are about 18 ° C. to about 50.
It is preferably 5 seconds to 3 minutes at ° C, and more preferably 6 seconds to 2 minutes at 24 ° C to 40 ° C. Within this range, the temperature and time in water washing (or stabilization) capable of sufficiently fixing and eluting the sensitizing dye to the extent that no residual color is generated are preferably 5 to 50 ° C. and 6 seconds to 3 minutes. 15-40 °
C, 8 seconds to 2 minutes are more preferable. The light-sensitive material which has been developed, fixed and washed (or stabilized) is squeezed out of washing water, that is, dried through a squeeze roller. The drying is performed at about 40 ° C to 100 ° C, and the drying time may be appropriately changed depending on the ambient conditions, but it is usually about 4 seconds to 3 minutes, particularly preferably 40 ° C to 80 ° C and about 5 ° C. Second to 1
Minutes. When developing for 100 seconds or less in dry to dry, a roller made of a rubber material as described in JP-A-63-151943 is used as the roller at the outlet of the developing tank in order to prevent development unevenness peculiar to rapid processing. And the discharge flow rate for stirring the developer in the developing tank is 10 m / min or more as described in JP-A-63-151944, and further, JP-A-63-264758. As described in No. 6, it is more preferable to stir more strongly than during standby at least during the development process. For further rapid processing, it is more preferable that the rollers of the fixing tank are opposed rollers in order to increase the fixing speed. By configuring with opposed rollers, the number of rollers can be reduced,
The processing tank can be made smaller. That is, the automatic processing machine can be made more compact.

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, and particularly is a straight chain, 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 an aryl group. Preferred as R ₁ is an aryl group, and particularly preferred is one containing a benzene ring. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include, for example, 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. Base,
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
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 the like, and as a preferable substituent, an alkyl group (preferably Are those having 1 to 20 carbon atoms, aralkyl groups (preferably those having 7 to 30 carbon atoms), alkoxy groups (preferably those having 1 to 20 carbon atoms), and substituted amino groups (preferably having 1 to 20 carbon atoms). Amino group substituted with alkyl group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 3 carbon atoms)
Those having 0), ureido groups (preferably having 1 to 3 carbon atoms)
Those having 0), phosphoric acid amide groups (preferably having 1 carbon atom)
~ 30) and the like. These groups may be further substituted.

In the general 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). Including rings). G
_{When 1} is a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom and an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group). , Phenylsulfonylmethyl groups, etc.), aralkyl groups (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, etc.), and particularly hydrogen. Atoms are preferred. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

Most preferably, G _{1 in the} general formula (II) is a —CO— group. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms Examples thereof include those described in JP-A-63-29751. A hydrogen atom is most preferable as A ₁ and A ₂ .

R ₁ or R _{2 in} the general formula (II) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, and examples thereof include 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, JP-A-1
The thing described in No. 100530 is mentioned.

R ₁ or R _{2 in} the general formula (II) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
U.S. Pat. No. 4,459,347, JP-A-59-195233.
No. 59-202331, 59-201045
Issue 59-201046 Issue 59-201047
Issue 59-201048, Issue 59-201049.
No. 61-170733 and No. 61-270744.
No. 62-270948 and 63-234244.
No. 63-234245 and No. 63-234246.

Among the general formula (II), R₁Or R₂of
At least one has a ballast group or R₁Or R₂
At least one of them strongly adsorbs on the silver halide grain surface.
Have a radical or R₁Is a trialkylammonium group
Have or R₁Is an alkylthio group (cycloalkylthio group
Or containing an arylthio group, or R₂G in ₁
The carbon atom bonded to is an electron-withdrawing group (eg halogen
Atom, cyano group, nitro group, sulfonyl group, etc.)
Those that have been described are preferable.

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

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

[0050]

[Chemical 25]

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

[0053]

[Chemical 28]

[0054]

[Chemical 29]

[0055]

[Chemical 30]

[0056]

[Chemical 31]

[0057]

[Chemical 32]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent No. 2,011,
391B, JP-A-60-179734, and JP-A 62-2.
70948, 63-29751, 61-170.
No. 733, No. 61-270744, and European Patent No. 21.
7,310, 356,898, U.S. Pat.
86,167, JP-A-62-178246, 63.
-32538, 63-104047, 63-1
21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
245, 63-234246, 63-2945.
No. 52, No. 63-306438, No. 64-10233
, JP-A-1-90439, 1-100530,
1-105941, 1-105943, 1-
276128, 1-280747, 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,
No. 2-198442, No. 2-220042, No. 2-
221953, 2-221954, 2-302
Nos. 750 and 2-304550 can be used.

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

The hydrazine derivative of the present invention is 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 sorb or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or an oil such as diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved to mechanically emulsify. It is also possible to prepare and use a dispersion. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The redox compound capable of releasing the development inhibitor by being oxidized according to the present invention will be described. The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinone groups, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones, and more preferably hydrazines. The hydrazines used as the redox compound capable of releasing the development inhibitor by being oxidized in the present invention are preferably represented by the general formula (R-1), the general formula (R-2) and the general formula (R-3). Be done. The compound represented by formula (R-1) is particularly preferable.

In the formula, R ₁ represents an aliphatic group or an aromatic group. G ₁ is a -CO- group, a -COCO- group, a -CS- group,
_{-C (= NG 2 R 2)} - represents the group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2). G ₂ is a mere bond, —O— group, —S— group or —N (R ₂ ) —
Represents a group, R ₂ represents a group having the same definition as R ₁ or a hydrogen atom, and when plural R ₂ are present in the molecule, they may be the same or different. A ₁ and A ₂ are hydrogen atoms,
It represents an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. General formula (R-
In 1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or -CH ₂ CH (A ₄ )-(Time) _t -PUG
Represents A ₄ is a nitro group, a cyano group, a carboxyl group,
A sulfonyl group or -G ₁ -G ₂ -R ₁ (in this case, two -G ₁ -G ₂ -R ₁ in the molecule may. For be the same or different) represent. Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

General formulas (R-1), (R-2), (R-
3) will be described in more detail. General formula (R-
In 1), (R-2) and (R-3), the aliphatic group represented by R ₁ is preferably one having 1 to 30 carbon atoms, particularly straight chain or branched one having 1 to 20 carbon atoms. Alternatively, it is a cyclic alkyl group. This alkyl group may have a substituent. In the general formulas (R-1), (R-2) and (R-3), 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 an aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group and a substituted group. Amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group,
Examples thereof include a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, and a phosphoric acid amide group. Chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), aralkyl group (preferably having 7 to 30 carbon atoms), alkoxy group (preferably having 1 to 30 carbon atoms), substituted amino Group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably 2 to 4 carbon atoms)
0), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), phosphoric acid amide group (preferably having 1 to 40 carbon atoms) ) And so on.

General formulas (R-1), (R-2), (R-
As G ₁ in 3), a —CO— group and a —SO ₂ — group are preferable, and a —CO— group is most preferable. A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, —CH _{2
-CH (A 4) - (Time} ) t -PUG are preferred.

General formulas (R-1), (R-2), (R-
In 3), Time represents a divalent linking group and may have a timing adjusting function. The divalent linking group represented by Time represents a group capable of releasing PUG from Time-PUG released from the oxidized product of the redox mother nucleus through a reaction in one step or more steps. Tim
Examples of the divalent linking group represented by e include U.S. Pat. No. 4,248,962 (JP-A-54-145,135).
Releasing PUG by an intramolecular ring closure reaction of the p-nitrophenoxy derivative described in U.S. Pat.
310,612 (JP-A-55-53,330) and 4,358,525, which release PUG by an intramolecular ring closure reaction after ring cleavage; US Pat. No. 4,330,617. Nos. 4,446,216, 4,483,919, JP-A-59-121,328, and the like, acid anhydrides by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its analogs. Release of PUG with the formation of a product; US Pat. No. 4,40
9,323, 4,421,845, Research Disclosure No. 21,228 (December 1981)
U.S. Pat. No. 4,416,977 (JP-A-57-57).
135,944), JP-A-58-209,736,
No. 58-209,738, etc., which produces quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. 4,420,5
54 (JP-A-57-136,640) and JP-A-57.
-135,945, 57-188,035, 5
8-98,728 and 58-209,737, which release PUG from the γ-position of the enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle; JP-A-57-56, No. 837, which releases PUG by an intramolecular ring-closing reaction of an oxy group formed by electron transfer to a carbonyl group conjugated with a nitrogen atom of a nitrogen-containing heterocycle; U.S. Pat. No. 4,146,396. 52-90932), JP-A-59-93,442,
JP-A-59-75475, JP-A-60-249148
Releasing PUG with the formation of aldehydes described in JP-A No. 60-249149;
146, 828, 57-179, 842, 59
-O-COOCR _a R _b- PUG which releases PUG with decarboxylation of the carboxyl group described in -104,641;
(R _a and R _b represent a monovalent group) and release PUG with decarboxylation and subsequent formation of aldehydes; JP-A-60-7,429 Examples thereof include those releasing PUG with the formation of isocyanate; those releasing PUG by a coupling reaction with an oxidized product of a color developing agent described in US Pat. No. 4,438,193 and the like. Specific examples of these divalent linking groups represented by Time are described in JP-A-61-23.
6,549, Japanese Patent Application No. 63-98,803, Japanese Patent Application No. 2
It is also described in detail in, for example, No. -93487.

General formulas (R-1), (R-2), (R-
In 3) PUG is a development inhibitor. PUG has a heteroatom, the general formula (R-1) via the heteroatom,
It is bonded to the other part of the compound represented by (R-2) or (R-3). An example of a commonly known development inhibitor is, for example, "The Theory of the Photographic Process" by TH James.
Theory of the Photographic Process) "4th Edition, 19
1977, Macmillan, 396-39.
Page 9 and Japanese Patent Application No. 2-93,487, pages 56 to 69. These development inhibitors may have a substituent. Examples of useful substituents include mercapto group, nitro group, carboxyl group, sulfo group, phosphono group, hydroxy group, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group. , Acylamino group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, An acyloxy group, a carbonamido group, a sulfonamide group, a phosphonamido group, etc. are mentioned, and these groups may be further substituted.

The development inhibitor represented by PUG used in the present invention is preferably a compound that inhibits nucleation infectious development. Nucleating infectious development is a new development chemistry used in the image forming method of the Fuji Film GRANDEX system (Fuji Photo Film Co., Ltd. and Kodak Ultratec system (Eastman Kodak Co., Ltd.). This development chemistry is Ordinary development of exposed silver halide grains, as described in The Journal of the Photographic Society of Japan, Vol. 52, No. 5, 390-394 (1989) and "Journal of Photographic Science", Vol. 35, 162 (1987). Nucleating active species are generated based on the cross-oxidation between the developing process of the main agent and the oxidation product of the developing agent and the nucleating agent, and the surrounding unexposed to weakly exposed halogenation by the active species. 2 of nucleation and development process of silver particles
It consists of two processes. Therefore, the whole development process is
Since it consists of the sum of the normal development process and the nucleation development process, in addition to the conventional development inhibitor conventionally known as a development inhibitor, a compound that newly inhibits the nucleation-infectious development process has an inhibitory effect. It can be demonstrated. The latter is referred to herein as a nucleation development inhibitor. The development inhibitor represented by PUG used in the present invention is preferably a nucleation development inhibitor. As the compound acting as a nucleation development inhibitor, conventionally known development inhibitors are also effective, but particularly effective compounds include compounds having at least one or more nitro group or nitroso group, pyridine, pyrazine, Compounds having a nitrogen-containing heterocyclic skeleton such as quinoline, quinoxaline, or phenazine, particularly compounds having a 6-membered nitrogen-containing heteroaromatic skeleton, compounds having an N-halogen bond, quinones, tetrazoliums, amine oxides, azoxy compounds, Such compounds include coordination compounds having an oxidizing ability. Among them, a compound having a nitro group and a compound having a pyridine skeleton are particularly effective.

These nucleation development inhibitors may have a substituent, and the properties of the substituent, such as electron withdrawing property, electron donating property, hydrophobicity, hydrophilicity, charge, and adsorptivity to silver halide. It is possible to control various characteristics such as strength of development inhibition and easiness of diffusion by such properties. Examples of useful substituents are those listed above as examples of common development inhibitor substituents. Specific examples of these nucleation development inhibitors useful in the present invention are described in detail in JP-A-4-13639, 4-136840 and the like, as well as JP-A-4-136841 and Japanese Patent Application No. No. 15648, No. 3-70411, No. 3-7
It is also described as Ind in 0388. Further, as another series of nucleation development inhibitors, an adsorptive compound to a silver halide grain having an anionic charged group or a dissociative group capable of dissociating in a developing solution to generate anionic charge is also effective. .

The general formulas (R-1), (R-2) and (R
-3), R ₁ or Time is a ballast group or a general formula (R-1), (R-2), (R-3) commonly used in a non-moving photographic additive such as a coupler. A group that promotes the adsorption of the compound represented by the formula (1) to silver halide may be incorporated. The ballast group is an organic compound giving a molecular weight sufficient to prevent the compounds represented by the general formulas (R-1), (R-2) and (R-3) from substantially diffusing into another layer or the treatment liquid. The group is a group consisting of one or more of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the adsorption promoting group for silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (If the carbon atom next to the -SH group is a nitrogen atom, this It has the same meaning as a cyclic thioamide group in a tautomeric relationship, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benz Imidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oki A 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon such as sol, oxazoline, thiadiazole, oxathiazole, triazine and azaindene, and a heterocyclic quaternary group such as benzimidazolinium Examples include salt. These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent of R ₁ . Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0072]

[Chemical 33]

[0073]

[Chemical 34]

[0074]

[Chemical 35]

[0075]

[Chemical 36]

[0076]

[Chemical 37]

[0077]

[Chemical 38]

[0078]

[Chemical Formula 39]

[0079]

[Chemical 40]

[0080]

[Chemical 41]

[0081]

[Chemical 42]

[0082]

[Chemical 43]

[0083]

[Chemical 44]

[0084]

[Chemical formula 45]

[0085]

[Chemical formula 46]

[0086]

[Chemical 47]

[0087]

[Chemical 48]

[0088]

[Chemical 49]

As the redox compound used in the present invention, in addition to the above compounds, for example, JP-A-61-213,8 can be used.
No. 47, No. 62-260, 153, Japanese Patent Application No. 1-10
No. 2,393, No. 1-102, 394, No. 1-10
No. 2,395, No. 1-114,455, No. 1-290
No. 563, No. 2-62337, No. 2-64717,
No. 2-258927, No. 2-258928, No. 2-
258929, 3-15648, 3-7041
No. 1 and No. 3-70388 can be used. The method for synthesizing the redox compound used in the present invention is described in the above-mentioned materials, and for example, US Pat. No. 4,684,604, Japanese Patent Application No. 63-98,803.
U.S. Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
78, JP-A-49-129,536 and JP-A-56-15.
3, 336, 56-153, 342, etc.

The redox compound of the present invention is used in the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. . The redox compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving in dimethyl sulfoxide, methyl cellosolve and the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The redox compound of the present invention is added to a silver halide emulsion layer or other hydrophilic colloid layer. Further, it may be added to at least one of a plurality of silver halide emulsion layers. Although some constitutional examples are given, the present invention is not limited to these. Structural Example 1) A silver halide emulsion layer containing the redox compound of the present invention and a protective layer are provided on a support. These emulsion layers or protective layers may contain the hydrazine derivative of the present invention as a nucleating agent. Structural Example 2) A first silver halide emulsion layer and a second silver halide emulsion layer are sequentially provided on a support, and the first silver halide emulsion layer or the adjacent hydrophilic colloid layer is provided. , The hydrazine derivative, and the redox compound in the second silver halide emulsion layer or the adjacent hydrophilic colloid layer. Structure Example 3) In Structure Example 2), the order of the two emulsion layers is reversed. In the constitution examples 2) and 3), an intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the two photosensitive emulsion layers. Structural Example 4) A silver halide emulsion layer containing the hydrazine derivative is provided on a support, and the hydrophilic layer containing the redox compound is provided on the emulsion layer or between the support and the silver halide emulsion layer. Having an organic colloid layer. A particularly preferred configuration is configuration example 2) or 3).

The silver halide photographic light-sensitive material of the present invention comprises
Nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives, and hydroxylamine derivatives are preferably added to the silver halide emulsion layer or other hydrophilic colloid layers.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives. As the amine derivative, for example, JP-A-60-140,340, JP-A-62-50,829, JP-A-62-222,241, JP-A-62-250,439, JP-A-62-280,733,
63-124,045, 63-133,145.
No. 63-286,840 and the like. More preferably as an amine derivative,
Compounds having a group capable of adsorbing to silver halide described in JP-A-63-124,045, 63-133,145, 63-286,840 and the like, or described in JP-A-62-222,241 and the like. Compounds with 20 or more carbon atoms in total, US 4,97
No. 5,354, EP 458 P706A, etc., amine compounds having an ethylene group, JP-A-62-50.
The compounds described in No. 829 and the like can be mentioned. The onium salt is preferably a pyridinium salt, an ammonium salt or a phosphonium salt. Examples of preferable pyridinium salts include the compounds described in Japanese Patent Application No. 5-97866. Further, examples of preferable ammonium salts include JP-A Nos. 62-250,439 and 62-62.
-280,733 etc. can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,939 and JP-A-62-280.
The compound described in No. 733 etc. can be mentioned. Examples of the disulfide derivative include, for example, JP-A-61-19
The compounds described in No. 8,147 can be mentioned. As the hydroxymethyl derivative, for example, U.S. Pat. No. 4,698,956
No. 4,777,118, EP 231,850, JP-A-6
2-50,829 etc. can be mentioned, More preferably, it is a diarylmethanol derivative. As the acetylene derivative, for example, Japanese Patent Application Laid-Open No. 3-1
68735, the compound of Unexamined-Japanese-Patent No. 2-271351, etc. can be mentioned. Examples of the urea derivative include compounds described in JP-A-3-168736.

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

[0095]

[Chemical 50]

[0096]

[Chemical 51]

[0097]

[Chemical 52]

[0098]

[Chemical 53]

[0099]

[Chemical 54]

[0100]

[Chemical 55]

[0101]

[Chemical 56]

[0102]

[Chemical 57]

[0103]

[Chemical 58]

[0104]

[Chemical 59]

[0105]

[Chemical 60]

These compounds are optimally added depending on their kind.
1.0 x 1 per 1 mol of hydrazine compound, although the amount added is different
0^-2Mol ~ 1.0 x 10²Mole, preferably 1.0 x
10 ^-1Desirable to use in the range of 5.0 to 10 mol
Good These compounds are suitable water-miscible organic solvents, eg
For example, alcohols (methanol, ethanol,
Nole, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethy
Used by dissolving in sulfoxide, methyl cellosolve, etc.
You can In addition, the well-known emulsion dispersion
Depending on the method, dibutyl phthalate, tricresyl phos
Fate, glyceryl triacetate or diethyl
Oils such as phthalates, ethyl acetate and cyclohexano
Dissolve using a co-solvent such as solvent and mechanically emulsify the dispersion
Can also be created and used. Or solid dispersion method
Powders of these compounds by known methods
In a water ball mill, colloid mill, or ultrasonic
It can also be used in a dispersed manner.

Examples of useful nucleation development accelerators contained in the developing solution used in the present invention include, for example, JP-A-56-106244 and 61-267759.
No. 61-230145 and No. 62-211647.
And amine compounds described in JP-A-63-50247, benzyl alcohol derivatives described in JP-A-60-200250, and the like. As the nucleation development accelerator, a compound represented by the general formula (III) is preferable. Formula _{(III) R 11 -N (R} 22) in -R _{23 formula, R 21, R 22, R} 23 are each H-R _21, H-
N-octanol / water partition logarithm as R ₂₂ and HR ₂₃
It represents a substituted or unsubstituted alkyl group having a sum of (log P) values of 2.6 or more and less than 10.0. Furthermore lo
A compound in which the sum of the values of g P falls within the range of 3.0 or more and less than 8.0 is particularly preferable.

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 thereof include a sulfo group, an aryloxy group and an amino group. Regarding the value of the logarithm (log P) of the n-octanol / water partition coefficient, the calculation method is as follows: Substituent Constants Hofo Correlation Analysis in Chemistry and Biology For Correlation Analy
sis in Chemistry and Biology) Handbook of
Handbook of Chemical Property Estimation Metho
ds) and is defined in the present invention. log P
The value of is also obtained by this. Typical H below
The values of log P of -R ₂₁ , HR _22, and HR ₂₃ are shown.
Value of logarithm (log P) of n-octanol / water partition coefficient of HR ₂₁ , HR ₂₂ , HR ₂₃

[0109]

[Chemical formula 61]

[0110]

[Chemical formula 62]

Specific examples of the amino compound represented by the general formula (III) include those described in JP-A-3-67250, but the present invention is not limited thereto. The amino compound represented by the general formula (III), unlike other amino compounds, remarkably promotes high contrast with a small amount, but may cause silver stains due to its weak action as a solvent of silver halide. It has excellent performance of not having. The amino compound represented by the general formula (III) is preferably 0.01 to liter per liter of the developing solution.
It is used in the range of 0.30 mol / liter, but it is particularly 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), and when it is attempted to reduce the volume of the developing solution by concentrating the developing solution than when using it for convenience of storage and transportation, The amino compound of formula (III) may precipitate / precipitate. However, the following general formula (IV)
Alternatively, when the compound represented by (V) is used, even if the liquid is concentrated, it is possible to prevent the occurrence of such precipitation and precipitation, and thus it may be used. General formula (IV)

[0112]

[Chemical formula 63]

General formula (V)

[0114]

[Chemical 64]

Here, M represents a hydrogen atom Na, K or 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 represented by the general formula (IV) include p
-Sodium toluene sulfonate, sodium benzene sulfonate, sodium 1-hexane sulfonate 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 and sodium n-caprate. The amount of the compound represented by the general formula (IV) or (V) to be used varies depending on the amount of the amino compound of the general formula (III) to be used, but is usually 0.005 mol / liter or more, particularly preferably 0.
A suitable range is 03 mol / liter to 0.1 mol / liter. Further, the range of 0.5 to 20 mol is suitable for 1 mol of the amino compound of the general formula (III). The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not limited in halogen composition, and silver chloride, silver chlorobromide, silver iodochlorobromide,
Any of silver bromide and silver iodobromide can be used. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of the silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.2 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100. It is preferable that the variation coefficient represented is 15% or less, more preferably 10% or less and the particle size distribution is narrow. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is P. Glafki.
des by Chimie et Physique Photographique (Paul Mon
tel, 1967), by GFDufin Photographic Emul
sionChemistry (The Forcal Press, 1966), VL
Making and Coating Photographic E by Zelikman et al
It can be prepared using the method described in mulsion (The Focal Press, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one type of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase where silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Patent Publication No. 48-36890.
No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium, ruthenium, osmium and iridium in order to achieve high contrast and low fog. can do. This content is silver 1
The range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol is preferable, and the range of 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol is more preferable. Two or more of these metals may be used in combination.
These metals can be uniformly contained in the silver halide grains, and they are disclosed in JP-A-63-29603 and JP-A-2 / 1983.
-306236, 3-167545, 4-76
No. 534, Japanese Patent Application Nos. 4-68305 and 4-25818.
As described in No. 7 or the like, it may be contained in the particles with a distribution.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having halogen, amines, oxalate, etc. as a ligand, for example, hexachlororhodium (III)
Examples thereof include complex salts, hexabromorhodium (III) complex salts, hexaamminerhodium (III) complex salts, and trisalatrodium (III) complex salts. These rhodium compounds are used by being dissolved in water or a suitable solvent, and a method that is generally performed to stabilize the solution of the rhodium compound,
That is, a method of adding an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The addition of these compounds can be appropriately carried out at each stage before the production of silver halide emulsion grains and before the coating of the emulsion, but it is added especially at the time of emulsion formation and incorporated into the silver halide grains. It is preferable.

Rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-1.
-2859451, 2-20852, 2-208
It is added in the form of a water-soluble complex salt described in No. 55, etc. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^-n Here, M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands, thionitrosyl ligands and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[0122] ^{_{ReCl 6 -3 ReBr 6 -3 ReCl 5}} (NO) -2 Re (NS) Br 5 -2 Re (NO) (CN) 5 -2 Re (O) 2 (CN) 4 -3 RuCl 6 - ³ RuCl ₄ (H ₂ O) ₂ ^-2 RuCl ₅ (NO) ^-2 RuBr ₅ (NS) ^-2 Ru (CN) ₆ ^-4 Ru (CO) ₃ Cl ₃ ^-2 Ru (CO) Cl ₅ ^-2 Ru (CO) Br ₅ ^-2 OsCl ₆ ^-3 OsCl ₅ (NO) ^-2 Os (NO) (CN) ₅ ^-2 Os (NS) Br ₅ ^-2 Os (CN) ₆ ^-4 Os (O) ₂ (CN ) ₄ ^-4

The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is added especially at the time of forming the emulsion and incorporated into the silver halide grains. It is preferable. To incorporate these compounds into the silver halide grains by adding them during the formation of silver halide grains, a powder of a metal complex or an aqueous solution dissolved together with NaCl or KCl is used to form a water-soluble salt or a water-soluble salt during grain formation. Method in which a silver halide grain is prepared by adding it into a water-soluble halide solution, or by adding as a third solution when a silver salt and a halide solution are mixed at the same time, and a three-liquid simultaneous mixing method, or grain formation There is a method in which a water-soluble amount of a required amount of the metal complex is charged into the reaction vessel. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the time of chemical ripening.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium and hexacyanoiridium.
These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg KCl,
NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The silver halide grains in the present invention may be doped with another heavy metal salt. Especially K ₄ [Fe (C
N) ₆ ] is preferably used to dope the Fe salt. Further silver halide grains used in the present invention, cobalt, nickel, palladium, platinum, gold, thallium, copper,
It may contain a metal atom such as lead. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention may be chemically sensitized, and known methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization can be used. , Alone or in combination. When used in combination, for example, sulfur sensitization method and gold sensitization method,
The sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, and the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, thiazoles, rhodanins, etc. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
No. 3489, Japanese Patent Application Nos. 2-130976 and 2-229.
The compounds described in No. 300, No. 3-121798 and the like can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, J. Chem. Soc. Chem. Commun.,
635 (1980), 1102 (1979), 645 (1979), J. Chem. So
c.Perkin.Trans., 1,2191 (1980), edited by S. Patai, The Che
mistry of Organic Serenium and Tellurium Compound
s, Vol. 1 (1986) and the same Vol. 2 (1987) can be used. Particularly preferred are compounds represented by formulas (II), (III) and (1V) in Japanese Patent Application No. 4-146739.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use molar amounts. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium auritin cyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of formation of silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in European Patent (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). Different conditions) may be used together.

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 following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and further described in JP-A Nos. 1-112235, 2-124560, 3-79928, 5-1389 and Japanese Patent Application No. 3-411064. Sensitized color element. 2) Surfactants, antistatic From JP-A-2-12236, page 9, upper right column, line 7 or the same, from antistatic agent, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 3) Antifoggant, Stability JP-A-2-103536, page 17, lower right column 19, agent line to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compounds having an acid group From JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 Page 11, upper left column, line 8. 6) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 8) Dyes, JP-A-2-103536, page 17, lower right column, line 1 to line 18, JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. Further, the solid dyes described in JP-A-2-294638 and JP-A-5-11382. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 11) Monomethine compound A compound of general formula (II) described in JP-A-2-287532 (particularly compounds II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12, lower left column, and EP 452,772A.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0135]

【Example】

<Preparation of Developer> A developer containing the compound of the present invention represented by formula (I) was prepared according to the formulation shown in Table 1. As a comparative example, a developing solution containing hydroquinone as a main component was also prepared.

[0136]

[Table 1]

<Adjustment of Sensitive Material> (Image Forming Layer Formulation) Formulation A Aqueous silver nitrate solution, potassium bromide, sodium chloride and silver 1
K ₂ Rh (H corresponding to 2.0 × 10 ⁻⁷ mol per mol
_An aqueous solution of halogen salt containing ₂ O) Cl ₅ is added to an aqueous solution of gelatin containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by a double jet method while stirring to obtain an average particle size of 0.2 μm and chloride. Silver chlorobromide grains having a silver content of 70 mol% were prepared.

Then, for each mole of silver in each emulsion
1 x 10^-3Conversion is performed by adding mol KI solution.
Wash with water by the flocculation method according to the usual method,
Add 40 g of gelatin to 1 mol of silver and add 1 mol of silver.
Sodium benzenethiosulfonate 7mg and benze
2 mg of sulfinic acid was added. pH 6.0, pAg7.
Adjusted to 5, 3 mg of 1,3,3-trier per mole of silver
Add chill-2-thiourea and 4 mg of chloroauric acid to give 65
Chemical sensitization was performed to obtain optimum sensitivity at ° C. Further stabilizer
As 4-hydroxy-6-methyl-1,3,3a, 7
-Add 150 mg of tetrazaindene as a preservative
100 mg of proxel was added. Each particle obtained
Average grain size 0.25 μm, silver chloride content 69.9
It was a mol% silver iodochlorobromide cubic grain. (Variation coefficient 1
0%) A silver sensitizing dye represented by the following structural formula (s) is added to the above emulsion.
5 × 10 per mole ^-FourAdd 1 mol of silver and 1 mol of silver
3 x 10^-FourMol of mercapto compound represented by the following (a)
Compound 4 × 10^-FourMolar mercaptoization represented by (b)
Compound 4 × 10 ^-FourMolar triazine conversion represented by (c)
Compound 2 × 10^-3Molar 5-chloro-8-hydroquinoli
And the hydrazine derivative and nucleation as shown in Table-2.
Accelerator was added. Furthermore, N-oleyl-N-methyl
Taurine sodium salt 30 mg / m²So that it is applied
The water-soluble latex represented by (d) is added to 200 mg /
m², Polyethyl acrylate dispersion 200mg / m²,
Methyl acrylate and 2-acrylamido-2-methyl
Propanesulfonic acid sodium salt and 2-acetoacetoxy
Latex copolymer of cyethylmethacrylate (weight ratio
88: 5: 7) 200 mg / m², As a hardener
1,3-divinylsulfonyl-2-propanol 20
0 mg / m²Was added. The pH of the solution was adjusted to 6.0.

[0139]

[Chemical 65]

Formulation B 0.37 M silver nitrate aqueous solution and 1 × 10 1 per mol of silver
^-7 moles of K ₂ Rh (H ₂ O) Cl ₅ and 2 × 10 ^-7 moles of K ₂ IrCl ₆ at 0.16 M potassium bromide and 0.
A halogen salt aqueous solution containing 22M sodium chloride
0.08M sodium chloride and 1,3-dimethyl-2-
Nucleation by adding to a 2% aqueous gelatin solution containing imidazolithion by a double jet method at 38 ° C. for 12 minutes with stirring to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 55 mol%. I went. Subsequently, similarly, a 0.63 M silver nitrate aqueous solution and a halogen salt aqueous solution containing 0.23 M potassium bromide and 0.43 M sodium chloride were added over 20 minutes by the double jet method. Then, 1 × 10 ⁻³ mol of KI solution was added per mol of silver for conversion, followed by washing with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver to pH 6.0 and pAg 7.3. Adjust, and further add 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, and 8 parts of chloroauric acid per mol of silver.
mg and 5 mg of sodium thiosulfate were added, and the mixture was stirred at 60 ° C for 45
After heating for a minute for chemical sensitization, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and proxel as a preservative were added.
The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10%).

Each of the emulsions thus obtained contained 7 × 10 ^-4 mol of 5- [3-mol as a sensitizing dye per mol of silver.
(4-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and 4 × 10 ⁻⁴ mol was further added. A short-wave cyanine dye represented by the following structural formula (A), 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 4 × 1
0 ^-4 mol of the mercapto compound represented by the following structural formula (B), 3 × 10 ^-4 mol of the mercapto compound represented by the following structural formula (C), 4 × 10 ^-4 mol of the following structural formula (D) The triazine compound represented by the formula, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, the hydrazine derivative of the present invention and the nucleation accelerator are added as shown in Table 2 and further N-oleyl-N-methyltaurine. Sodium salt was added to be coated at 30 mg / m ² . To this was added 1,2-bis (vinylsulfonylacetamide) ethane 30 mg / m ² as a polyethyl acrylate dispersion (500 mg / m ² ) hardener.

[0142]

[Chemical formula 66]

Formulation C Controlled Double Jet Method
25μ cubic monodisperse silver iodobromide emulsion (coefficient of variation 0.1
5, silver iodide 1.0 mol% and iodine distribution were uniform). K ₃ IrCl ₆ was added to this silver iodobromide emulsion at 4 × 10 ^7.
Mol / Ag mol was added. This emulsion was desalted by the flocculation method and then kept at 50 ° C. to obtain a solution of 10 ⁻³ mol of potassium iodide per mol of silver and 4-hydroxy-6-methyl-1,3,3 as a stabilizer.
a, 7- and tetrazaindene per mol of silver 5 × 10 ^-4
Mol added. A hydrazine derivative and a nucleation accelerator were added to this emulsion as shown in Table 2.

Further, 5,5'-dichloro-3,3'-
Di (3-sulfopropyl) -9-ethyl-oxacarbocyanine sodium salt was added at 3.4 × 10 ⁻⁴ per mol of silver.
2 mol of 1-phenyl-5-mercaptotetrazole
× 10 ^-4 mol, 5 × 10 ^-4 mol of the short-wave cyanine dye represented by the following structural formula (a), a water-soluble latex (200 mg / m ² ) represented by (b), and a dispersion of polyethyl acrylate (200 mg). / M ² ) and 1,3 as a hardening agent
-Divinylsulfonyl-2-propanol (200 mg /
m ² ) was added.

[0145]

[Chemical formula 67]

(Redox compound-containing layer formulation) 1.0M
And a halogen salt aqueous solution containing 0.3M potassium bromide and 0.74M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ corresponding to 3 × 10 ^-7 mol per mol of silver, 0.08M sodium chloride and 1,3-dimethyl-
To a 2% gelatin aqueous solution containing 2-imidazoline thione, the mixture was added by a double jet method at 45 ° C. for 30 minutes while stirring to obtain silver chlorobromide grains having an average grain size of 0.30 μm and a silver chloride content of 70 mol%. It was Then, 1 × 10 ⁻³ mol of KI solution was added per mol of silver for conversion, followed by washing with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver to give a pH of 6.
0, pAg 7.6, and further, per mol of silver, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid and 5 parts of sodium thiosulfate.
After adding mg and heating for 60 minutes at 60 ° C. for chemical sensitization, 4-hydroxy-6-methyl-1, as a stabilizer,
350 mg 3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.30 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%)

Each of the emulsions thus obtained contained 5 × 10 ⁻⁴ mol of 5- [3-mol as a sensitizing dye per mol of silver.
(4-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and the following structural formula (J) was added. 10 mg / m ^{2 of the} dye represented by the formula ( ¹ ), a dispersion of polyethyl acrylate (250 mg / m ² ) and the redox compound of the present invention were added as shown in Table 2.

[0148]

[Chemical 68]

[0149] (Intermediate layer Formulation) to the gelatin solution, ethanethiolate of sodium 5 mg / m ^2, dye 100 mg / m ² expressed by (K), hydroquinone 100 mg / m ^2,
The triol compound represented by (L) was added in an amount of 50 mg / m ² and the polyethyl acrylate dispersion was added in an amount of 350 mg / m ² to prepare an intermediate layer coating solution.

[0150]

[Chemical 69]

Then, a layer of gelatin 0.2 g / m ² containing 40 mg / m ² of bis (vinylsulfonyl) ethane was coated on the polyethylene terephthalate film undercoated with gelatin, and the image forming method (Ag 3.4 g / m ² was used as the lowermost layer). ² , gelatin 1.6 g / m ² ) and a layer containing a redox compound (Ag 0.2 g / m ² ) via an intermediate layer (gelatin 0.8 g / m ² ).
m ² , gelatin 0.2 g / m ² ), and as a protective layer thereover gelatin 0.3 g / m ² , average particle size about 3.5 μm
60 mg / m ^{2 of} amorphous SiO ₂ matting agent, 0.1 g / m ^{2 of} methanol silica, 50 mg / m ^{2 of} liquid paraffin, and 5 mg / m ^{2 of} fluorosurfactant represented by the following structural formula (F) as a coating aid. And sodium dodecylbenzene sulfonate 20
mg / m ² was applied to prepare a sample as shown in Table-2.

[0152]

[Chemical 70]

[0153]

[Table 2]

The back layer was coated according to the following formulation. (Back layer formulation) Gelatin 3.2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² Gelatin hardening agent 1,3-Divinylsulfonyl- 2-Propanol 200 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 300 mg / m ² dyes The following dyes (M), (H), (I), (J) Mixture of Dye (M) 20 mg / m ² Dye (H) 50 mg / m ² Dye (I) 20 mg / m ² Dye (J) 30 mg / m ²

[0155]

[Chemical 71]

(Back protective layer) Gelatin 1.3 g / m ² polymethylmethacrylate fine particles (average particle size 2.5 μ) 20 mg / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² dihexyl-α-sulfosuccinate Sodium salt 15 mg / m ² Sodium acetate 60 mg / m ²

The pH of the film surface of the prepared light-sensitive material was measured (Japanese Patent Laid-Open No. Sho 6-62).
The method described in No. 1-223834) is shown in Table 3.

[0158]

[Table 3]

Example 1 According to JIS K 0102, the COD (Chemical Oxygen Demand) of the developers prepared in Table 1 was measured. The results are also shown in Table 1. As can be seen from the table, the developer of the present invention has a very low COD value as compared with the developer using the conventional hydroquinone type developing agent. This developer itself is not only dangerous from an ecological and toxicological point of view, but it is also subjected to development processing using a well-known automatic processor which undergoes the steps of development, fixing, washing and drying using this developer. At that time, it is shown that the degree of pollution to the environment due to the developer component mixed in the overflow of the washing tank is low.

Example 2 The light-sensitive material shown in Table 3 was exposed with a tungsten light of 3200 ° K through an optical wedge and a contact screen (Fuji Film, 150 L chain dot type), and then the table-
The developer shown in FIG. 3 was processed at 34 ° C. for 30 ″ using an FG-680AG automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.). As a fixing solution, GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used. .

[0161]

[Table 4]

The gradation γ is expressed by the following equation. The larger this value, the harder the photographic characteristics. * Γ = (3.0-0.3) / [log (exposure dose that gives a density of 3.0)-
log (exposure that gives a density of 0.3)]

The halftone is expressed by the following equation. The larger this value, the better the original reproducibility. * Amount of exposure that gives a halftone dot area ratio of halftone = 95% (log E95
%)-Exposure amount giving a dot area ratio of -5% (log E5%)

Regarding the halftone dot quality, the halftone dots of the light-sensitive material exposed through the contact screen were observed with a magnifying glass, and the sharpness and smoothness were evaluated on a 5-point scale. "5" represents the best level for both sharpness and smoothness, and "1" represents the lowest level. “3” is the practically allowable limit level.

(Results) By comparing Experiments No. 1 to No. 9 and No. 10 to 12, it can be seen that even when the developer of the present invention is used, it is possible to obtain the characteristics of high contrast and excellent original reproducibility. In addition, the dot quality was better with the combination of the present invention. Comparing Experiment Nos. 1 to 9 and Nos. 13 to 15, it is understood that the redox compound of the present invention greatly contributes to the improvement of original reproducibility. From the above, according to the present invention, it is possible to provide a system having a low environmental pollution degree and excellent image quality.

Example 3 Using the photosensitive materials and developing solutions shown in Table 4, the same evaluations as in Example 2 were carried out.

[0167]

[Table 5]

(Results) It is understood that good photographic characteristics can be obtained in a wide range of pH of the developing solution by using the combination of the suitable hydrazine nucleating agent, redox compound and nucleating accelerator of the present invention.

Example 4 The same evaluations as in Example 2 were carried out using the photosensitive materials and developing solutions shown in Table 5. Then, after leaving the developing solutions as they were for 5 days, the same evaluation was performed again.

[0170]

[Table 6]

(Results) Experiment Nos. 1, 3, 5 or 2, 4,
Comparing the results of the treatment with the fresh solution of No. 6 shows that the addition of the nucleation development accelerator (N-n-butyldiethanolamine) to the developer can lower the pH of the developer while maintaining the high contrast. Comparing Experiment Nos. 1, 5 or 2, 6 reveals that the gradation changes with time of the developing solution
It can be seen that is smaller and has better stability. The developing agent of the present invention causes a decrease in pH due to decomposition, but the decomposition rate tends to decrease as the pH decreases. Therefore, a developing solution in which nucleation development sufficiently occurs at a lower pH is preferable, and as a method therefor, addition of a developing solution of a nucleation development accelerator is effective.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one hydrazine derivative is contained in at least one layer of the emulsion layer or other hydrophilic colloid layer, and at least one layer is oxidized in at least one layer of the emulsion layer or other hydrophilic colloid layer to suppress development. A silver halide photographic light-sensitive material characterized by containing a redox compound capable of releasing a developing agent, is substantially free of a dihydroxybenzene-based developing agent as a developing agent, and is a developing agent represented by the following general formula (I). An image forming method comprising developing with a developing solution containing General formula (I) In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group,
It 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,
Represents a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are bonded to each other, and two vinyl carbon atoms substituted by R ₁ and R ₂ are substituted by Y; Represents a group of atoms forming a 5- to 7-membered ring together with the carbon atom. Y represents = O or = N-R _3,. R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group,
Acyl group, hydroxyalkyl group, sulfoalkyl group,
Represents a carboxyalkyl group. 2. The image forming method according to claim 1, wherein the hydrazine derivative is represented by the following general formula (II). General formula (II) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group,
Represents an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group, or an oxycarbonyl group, and G ₁ represents a —CO— group, a —SO ₂ — group, a —SO— group, or Represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group, and 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 unsubstituted Represents an arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the group defined for R ₂ ,
It may be different from R ₂ . 3. A redox compound as a redox group
General formula (R-1), general formula (R-2), general formula (R-
The image according to claim 1, which is represented by 3).
Forming method. [Chemical 4]In these formulas, R₁Represents an aliphatic group or an aromatic group.
G₁Is -CO- group, -CO-CO- group, -CS- group, -C (= NG₂R
₂) -Group, -SO- group, -SO₂-Group or -P (O) (G ₂R₂) -Group
Represents G₂Is a mere bond, -O- group, -S- group or
Is -N (R₂) -Represents a group, R₂Is R₁The same definition as or
Represents a hydrogen atom, and multiple R in the molecule₂If it exists
They may be the same or different. A₁, A₂
Is a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group
Represents an alkyl group or an acyl group and may be substituted. General
In formula (R-1), A₁, A₂At least one of
Is a child. A₃Is A₁Synonymous with or -CH₂CH (A_Four)-(Time)
_t-Represents PUG. A_FourIs nitro group, cyano group, carboxy
Group, sulfonyl group or -G₁−G₂-R₁(In this case, minutes
Two -G in the child₁−G₂-R₁Are the same but different
May be. ) Represents. Time represents a divalent linking group, and t is
Represents 0 or 1. PUG represents a development inhibitor. 4. The image forming method according to claim 1, wherein the developer contains a nucleation development accelerator. 5. The image forming method according to claim 4, wherein the nucleation development accelerator contained in the developer is represented by the following general formula (III). General formula (III): In the formula, R ₂₁ , R ₂₂ and R ₂₃ are HR ₂₁ and H-, respectively.
It represents an R _22, the sum of the H-R ₂₃ of n- octanol / water partition coefficient log (logP) is in the range of less than 2.6 or more and 10.0 or a substituted or unsubstituted alkyl group.