JP3423504B2 - Developing method of silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of developing a silver halide photographic light-sensitive material for plate making.

[0002]

2. Description of the Related Art A method of producing a high contrast image using a hydrazine derivative is well known and widely used for photolithography. However, since a high pH is generally required, the developer is easily oxidized by air and is unstable.

Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. JP-A-1-17993
No. 9 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorbing group for silver halide emulsion grains and a nucleating agent also having an adsorbing group was used to obtain a pH of 11.0. The processing method of developing with the following developing solution is described. U.S. Pat. Nos. 4,998,604 and 4,994,365 disclose hydrazine compounds having a repeating unit of ethylene oxide and hydrazine compounds having a pyridinium group. However, as is clear from these examples, the high contrast is not sufficient, and the high contrast and the required D
Getting max is difficult.

Further, the pH of the developing solution is increased by the concentration of the developing agent due to air oxidation and evaporation of water, or is lowered by the absorption of CO ₂ gas in the air and the development processing of the exposed photosensitive material. It is not always kept constant. If the pH of the developer changes, the photographic performance also changes, and especially the contrast adjustment performance changes, so it was necessary to add a large amount of replenisher.

As described above, there has been a demand for an image forming method in which the development pH is further lowered and the change in photographic performance due to the pH change is small, but the conventional technique cannot satisfy the demand.

On the other hand, in order to reduce the influence on the environment, attempts have been made to replace hydroquinone, which has been conventionally used universally, with ascorbic acid. Special table flat 6
-505574 (corresponding WO Patent 93/11456),
US 5,236,816 and US 5,264,3
No. 23 discloses an image forming method in which a silver halide light-sensitive material containing a hydrazine derivative and a developing solution containing ascorbic acid are used for processing. According to the description, a high-contrast image cannot be obtained unless a 3-pyrazolidone derivative is used as a super-additive auxiliary developing agent together with an ascorbic acid developing agent and the pH of the developing solution is relatively high. In fact, as a result of our additional test, the ultra-high contrast performance could not be obtained unless the pH was high such as pH ≧ 11.0. It has also been found that, as a serious drawback of this system, when the developer is air-oxidized or fatigued during film processing, the pH is remarkably lowered and the ultra-high contrast performance is extremely impaired.

Further, EP 573,700 discloses a development processing method in which a developing solution in which ascorbic acid and a 3-pyrazolidone derivative are used in combination uses a replenishing solution having a higher pH and substantially the same components. There is. However, EP 573,700 does not describe a super-high contrast sensitive material using a hydrazine derivative. Further, as described above, in the developer using ascorbic acid and the 3-pyrazolidone derivative, the developer pH is 9.0 to 10.
In the range of 5, the ultrahigh contrast performance of the hydrazine ultrahigh contrast sensitive material cannot be obtained. When the alkalinity is high such that pH ≧ 11.0, ultra-high contrast performance can be obtained, but the pH drop due to the air oxidation of the developer becomes severe, and the tendency becomes even stronger when a replenisher having a higher pH is used, and the development during running processing is promoted. It becomes almost impossible to keep the liquid pH constant.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
A silver halide photograph for platemaking that achieves super-high contrast performance by using a developer having a low pH of ≤ 10.5, and minimizes fluctuations in pH during processing and running, and that has a low environmental load. The present invention relates to a method for developing a photosensitive material.

[0009]

The above-mentioned object of the present invention is to have at least one silver halide emulsion layer on a support, wherein the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative and nucleation promoting substance. A silver halide photographic light-sensitive material containing a developing agent, which contains at least one first developing agent selected from ascorbic acid or a derivative thereof and a second developing agent selected from aminophenol or a derivative thereof, and has a pH of 9.0. ~ 1
In the processing method of processing with a developing solution of 0.5, the solution is solved by a developing processing method characterized in that a solution having a pH higher than that of the development starting solution is used as a development replenisher.

Further, as an unexpected effect of the present invention, it was also found that the replenishing amount of the replenishing liquid can be extremely reduced to 200 ml or less per 1 m ^{2 of the} light-sensitive material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below. The developer (development starter and developer replenisher) of the present invention contains at least one ascorbic acid or its derivative as the first developing agent. Preferred ascorbic acid or its derivative is a compound represented by the general formula (II).

[0012]

[Chemical 1]

In the general formula (II), R ₁ and R ₂ are each a hydroxy group or an amino group (having 1 carbon as a substituent).
-10 alkyl groups such as methyl, ethyl, n-
Those having a butyl group, a hydroxyethyl group or the like as a substituent are included. ), An acylamino group (acetylamino group, benzoylamino group, etc.), an alkylsulfonylamino group (methanesulfonylamino group, etc.), an arylsulfonylamino group (benzenesulfonylamino group, p-
It represents a toluenesulfonylamino group), an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, 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 group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group, or P and Q are combined to form two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y, and It represents an atomic group necessary for forming a 7-membered ring. Specific examples of the ring structure, -O -, - C (R 4) (R 5) -, -
_{C (R 6) =, -} C (= O) -, - N (R 7) -, - N =,
It is configured by combining. However, R ₄ , R ₅ , R ₆ ,
R ₇ represents 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 can be mentioned as the substituent), a hydroxy group or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

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- to 7-membered ring are:
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 (II) are shown below, but the invention is not limited thereto.

[0017]

[Chemical 2]

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

Of these, ascorbic acid and erythorbic acid (diastereomers of ascorbic acid) are preferred. The general range of the amount of the compound of the general formula (II) used is 5 × 10 ⁻³ per liter of the developing solution.
The amount is 1 to 1 mol, particularly preferably 10 ^{-2 to} 0.5 mol.

Aminophenols are used as the second developing agent. The amino phenol compounds 4-aminophenol, 4-amino-3-methylphenol, 4- (N
-Methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, N-β -Hydroxyethyl-4-aminophenol, N- (4'-hydroxyphenyl) pyrrolidine, N-γ-hydroxypropyl-4-aminophenol, 6-hydroxyl-
Examples include 1,2,3,4-tetrahydroquinoline, N, N-dimethyl-4-aminophenol, N, N-diethylaminophenol, and hydrochlorides and sulfates of these compounds.

The amount of aminophenols used is generally in the range of 5 × 10 ^-4 to 0.5 mol, preferably 10 ^-3 to 0.1 mol, per liter of the developing solution.

The addition ratio of the first developing agent and the second developing agent can be arbitrarily selected as long as they are within the ranges of the above respective addition amounts.

[0025]

The developer of the present invention preferably contains a preservative and an alkali in addition to the above essential components. Sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite and potassium metabisulfite. The greater the amount of preservative added, the better the preservability of the developer, but on the other hand, the amount of silver ions dissolved from the photosensitive material into the developer increases, and silver sludge gradually accumulates in the developer. It has an adverse effect. Since the developing solution of the present invention has high stability, it is possible to obtain sufficient preservability by reducing the amount of sulfite added. Therefore, the amount of sulfite added is preferably 0.5 mol or less per liter of the developing solution. More preferably 0.0
2 to 0.4 mol / liter is preferable. Particularly preferably 0.
02 to 0.3 mol / liter is preferable.

Additives other than those mentioned above include
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or its derivatives; mercapto Compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds may be included as antifoggants or black pepper inhibitors. 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-thiadiazole-
2-yl) thio] butanesulfonic acid sodium salt, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.05 to 2 mmol, per liter of the developing solution.

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

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriamine pentaacetic acid. Acetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554, and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730 and 54.
-112127, 55-4024, 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of alkali metal salts or ammonium salts. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 ×, per 1 liter of the developing solution.
It is 10 ⁻³ to 1 × 10 ⁻² mol.

Further, if necessary, a toning agent, a surfactant,
You may also contain a defoaming agent, a hardening agent, etc.

The developer used in the present invention contains a carbonate, boric acid and borate as a pH buffer (for example, boric acid,
Borax, sodium metaborate, potassium borate) Sugars (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphate described in JP-A-60-93433. (For example, sodium salt, potassium salt), aluminate (for example, sodium salt) and the like are used, and preferably carbonate and borate are used. The pH buffer is 0.1-1.
The amount used is 2 mol / liter, preferably 0.2 to 0.8 mol / liter. Development temperature and time are interrelated and are determined in relation to the total processing time, but generally the development temperature is from about 20 ° C to about 50 ° C, preferably from 25 to 45 ° C.
The development time is 5 seconds to 2 minutes, preferably 7 seconds to 60 seconds, at ℃.

The pH of the development initiating solution of the present invention is 9.0-1.
It is 0.5. As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate) can be used.

The composition of the developing replenisher is basically the same as that of the developing starter except for pH. The pH of the development replenisher is set higher than the pH of the development starter. Preferably, the pH of the development replenisher is 0.2 to
It is set to 1.5 units, particularly preferably 0.3 to 1.0 unit higher. However, if the pH of the replenisher is too high, the replenisher itself is likely to be oxidized by air.
The upper limit of H is preferably about 11.2. By performing the running process while replenishing the developing replenisher, it is possible to almost eliminate the fluctuation of the pH value of the developer which is actually processing the light-sensitive material, and the p
The photosensitive material is processed at a pH value almost the same as H (that is, the pH value of the development starter solution). The pH of the development starter solution and the development replenisher solution may be adjusted by adding the above-mentioned alkaline agent to the development starter solution to prepare a development replenisher solution. Alternatively, based on the development replenisher solution, acetic acid, glacial acetic acid, or sulfamic acid may be added. Alternatively, an acid such as sulfuric acid may be added to lower the pH to obtain a developing starter solution.
Alternatively, the development initiating solution and the development replenishing solution may be separately prepared to have compositions optimized within the above-mentioned addition amounts.

In the present invention, the processing is carried out while replenishing the development replenisher in accordance with the processing amount of the silver halide light-sensitive material. The replenishment amount of the developing replenisher is usually 500 ml or less per square meter of the light-sensitive material, but can be made smaller than usual by the present invention, and low replenishment of 200 ml or less per square meter of the light-sensitive material, and further 150 ml or less. However, stable processing is possible.

The developed light-sensitive material is usually fixed, washed with water (stabilized) and dried. The fixing solution used in the fixing step is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid,
It is an aqueous solution containing Tylon, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid and their salts. From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, 0.2 to 1.5 mol /
It is a liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH adjuster (eg, ammonia, sulfuric acid). ), A chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include JP-B-45-35754 and JP-A-58-122535.
No. 58-122536, thiourea derivatives, alcohol having triple bond in the molecule, US Pat.
A thioether compound described in JP-A-126459, JP-A-4-
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid, and inorganic acids such as boric acid, phosphate, and sulfite. A buffer can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developer,
Mol / l, more preferably about 0.02-0.6 mol / l. The pH of the fixing solution is preferably 4.0 to 6.5, and particularly preferably 4.5 to 6.0. Further, as a dye elution accelerator, JP-A 64-473
The compounds described in No. 9 can also be used.

As the hardening agent in the fixing solution, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferred addition amount is
0.01 mol to 0.2 mol / liter, more preferably 0.03
~ 0.08 mol / l. The fixing temperature is about 20 ° C
At about 50 ° C, preferably 25-45 ° C, the fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is 500 ml / m ² or less, and particularly preferably 300 ml / m ² or less with respect to the processing amount of the light-sensitive material.

As the treatment proceeds, silver salts accumulate in the fixer. The fatigued fixing solution can be recycled for removing silver salts by a known silver recovery means. It is possible to use a method of removing silver ions into metallic silver by electrolytic reduction and then filtering and removing with a filter, a method of removing silver ions by adsorbing it on a strongly adsorbing compound, and a method of protruding the silver ions on the surface of a metal filament to remove them. These silver recovery devices may be installed in the fixing solution circulation line or may be processed offline.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. For washing or stabilizing treatment, the amount of washing water is usually ² per 1 m ^{2 of} silver halide light-sensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
It can also be carried out by including, that is, washing with water. 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 gradually processed in the normal direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed. Washed with water. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287252. Alternatively, or it may be combined various oxidation agent addition and filtration for Do that pollution load reduction problematic when a small amount water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the method according to the present invention is disclosed in JP-A-60- 23
As described in No. 5133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in the washing tank. In addition, in some cases, stabilization treatment may be performed following the water washing treatment,
As examples thereof, JP-A-2-201357 and JP-A-2-132
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time is 0-5
0 ° C. and 5 seconds to 1 minute are preferable.

The processing liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer. The treatment liquid used in the present invention may be powdered or solidified. As the method, a known method can be used.
259921, JP-A-4-85533, JP-A-4-
It is preferable to use the method described in 16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 35,
No. 45971, etc., and is herein simply referred to as a roller transport type processor. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Instead of the water washing step, four stable steps may be used.

Next, the silver halide photographic light-sensitive material to which the developing method of the present invention is applied will be described. Although any of the hydrazine derivatives used in the present invention can be used, compounds represented by the following general formula (I) are preferable. General formula (I)

[0043]

[Chemical 6]

In the formula (I), R ₁ is an aliphatic group, an aromatic group,
Alternatively, it represents a heterocyclic group, and R ₂ is a hydrogen atom or a blocking group. G ₁ is a —CO— group, a —SO ₂ — group, a —S
O- group, -CO-CO- group, a thiocarbonyl group, an iminomethylene group or _{-P (O) (R 3)} - represents a group, R ₃
It is selected from the same range as the groups defined in R _2, may be different from R _2.

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, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. In the general formula (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, particularly 1 to 3 carbon atoms.
20 straight, branched or cyclic alkyl groups. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (I), 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 a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group. The aliphatic group, aromatic group or heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, and pyridinium. Group, hydroxy group,
Alkoxy group, aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having a hydrazide structure, 4 A group having a primary ammonium structure, an alkyl or arylthio group,
An alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carboxyl group, a sulfo group,
Acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoramide group, diacylamino group, imide group, group having acylurea structure, group containing selenium atom or tellurium atom, 3 Examples thereof include a group having a primary sulfonium structure or a quaternary sulfonium structure, and preferable substituents include a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20) and an aralkyl group (preferably an alkyl moiety Mono- or bi-cyclic C1 to C3), alkoxy groups (preferably C1 to C20), substituted amino groups (preferably amino groups substituted with C1 to C20 alkyl groups) ), An acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 carbon atom) Those with 30), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably those having 1 to 30 carbon atoms).

As the blocking group for R ₂ , an alkyl group,
There are aryl groups, unsaturated heterocyclic groups, alkoxy groups, aryloxy groups, amino groups, or hydrazino groups.

In the general formula (I), 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. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and the alkylamino group having 1 to 10 carbon atoms. A group and an arylamino group are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable.

Preferred among the groups represented by R ₂ are alkyl groups (eg, methyl group, trifluoromethyl group, 2-carboxy-tetrafluoroethyl group, 3 and 3 when G ₁ is —CO— group. -Hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, methyl group substituted with pyridinium group, etc.), aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-
Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), especially a hydrogen atom,
A trifluoromethyl group is preferred. Also, G ₁ is -SO ₂
In the case of a group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, dimethylamino group). Etc.) are preferred.

When G ₁ is a --COCO-- group, an alkoxy group, an aryloxy group and a substituted or unsubstituted amino group are preferred. As G in the general formula (I), -CO- group, -CO
A CO- group is preferred, and a -CO- group is most preferred. or,
R ₂ splits the portion of G ₁ -R ₂ from the rest of the molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing atoms of the _1- R ₂ moiety, and examples thereof include those described in JP-A-63-29751. To be

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R ₂ of the general formula (I) may be a skeleton in which a group which enhances adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108 and 4,459,34.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The group described in 3-234246 is mentioned.

Particularly preferred hydrazine derivative in the present invention is that R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, or a phenyl group having an alkylthio group, G is -CO- group or -COCO- group, hydroxymethyl R ₂ is the electron withdrawing group or 2-position as a substituent alkyl group or a substituted aryl group (substituent Group), or a hydrazine derivative which is a substituted or unsubstituted amino group. Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to the following compounds.

[0057]

[Chemical 7]

[0058]

[Chemical 8]

[0059]

[Chemical 9]

[0060]

[Chemical 10]

[0061]

[Chemical 11]

[0062]

[Chemical 12]

[0063]

[Chemical 13]

[0064]

[Chemical 14]

[0065]

[Chemical 15]

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
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
285343, 2-289843, 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3, No. 3-54549, No. 3-125134, No. 3
-184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, No. 3-228536, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230.
No. 233, No. 4-96053, No. 4-216544.
No. 5, No. 5-45761, No. 5-45762, No. 5-
No. 45763, No. 5-45764, No. 5-45765.
And those described in Japanese Patent Application No. 5-94925 can also 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, particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol. The hydrazine derivative in the present invention is contained in the emulsion layer and / or other hydrophilic colloid layer. Here, examples of the other hydrophilic colloid layer include a protective layer, a layer provided between the emulsion layer and the support, and an intermediate layer.

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, dimethylsulfoxide, methylcellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. 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 silver halide photographic light-sensitive material of the present invention has a silver halide emulsion layer or at least one other hydrophilic colloid layer formed of an amine derivative, an onium salt, a disulfide derivative and a hydroxymethyl derivative. Contains a nuclear promoter. These nucleation accelerators may be used alone or in combination of two or more. Examples of amine derivatives include those disclosed in JP-A-60-140,340 and JP-A-60-340.
2-50,829, 62-222,241, 6
2-250,439, 62-280,733, 63-124,045, 63-133,145,
Examples thereof include the compounds described in JP-A No. 63-286,840. The amine derivative is more preferably JP-A-63-124,045 and JP-A-63-133,145.
No. 63-286,840, etc., or a compound having a group capable of adsorbing to silver halide, or JP-A-62-62
-222,241, etc., the sum of carbon numbers is 2
0 or more compounds. The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A-62-250,43.
The compounds described in No. 9, No. 62-280, 733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,939 and JP-A-6-167,939.
The compound described in 2-280,733 etc. can be mentioned. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198,147. Examples of hydroxymethyl derivatives include, for example, U.S. Pat. Nos. 4,693,956 and 4,777,11.
8, EP 231,850, JP-A-62-50,82.
Examples thereof include compounds described in No. 9 and the like, and more preferably a diarylmethanol derivative.

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

[0071]

[Chemical 16]

[0072]

[Chemical 17]

[0073]

[Chemical 18]

[0074]

[Chemical 19]

[0075]

[Chemical 20]

[0076]

[Chemical 21]

[0077]

[Chemical formula 22]

[0078]

[Chemical formula 23]

[0079]

[Chemical formula 24]

[0080]

[Chemical 25]

[0081]

[Chemical formula 26]

The optimum addition amount of these compounds varies depending on the kind thereof, but is 1.0 × 1 per mol of the hydrazine compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is desirable to use it in the range of 10 ⁻¹ mol to 1.0 × 10 mol. These compounds are dissolved in a suitable solvent (H ₂ O) alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide, silver iodobromide and salts. Silver iodobromide or the like can be used. Silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferable. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol or less. 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 silver halide is preferably 0.01 μm to 0.7 μm, more preferably 0.05 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100 It is preferable that the variation coefficient 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 described by P. Glafkides C
himie et Physique Photographique (Paul Montel, 1967), GFDufin, Photographic Emulsi
on Chemistry (The Focal Press, 1966), V.
Making and Coating Photographi by L. Zelikman et al
c Emulsion (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, a combination thereof and the like 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 form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which 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 Examined Patent Publication No. 48-3689.
As described in No. 0 and 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. 4,242,4
It is preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-45-58-158124, and to grow it quickly within a range not exceeding the critical saturation.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, the sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, 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 such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. 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.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. It is particularly preferable to use the compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride presumed to be 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 Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), ibid. 1102 (1979), ibid. 645 (1979), J. Chem. Soc. Perkin. Trans., 1,
2191 (1980), edited by S. Patai, The Chemistry of
OrganicSerenium and Tellurium Compounds, Vol1
(1986) and Vol 2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) 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, about 10 ^-7 to 10 ^-3 mol is used. 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 aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. 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 or physical ripening of silver halide grains. 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 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.

The silver halide photographic light-sensitive material of the present invention preferably contains a rhodium compound in order to achieve high contrast and low fog. 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 a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaamminerhodium ( Examples thereof include III) complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the rhodium 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, Na
A method of adding Br or the like) 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 total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of silver halide finally formed.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Although various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize 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 (for example, 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 total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ^-6 mol is suitable, and preferably 5 × 10 ^-8 to 1 ×.
It is 10 ^-6 mol. 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 particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. 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.

Further, contact films and contact papers which can be handled in a bright room are generally called bright room return sensitive materials, and silver chloride emulsions are preferable for such sensitive materials.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) Silver halide emulsion JP-A-2-97937, page 20, lower right column, line 12 and its manufacturing method, see page 21, left lower column, line 14; JP-A-2-12236. The selenium sensitization method described on page 7, upper right column, line 19 to page 8, lower left column, line 12 and Japanese Patent Application No. 2-189532. 2) Spectral sensitizing dyes, JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; 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, Japanese Patent Application Nos. 3-189532, 3-411064 and 6-103272. Sensitizing dye. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to same, lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to page 4, right Lower column, line 18, Japanese Patent Application No. 5-204325. 4) Antifoggant 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; and JP-A-1-237538 The thiosulfinic acid compounds described in Japanese Patent Publication No. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 9) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 9) Dyes The dyes described in JP-A-2-103536, page 17, lower right column, lines 1 to 18; solid dyes described in JP-A 2-294638 and Japanese Patent Application No. 3-187573. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 12) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 13) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column to first benzene, page 2, lower left column, and EP 452772A.

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

[0100]

【Example】

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
An aqueous solution of halogen salt containing (H ₂ O) Cl ₅ , sodium chloride, and an aqueous solution of gelatin containing 1,3-dimethyl-2-imidazolidinethione were added by a double jet method with stirring to obtain an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

Thereafter, the product was washed with flocculation according to a conventional method, 40 g of gelatin was added per 1 mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver, and the pH was adjusted to 6.0. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained particles each have an average particle size of 0.25μ.
m and a silver chlorobromide cubic grain having a silver chloride content of 70 mol%. (Variation coefficient 10%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moisture-proof undercoat containing vinylidene chloride, from the support side,
A UL layer, an EM layer, a PC layer, and an OC layer were applied in this order to form a sample, and a sample was prepared. The preparation method and coating amount of each layer are shown below.

(UL layer) A dispersion of polyethyl acrylate in an amount of 30 wt% with respect to gelatin was added to an aqueous gelatin solution and coated so as to have a gelatin content of 0.5 g / m ² .

[0104] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of the following compound (p), and 4 × 10 ⁻⁴ mol of the following compound (A) as a nucleation accelerator. Was added. Furthermore, hydroquinone 100 mg and N-oleyl-N-methyltaurine sodium salt 30 mg / m ²
Added as applied. Next, the hydrazine derivative (Compound No. 17) was 1 × 10 ⁻⁵ mol / m ² , the water-soluble latex represented by (d) was 200 mg / m ² , the polyethyl acrylate dispersion was 200 mg / m ² , and methyl acrylate was used. And a latex copolymer of 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5:
7) 200 mg / m ² , colloidal silica having an average particle size of 0.02 μm 200 mg / m ² , sodium dodecylbenzenesulfonate 30 mg / m ² , and 1,3-divinylsulfonyl-2-propanol 20 as a hardening agent.
0 mg / m ² was added. The pH of the solution is 5.
Prepared to 65. They were coated such that the coated silver amount was 3.5 g / m ² .

(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
The following surfactant (w) was added at 5 mg / m ² , 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² so as to be coated, and gelatin was coated at 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 4 having an average particle size of about 3.5 μm 4
0 mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0107]

[Chemical 27]

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0109]

[Chemical 28]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0111]

[Chemical 29]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 488 nm and a step wedge to emit light at a light emission time of 10 ⁻⁵ se.
After being exposed with the xenon flash light of c and developed with the developing solutions A to C shown in Table 1 at 35 ° C. for 30 seconds, fixing, washing and drying treatments were performed. The amount of sodium sulfite in Table 1 is 0.08 mol / liter. Developer B is a comparative developer in which N-methyl-p-aminophenol of developer A is replaced with equimolar 1-phenyl-3-pyrazolidone. Developer C is a comparative developer having the same formulation as developer DC described in the examples of EP 573,700A1.

[0114]

[Table 1]

The fixing solution used had the following formulation. (Fixer formulation)   Ammonium thiosulfate 359.1 g   Ethylenediaminetetraacetic acid 2Na dihydrate 0.09g   Sodium thiosulfate pentahydrate 32.8g   Sodium sulfite 64.8g   37.2g of NaOH   Glacial acetic acid 87.3g   Tartaric acid 8.76g   Sodium gluconate 6.6g   Aluminum sulphate 25.3g   pH (adjusted with sulfuric acid or sodium hydroxide) 4.85   Add 3 liters of water

(2) Evaluation of Image Contrast and Sensitivity As an index (gamma) indicating the image contrast, from the point of fog + density 0.1 of the characteristic curve to fog + density 3.
The point of 0 was connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = (3.0-0.1) / [l
og (exposure amount that gives a density of 3.0)-(exposure amount that gives a density of 0.1)], and the larger the gamma value, the harder the photographic characteristics are. The gamma of the light-sensitive material for graphic arts is preferably 10 or more, more preferably 15 or more. The photographic sensitivity is the logarithm of the reciprocal of the exposure amount that gives a density of 1.5,
It was expressed as a relative value with respect to the developer A. (3) Evaluation of halftone dot quality (DQ) 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. When the level is [3] or higher, the sharpness and smoothness of the on / off portions of the image when the scanner exposure is actually performed can be practically allowed.

The above results are shown in Table 2. The developer A gives extremely high contrast and Dmax, and has high sensitivity and high halftone dot quality, while the comparative developers B and C
Is insufficiently hardened.

[0118]

[Table 2]

The difference between the developing solutions A and B is the difference between N-methyl-p-aminophenol and 1-phenyl-3-pyrazolidone, and it is totally unexpected that the super-high contrast property is so different. Is the effect of.

<Evaluation of Processing Running Performance> With the automatic developing machine FG-680AG manufactured by Fuji Photo Film Co., Ltd., the processing was continued for 2 weeks while the photosensitive material was processed at 10 m ² per day. As a replenishing solution, a solution having the same formulation as that of the developing solution A and containing sodium hydroxide to raise only the pH as follows was used to replenish 150 ml per 1 m ² of the light-sensitive material. Replenisher No. A-1 A-2 A-3 A-4 A-5 A-6 pH 9.7 10.0 10.3 10.5 10.7 11.0 (Difference from mother liquor) (0) (+0.3) (+0.6) (+0.7) Table 3 shows the changes in (+1.0) (+1.3) days of running, pH of developer and photographic performance. The following can be read from the results in this table. 1) As the pH of the replenisher increases, the decrease in pH due to running decreases, and at A-5 or higher, it starts to increase. 2) On the other hand, the contrast and halftone dot quality depend on the replenisher pH.
The higher the value is, the better level is maintained after running, but the quality deteriorates in the region where the pH of A-5 or A-6 increases during running. It was A-2 to A-5 that the halftone dot quality could be maintained at 4 or more even after running for 2 weeks, that is, the replenisher pH was within the range of +0.3 to +1.0 of the pH of the development starter.

[0121]

[Table 3]

Example 2 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion B] Emulsion except that 1 mg of selenium sensitizer having the following structural formula, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid are added per 1 mol of silver and chemically sensitized to obtain optimum sensitivity at 60 ° C. It adjusted like A.

[0123]

[Chemical 30]

Preparation of Coating Sample Instead of the sensitizing dye in the EM layer of Example 1, 2.1 × 10 ⁻⁴ mol of the following compound (S-3) was added per 1 mol of silver to prepare an emulsion for the EM layer. A sample was prepared in the same manner as in Example 1 except that Emulsion B was used.

[0125]

[Chemical 31]

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 633 nm and a step wedge to emit light at a light emission time of 10 ⁻⁶ se.
Exposed to xenon flash of c. As a developer
A solution in which the amount of sodium sulfite added was changed as follows with the developer A was prepared and treated in the same manner as in Example 1. Developer No. A-21 A-22 A-23 A-23 A-24 A-25 A-26 Sodium sulfite 0.01 0.02 0.08 0.20 0.30 0.40 (mol / liter) As a result, the contrast, Dmax, and halftone dot quality were found in Example 1.
It showed a good value as well.

Next, the residual color was evaluated. The residual color means that the applied dye or sensitizing dye is sufficiently eluted and is not completely decolorized when it undergoes development, fixing and washing with water, and the processed film is colored. Generally, the residual color is deteriorated when the temperature of the fixing solution or the washing water is low, so the test was performed by cooling to 5 ° C. The visually residual color level 1 indicates the degree to which the tint is strongly recognized, the level 2 is the level at which the tint is slightly recognized, and the level 3 is the level at which the tint is not recognized. The results are shown in Table 4.

Next, the silver sludge was evaluated. The silver sludge of the developing solution was evaluated by visual evaluation of the developing solution after treating the photosensitive material with 16 m ² using 2 liter of the developing solution without replenishing the solution. Rank 1 is a stain in which the developer is turbid and deposits are recognized on the bottom of the developing tank, Rank 2 is a case where the developer is slightly turbid, and Rank 3 is
Indicates the case where no turbidity was observed at all.

[0129]

[Table 4]

From the data in Table 4, the sulfite concentration was 0.4.
It is not more than mol / liter, preferably 0.02 to 0.3 mol / liter, and the residual color and silver sludge are good.

Example 3 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1 except that the sensitizing dye in the EM layer of Example 1 was changed to the following compound (S-4). Created.

[0132]

[Chemical 32]

<Evaluation of Photographic Performance> 780 n
Through an interference filter having a peak at m, it was exposed with a xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge. After developing with the developer A described in Example 1 for 30 seconds at 35 ° C., fixing (the same as in Example 1), washing with water, and drying were performed. Evaluation of various performances was performed in the same manner as in Examples 1 and 2. <Results> By using the light-sensitive material of the present invention and the developer, a light-sensitive material for a semiconductor laser scanner having high image quality and good processing stability could be obtained.

Example 4 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1 except that the sensitizing dye in the EM layer of Example 1 was changed to the following compound (S-5). Created.

[0135]

[Chemical 33]

<Evaluation of Photographic Performance> The above sample was exposed to 3200 ° K tungsten light through a step wedge. The developer A described in Example 1 was used for 30 at 35 ° C.
After developing for a second, fixing, washing with water and drying were performed. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) as the fixer
Was used. Various performances were evaluated in the same manner as in Examples 1 and 2.

<Results> As in Example 1, by using the photosensitive material of the present invention and the developing solution, a photographic photosensitive material having high image quality and good processing stability could be obtained.

Example 5 A coating sample containing the hydrazine derivative of the present invention was prepared on the basis of the photosensitive material formulation of Example 5 of Japanese Patent Application No. 5-202547, and development processing was carried out in the same manner as in Examples 1 and 2. , Evaluated. As in Example 1 of the present specification, a good photographic light-sensitive material could be obtained.

Example 6 <Emulsion preparation> Emulsion C: 3 × 10 ⁻⁵ mol of the following compound (f) per mol of sodium chloride and silver kept at 40 ° C.
Containing 1.5% gelatin aqueous solution of pH = 2.0 containing silver nitrate solution and 3.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh per 1 mol of silver.
An aqueous sodium chloride solution containing (H ₂ O) Cl ₅ was simultaneously added by a double jet method at a potential of 95 mV for 3 minutes and 30 seconds to prepare core particles of 0.12 μm. Then, 10.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ per mol of gold and an aqueous solution of silver nitrate were used.
A sodium chloride aqueous solution containing Rh (H ₂ O) Cl ₅ was added in the same manner as above for 7 minutes to prepare silver chloride cubic particles having an average particle size of 0.15 μm. (Coefficient of variation 12%) After that, 4-hydroxy-6-methyl-1,3,3a,
1.5 × 10 ^{−3 of} 7-tetrazaindene per 1 mol of silver
Mol added. Further, after this, the product is washed with water by a flocculation method well known in the art to remove soluble salts, gelatin is added, and the following compound (g) and phenoxyethanol are added as preservatives without chemical ripening per mol of silver. 50 mg, 4-hydroxy-6-methyl- as stabilizer
1,3,3a, 7-Tetrazaindene was added at 3 × 10 ⁻³ mol per mol of silver (pH = 5.7, pAg = 7.
5, Rh = 6 × 10 ⁻⁵ mol / Ag mol).

<Preparation of Coating Solution for Emulsion Layer and Its Coating> Emulsion C
The following compound was added to the gelatin coating amount of 1.1 g /
m ^2, the coating amount of silver coated with silver halide emulsion layers so that 2.5 g / m ^2. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² compound (h) 10 mg / m ² compound (i) 20 mg / M ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² compound (j) (hardener) 150 mg / m ² Further nucleation accelerator ( k) was added at 20 mg / m ² , and a nucleating agent was added so as to be coated as shown in Table 3.

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer.

<Preparation and Coating of Emulsion Protecting Lower Layer Coating Liquid>
The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.7 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² compound (g) 5 mg / m ² compound (l) 10 mg / m ² compound (m) 20 mg / m ²

<Preparation of Emulsion Protection Upper Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8g / m ² amorphous silica matting agent 40 mg / m ² (average particle size 3.5 [mu], pore diameter 25 Å, surface area 700m ² / g) amorphous silica matting agent 10mg / m ² (average particle size 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine sympottadium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound (g) 5 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

<Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 77.
It was applied so as to be mg / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² Gelatin (Ca ⁺⁺ content 3000 ppm) 77 〃 Sodium dodecylbenzene sulfonate 10 〃 Sodium dihexyl-α-sulfosuccinate 40 〃 Polystyrene Sodium sulfonate 9〃 Compound (g) 7〃

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 2.92 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 2.92 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² Compound (h) 140 〃 Compound (r) 140 〃 Compound (s) 40 〃 Dodecyl Sodium benzene sulfonate 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound (t) 5 〃 N-perfluorooctane sulfonyl-N-propyl glycine potassium 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃

(Support, Undercoat Layer) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following compositions. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 〃 Polystyrene fine particles (average particle size 3 µ) 0.05 〃 Compound (u) 0. 20〃 colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12〃 Water added 100〃 Furthermore, 10 wt% KOH was added to adjust the coating solution to pH = 6. When the drying temperature is 180 ° C. for 2 minutes, the dry film thickness is 0.
It was applied so as to be 9μ.

<Undercoat Second Layer> Gelatin 1 Methylcellulose 0.05 〃 Compound (v) 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 〃 Compound (g) 3. 5 × 10 ⁻³ 〃 acetic acid 0.2 〃 water was added and 100 〃 This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

[0149]

[Chemical 34]

[0150]

[Chemical 35]

[0151]

[Chemical 36]

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The sample thus obtained was exposed by an optical wedge to a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and automatically developed by Fuji Photo Film Co., Ltd. Machine FG-680AG and Developer A of Example 1 were treated at 38 ° C. for 20 seconds, fixed, washed with water, and dried. The same fixing solution as in Example 1 was used. Evaluation of various performances was performed in the same manner as in Examples 1 and 2. <Results> It was possible to obtain a bright room return photosensitive material having a high gamma and good processing stability.

Example 7 Developer A of Example 1 was prepared from a pack stored in the solid state. In the method for manufacturing the pack of the solid processing agent, the components of the developing solution are solidly laminated and packed in a bag made of an aluminum foil coated with a plastic material. The order of stacking is from the top, 1st layer sodium erythorbate 2nd layer other components 3rd layer sodium bisulfite 4th layer potassium carbonate 5th layer potassium hydroxide pellets, evacuate in a conventional manner and vacuum the system. And sealed.

<Results> Even if a developing solution prepared from this solid processing agent was used in the development processing of Examples 1 to 6, Example 1 was used.
Similar results to ~ 6 were obtained.

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 5/29 G03C 5/31

Claims (4)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising a support having at least one silver halide emulsion layer, and the emulsion layer or another hydrophilic colloid layer containing a hydrazine derivative and a nucleation accelerator. Processing with a developer having a pH of 9.0 to 10.5 containing at least a first developing agent selected from ascorbic acid or a derivative thereof and a second developing agent selected from an aminophenol or a derivative thereof. In the method, a development processing method is characterized in that a solution having a pH higher than that of a development initiation solution is used as a development replenisher. ^2. The development processing method according to claim 1, wherein the replenishment amount of the development replenisher is 200 ml / m ² or less. 3. The developing starter solution and the developing replenisher contain 0.3 mol / liter or less of sulfite, and the replenishing amount of the developing replenisher is 150 ml / m ² or less.
Development processing method. 4. The pH of the replenisher is 0.3 than that of the development starter.
The development processing method according to claim 1, wherein the development processing method is high.