JP2001272754A - Method for processing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing a black-and-white silver halide photographic sensitive material which ensures stable photographic performance even in running processing over a long period of time, particularly processing under reduced replenishment. SOLUTION: A black-and-white silver halide photographic sensitive material having a built-in auxiliary developing agent containing a 1-phenyl-3-pyrazolidone derivative with a specified structure is processed by using a developing solution containing ascorbic acids as a developing agent (and not containing a dihydroxybenzene type developing agent) without incorporating an auxiliary developing agent comprising 1-phenyl-3-pyrazolidones.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a black-and-white silver halide photographic light-sensitive material, and more particularly, has a stable photographic performance even when running in an ascorbic acid type developer with a small amount of replenisher. The present invention relates to a method for processing a black-and-white silver halide photographic material.

[0002]

2. Description of the Related Art From the viewpoint of environmental protection, it has been proposed to use ascorbic acids instead of hydroquinones as developing agents. Conventionally, a developing solution using ascorbic acids as a developing agent has a longer running process stability than a developing solution using hydroquinones as a developing agent or an oxidizing reaction due to a characteristic of generating more acid during a developing reaction or an oxidizing reaction. In order to solve this problem, the pH of the developer has been lowered and a high concentration of a buffer (buffer) such as carbonate has been added. However, in this method, the running stability is insufficient, and in particular, the stability is insufficient when the amount of the developing replenisher is small, and improvement thereof has been demanded.

Further, Japanese Patent Application Laid-Open No. 11-338094 discloses a method in which 1-phenyl-3-pyrazolidones having a water-soluble group are contained in a light-sensitive material and processed with a developing solution containing ascorbic acids. I have. However, the photographic performance of the running process over a long period was still insufficient. Similarly, JP-A-10-394
According to the description of No. 60, reductones,
A method has been proposed in which a developing agent selected from 3-pyrazolidones and amiphenols is contained, and processing is carried out with a developer containing reductones, but this method is still insufficient.

On the other hand, environmental measures are being called out on a global scale, and with the ban on the dumping of waste liquid into the sea enacted in 1995, a reduction in the amount of replenishment aimed at reducing the amount of waste liquid has been studied and implemented. Among them, in a developing solution containing ascorbic acids as a developing agent, long-term running stability due to low replenishment is a major problem, and therefore, improvement is necessary.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing a black-and-white silver halide photographic material having stable photographic performance even when running for a long period of time. A further object is to provide a method for processing a black-and-white silver halide photographic material having stable photographic performance even when processed with a low replenisher volume.

[0006]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies on the low replenishment of a developer containing ascorbic acid as a developing agent, and as a result, have found that the low replenishment results in a decrease in the exchange rate of the developer in the developing tank. As a result, the present inventors have found that 1-phenyl-3-pyrazolidones which are used as an auxiliary developing agent and are present in a developing solution are destabilized, and studies for improvement have been made, and the present invention has been accomplished.

That is, the present invention is as follows. (1) A method of processing a black-and-white silver halide photographic material with a developer containing ascorbic acids as a developing agent and not containing a dihydroxybenzene-type developing agent, wherein the developer is 1-phenyl-3-pyrazolidone. Does not contain, the black and white silver halide photographic material,
A method for processing a black-and-white silver halide photographic material, comprising an auxiliary developing agent represented by the following formula (1) or (2).

[0008]

Embedded image

[In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group. X represents a substituent that can be substituted on a benzene ring;
Represents an integer of from 5 to 5. When m represents an integer of 2 or more, a plurality of Xs may be the same or different. Where R ₁
-R ₄ and the total number of carbon atoms of the m groups represented by X is
It is 3 or more and 30 or less, and the groups represented by R _{1 to} R ₄ and X are not substituted with a water-soluble group. In the formula (2), R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom, an alkyl group or an aryl group. Y represents a substituent that can be substituted on a benzene ring, and n represents an integer of 0 to 5. When n represents an integer of 2 or more, a plurality of Ys may be the same or different. R ₉ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamino group. Where R _{5 to} R ₈ , R
The total number of carbon atoms of the group represented by ₉ and n Y is 2 or more and 30 or less. (2) Processing is performed by replenishing the developing solution, and the replenishing solution for replenishment contains a carbonate, and the concentration of the carbonate is 0.1%.
4 mol / l or more and 1.2 mol / l or less, and this development replenisher is used in an amount of 50 to 350 mol / m ² of a black-and-white silver halide photographic material.
The method for processing a black-and-white silver halide photographic light-sensitive material according to the above (1), wherein ml is supplemented.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, a black-and-white silver halide photographic material is processed using a developing solution containing ascorbic acids having a low environmental load as a developing agent. Such a developer does not contain a dihydroxybenzene-type developing agent such as hydroquinone which is problematic in terms of toxicity and safety, and further does not contain an auxiliary developing agent such as 1-phenyl-3-pyrazolidone. It is. And preferably, it does not contain not only 1-phenyl-3-pyrazolidones but also other auxiliary developing agents such as aminophenols. On the other hand, a light-sensitive material used in combination with this is 1-phenyl-3-pyrazolidone (phenidone) having a specific structure represented by formula (1) or (2).
A photosensitive material containing a derivative and containing an auxiliary developing agent. Thus, the developing solution of the present invention comprises 1-phenyl-3
-Since it does not contain pyrazolidones, it is possible to prevent deterioration of the performance of the developing solution caused by the instability of this compound during long-term running processing, especially low replenishment processing, thereby improving photographic performance. Deterioration can be prevented and stable photographic performance can be obtained. Therefore, good photographic performance obtained by incorporating the compounds of the formulas (1) and (2) into the light-sensitive material can be maintained for a long time.

The developing solution used in the present invention does not contain a dihydroxybenzene type developing agent and an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, and the content of these compounds is 10 ^-4 mol / l. Liters or less, preferably zero. The developing agent and auxiliary developing agent used in the developer are only ascorbic acids. That is, the compound is not actively added to the mother liquor or replenisher of the developer. The compound of formulas (1) and (2) (1-phenyl-
The amount of the 3-pyrazolidone derivative) eluted by the running treatment is almost nonexistent, and within the above range even if it is very slight.

The developing agents of ascorbic acids include sodium erythorbate, L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, D-glucoascorbic acid, 6-deoxy-L-ascorbic acid and L-rhamnoic acid. Ascorbic acid, D-glucoheptoascorbic acid, imino-L-erythroascorbic acid, imino-D-glucoascorbic acid, imino-6-deoxy-L-ascorbic acid, imino-D-glucoheptoascorbic acid, isoascorbin Acid sodium (sodium erythorbate), L-glycoascorbic acid, D
-Galactascorbic acid, L-araboascorbic acid, sorbascorbic acid, sodium ascorbate, and the like.

These ascorbic acid-based developing agents may be used alone or in combination of two or more.

The content of these developing agents is 0.05 to 0.5 mol / l per liter of working solution.
More preferably, it is 0.1 to 0.4 mol / liter.

The sulfite used in the developer of the present invention includes sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and the like. The sulfite is used in an amount of 0.01 mol / liter or more, particularly 0.03 mol /
Liter or more is preferred. The upper limit is preferably up to 2.5 mol / l, especially up to 1.2 mol / l.

The developing solution of the present invention may contain a compound described in US Pat. No. 5,474,879 for accelerating the development. Further, an amino compound may be contained, and in particular, JP-A-56-106244, JP-A-61-267759, and Japanese Patent Application No. 1-29.
The amino compound described in No. 418 may be used.

The pH value of the developer used in the present invention is preferably 11.0 or less. In particular, it is preferably 10.5 or less. As the alkali agent used for setting the pH value, a common water-soluble inorganic alkali metal salt, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, or the like can be used. It is particularly preferable to contain a carbonate, and the carbonate in the working solution is at least 0.3 mol / L and at most 1.5 mol / L, particularly at least 0.4 mol / L and at least 1.2 mol / L.
It is preferable to use it at a mole / liter or less. This amount is the same in the developing replenisher.

The developer of the present invention may further include a pH buffer such as boric acid, borax, sodium diphosphate, potassium diphosphate, sodium monophosphate, potassium monophosphate, and the like. The pH buffers described in JP-A-60-93433 can be used; development inhibitors such as potassium bromide and potassium iodide, and organics such as dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol. Solvent: 5 as the benztriazole derivative
Examples include -methylbenztriazole, 5-bromobenztriazole, 5-chlorobenztriazole, 5-butylbenztriazole, and benztriazole, with 5-methylbenztriazole being particularly preferred.

Further, if necessary, a color tone agent, a surfactant, a water softener, a hardener and the like may be contained. As the toning agent, those described in Japanese Patent Application No. 7-176909 can be used.

The following compounds are listed as chelating agents in the developer. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid,
-Hydroxyethylidene-1,1-diphosphonic acid, 1,
1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, Examples thereof include sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid. 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydro Shipuropiriden 1,1-diphosphonic acid, 1-amino-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof. Further, a chelating agent having good biodegradability described in Japanese Patent Application No. 9-266799 can be used.

In addition, the developer of the present invention may contain a dialdehyde hardener or a bisulfite adduct thereof. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleic dialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α -N-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, and bisulfite adducts thereof. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time is not significantly increased. Specifically, the amount is 1 to 50 g, preferably 3 to 10 g, per liter of the developing solution (used solution). Among them, glutaraldehyde or its bisulfite adduct is most commonly used. However, when a bisulfite adduct of a dialdehyde hardener is used, the bisulfite of this adduct is also calculated as a sulfite in the developer. However, it is preferable that the light-sensitive material to be used is previously hardened, and that a dialdehyde hardener is not used in the developer.

In addition, L. F. A. Using the additives described in Mason, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-64933. You may.

In the present invention, the above-mentioned developing solution (working solution) is used as a replenishing solution for development in the range of 50 ml to 3 ml per m ² of the light-sensitive material.
It is preferable to carry out the development processing while replenishing in the range of 50 ml.

As the developing solution to be poured into the developing tank of the automatic developing machine at the beginning of development, a solution having the same composition as the above-mentioned developing solution or a solution having a partially changed composition may be used.

The fixing solution used in combination with the above-mentioned developing solution is an aqueous solution containing thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 6.0.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to about 3 mol / l.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like. Tartaric acid, citric acid, gluconic acid or derivatives thereof 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 or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective.

The fixing solution may optionally contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, succinic acid,
Acetic acid, boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water and a compound described in JP-A-62-78551.

Commercially available fixing solutions may be used, for example, Fuji-F, CE-F1, CE-F4, and R-F, manufactured by Fuji Photo Film Co., Ltd.
F-10 and HiRen-Fix.

In the processing method of the present invention, after the development and fixing steps, the film is treated with washing water or a stabilizing solution, and then dried.

As an automatic developing machine (automatic developing machine) for processing the photosensitive material, various types such as a roller conveying type and a belt conveying type can be used, but a roller conveying type automatic developing machine is preferable. Japanese Patent Application Laid-Open No. 1-166040 and Japanese Patent Application No. 63-1
Use of a developing machine having a small opening ratio as described in JP-A-8631 reduces air oxidation and evaporation, enables stable operation in a processing environment, and further reduces the amount of replenisher. .

As a method for reducing the amount of replenisher for washing water, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. If this multi-stage countercurrent method is applied, the photosensitive material after fixing is gradually processed in a clean direction, that is, a processing solution that is not stained with the fixing solution is sequentially contacted, so that more efficient water washing is performed. You.

In the water-saving treatment or the non-pipe treatment, it is preferable to provide a means for preventing the washing water or the stabilizing solution.

Japanese Patent Laid-Open No. Sho 60-263 discloses a means for preventing erosion.
No. 939, No. 60-26394.
Method using magnetic field described in No. 0, 61-13163
No. 2, a method of making pure water using an ion exchange resin, JP-A Nos. 61-115154 and 62-15395.
No. 2, Japanese Patent Application No. 61-63030 and No. 61-51396
The method using the antibacterial agent described in the above item can be used in combination.

Further, LFWest, "Water Qulity Crit
eria "Photo.Sci. & Eng., Vol.9, No.6 (1965), MWBea
ch, "Microbiological Growths in Motion-picture Proc
essing "SMPTE Journal Vol.85 (1976), RDDeegan," Ph
oto Processing Wash WaterBiocides "J. Imaging Tec
h., Vol. 10, No. 6 (1984) and JP-A-57-8542.
No. 57-58143, No. 58-105145,
57-132146, 58-18631, 5
Antibacterial agents, antibacterial agents, surfactants, and the like described in JP-A-7-97530 and JP-A-57-157244 can also be used in combination.

Further, a washing bath or a stabilizing bath may include RT.
Research Disclosure, an isothiazoline compound described in Kreiman, J. Image.Tech., 10 (6) p. 242 (1984).
Vol. 205, No. 20526 (May 1981), published isothiazoline compounds, Vol. 228, No. 22845 (1983, 4
), Japanese Patent Application No. Sho 6
Compounds described in No. 1-51396 are used as antibacterial agents (Mic
robiocide).

In addition, it is described in "The Chemistry of Bactericidal and Fungicide" by Hiroshi Horiguchi, Mitsui Publishing (Showa 57), "Handbook of Bacterial and Fungicide Technology", Japan Society of Bacteria and Bacteria, Hakuhodo (Showa 61). May be included.

When washing with a small amount of washing water, see
It is more preferable to provide a squeeze roller washing tank described in No. 3-18350. Also, JP-A-63-1435
It is preferable to adopt a configuration of a washing step as in No. 48.

Further, part or all of the overflow from the washing or stabilizing bath caused by replenishment of the water subjected to the means for preventing the washing or stabilizing bath according to the treatment is described in JP-A-60-235133. As described, it can be used for a processing solution having a fixing ability, which is the preceding processing step.

In the present invention, the term "development step time" or "development time" refers to the time from when the leading end of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine until it is immersed in the next fixing liquid. "Fixing time" is the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution),
"Washing time" refers to the time of immersion in the washing tank liquid.

The term "drying time" generally refers to a drying zone in which hot air of 35 ° C to 100 ° C, preferably 40 ° C to 80 ° C is blown, or 150 ° C to 500 ° C.
Drying zone drying with a radiant object, or 90 ° C-1
A drying zone or the like for drying with a heat transfer body at 20 ° C. is provided, and the time during which the user enters the drying zone. The drying zone for radiating objects and heat transfer bodies is described in
No. 173279, No. 4-159550, No. 3-25
No. 3855 and the like.

In the development processing in the present invention, the development time is 5 seconds to 1 minute, preferably 8 seconds to 30 seconds, and the development temperature is preferably 18 ° C. to 50 ° C., more preferably 20 ° C. to 40 ° C.

The fixing temperature and time are preferably about 18 ° C. to 50 ° C. for 5 seconds to 1 minute, more preferably 20 ° C. to 40 ° C. for 6 seconds to 30 seconds. Within this range, sufficient fixing can be performed, and the sensitizing dye can be eluted to such an extent that no residual color is generated.
The replenishing amount of the fixing solution may be the same as that of the developing solution.

The temperature and time in the washing (or stabilizing bath) are preferably from 0 to 50 ° C. for 6 seconds to 1 minute, and from 15 ° C. to 4 minutes.
6 seconds to 30 seconds at 0 ° C. is more preferred.

The developed, fixed and washed (or stabilized) photosensitive material is squeezed with washing water, that is, dried through a squeeze roller. Drying is about 40 ° C to about 100
C., and the drying time may be appropriately changed depending on the surrounding conditions, but is usually about 5 seconds to 1 minute, particularly preferably 40 to 80.degree. C. for about 5 seconds to 30 seconds.

When rapid processing with a total processing time (Dry to Dry) of 100 seconds or less is performed in the light-sensitive material / processing system of the present invention, Japanese Patent Application Laid-Open No.
A roller made of a rubber material as described in Japanese Patent Application Laid-Open No. 3-151943 may be used as a roller at the outlet of a developing tank, or a developer may be stirred in a developing tank as described in Japanese Patent Application Laid-Open No. 63-151944. Discharge flow rate for
0 m / min or more.
As described in JP-A-758-758, it is more preferable to perform stronger stirring at least during development processing than during standby. For more rapid processing, the configuration of the roller of the fixing tank is more preferably an opposing roller to increase the fixing speed. By using the opposing rollers, the number of rollers can be reduced, and the processing tank can be reduced. That is, it is possible to make the self-developing machine more compact.

Examples of the automatic developing machine suitable for performing the developing process of the present invention include FPM-9000, CE manufactured by Fuji Photo Film Co., Ltd.
PROS-M2, CEPROS-30, CEPROS-S, CEPROS-SV, CEPROS-
P, FPM-800A, FL-IMD and the like.

The phenidone derivatives represented by the formulas (1) and (2) used in the black-and-white silver halide photographic material of the present invention will be described.

[0049]

Embedded image

In the formula (1) or (2), the substituent which can be substituted on the benzene ring represented by X or Y includes, for example, a halogen atom, an alkyl group (including a cycloalkyl group),
Alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, acylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, Hydroxy group, alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy group), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyl Oxy group, amino group,
(Alkyl, aryl, or heterocyclic) amino group, acylamino group, ureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, acylureido group, nitro group, mercapto group, (Alkyl, aryl,
Or heterocycle) thio group, (alkyl or aryl)
A sulfonyl group, a group containing a phosphoric acid amide or a phosphoric ester structure, and the like.

These substituents may be further substituted with these substituents.

In the formula (1) or (2), R _l
The alkyl group represented by to R ₄ or R ₅ to R _8, linear or branched, substituted or unsubstituted alkyl group, examples of the substituent, mentioned above, in the formula (1) or (2) X or Y
Examples of the substituents that can be substituted on the benzene ring represented by are as they are.

In the formula (1) or (2), R _l
The aryl group represented by -R ₄ or R ₅ -R ₈ is specifically preferably a phenyl group or a naphthyl group, and these may have an arbitrary substituent. Examples of the above-mentioned substituents that can be substituted on the benzene ring represented by X or Y in the formula (1) or (2) can be given as they are.

However, in the formula (1), R _{1 to} R ₄ and m
The total number of carbon atoms of the groups represented by X is 3 or more and 30 or less, and these groups are not substituted with a water-soluble group. Here, the water-soluble group is a carboxy group (—COO
H) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a sulfonamide group, a sulfamoyl group, and a polyhydroxyalkyl group.

In the formula (2), R ₉ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, or an arylamino group. These groups may have a substituent, and examples of the substituent include those described above as the substituents that can be substituted on the benzene ring represented by X or Y in the formula (1) or (2). An example is given as is.

The preferred range of the phenidone derivative used in the black-and-white silver halide photographic light-sensitive material of the present invention will be described.

In the formula (1), R_l~ R_FourIs preferably
It is a hydrogen atom, an alkyl group, or a phenyl group. R_l~
R_FourWhen represents an alkyl group, preferred as the substituent
Represents a hydroxy group, an acyl group, an oxycarbonyl group,
Rubamoyloxy group, sulfonyloxy group, amino group,
Heterocyclic group, phenyl group, alkoxycarbonyloxy
And acyloxy groups. Also, R_l~ R_FourIs
When representing an enyl group, the substituent is preferably alkenyl
Coxy group, hydroxy group, acylamino group, halogen source
(Particularly a chloro atom) and an alkyl group. formula
In (1), R _l~ R_FourIs particularly preferably a hydrogen source
, A methyl group, a substituted methyl group (eg, hydroxymethyl
Group, acyloxymethyl group, alkoxycarbonyloxy
A unsubstituted phenyl group.

In the formula (2), the preferred range of R _{5 to} R ₈ is the same as the preferred range of R _{1 to} R _{4 in} the formula (1). R ₉
Is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group.

In the formula (1), X is preferably an alkyl group, a halogen atom (particularly a chloro atom), an acylamino group, a carbamoyl group, an alkoxy group, a ureido group, an alkoxycarbonyl group or an aryloxycarbonyl group. m is preferably 0, 1 or 2.

In the formula (2), the preferable range of Y is the same as the preferable range of X in the formula (1). n is preferably
It is 0, 1 or 2.

In the formula (1), R _{1 to} R ₄ and m Xs
The total number of carbon atoms of the group represented by is 3 or more and 30 or less, preferably 5 or more and 20 or less, more preferably 5 or more and 16 or less.

In the formula (2), the total number of carbon atoms of R ₉ , R _{5 to} R ₈ , and n groups represented by Y is 2 or more and 30 or less, preferably 5 or more and 20 or less. Or less, more preferably 5 or more and 16 or less.

Next, with respect to the phenidone derivative of the present invention,
Specific examples of the compounds will be given, but the present invention is not limited to these.

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

The phenidone derivative of the present invention can be synthesized by a known method. For example, Journal of Chemical Society (J. Chem. Soc.), P. 408 (1954), U.S. Pat. No. 2,743,279 (1953), and U.S. Pat.
Year), or a method analogous thereto.

These compounds can be added to either the emulsion layer or the protective layer.

The addition amount of these is preferably from 1 × 10 ^-5 mol to 1 × 10 ^-1 mol per mol of silver halide.

The phenidone derivative of the present invention may be contained in a coating solution by any method such as a solution form (for example, a methanol solution or an aqueous solution), an emulsified dispersion form, or a solid fine particle dispersion form. It can be contained in the material.

The black-and-white silver halide photographic light-sensitive material of the present invention is not particularly limited, but is preferably a medical X-ray film for direct or indirect photography, a medical CRT image photographic material, an industrial X-ray film. Ray photographic materials, X-ray duplicate photographic materials, and ultra-high contrast photographic materials for graphic arts are preferred. These are described in JP-A-5-232.
No. 639, JP-A-63-136043, JP-A-4-3
No. 28737, No. 4-107442, No. 5-7267
No. 9, 7-77781, 7-13306, 7
-84343.

A silver halide photographic material having an aspect ratio of silver halide grains of 3.0 or more, which can be used in the present invention, will be described. The diameter of a sphere having the same volume as the tabular emulsion grains is preferably 0.2 μm or more and less than 2.0 μm, and more preferably 0.5 μm or more and 1.5 μm or less.
Preferably, it is less than m. The particles have a particle thickness of 3
Twice or more tabular grains are preferably used in the present invention. The upper limit of the aspect ratio is preferably 15.
For details, see RESEARCH DISCLOSURE Volume 225, Item 225
34, pages 20 to 58, January, 1983, and JP-A-58-127921 and JP-A-58-113926. The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are described in
It can be easily prepared by referring to the methods described in Japanese Patent No. 127921, JP-A-58-113927, JP-A-58-11392 and U.S. Pat. No. 4,439,520.

In order to effectively utilize the effects of the present invention,
As the selenium sensitizer, a selenium compound disclosed in a conventionally known patent can be used. The non-labile selenium compound used in the present invention is disclosed in JP-B-46-45.
No. 53, JP-B No. 52-34492 and JP-B No. 52-
The compound described in No. 34491 is used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof.

Examples of the silver halide solvent which can be used in the present invention include US Pat. Nos. 3,271,157 and 35.
No. 31289, No. 3574628, JP-A-54-1
(A) Organic thioethers described in JP-A Nos. 019 and 54-158917;
(B) thiourea derivatives described in JP-A Nos. 55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group interposed between an oxygen or sulfur atom and a nitrogen atom described in JP-A-19, (d) imidazoles described in JP-A-54-100717, e) sulfites, and (f) thiocyanate. Particularly preferred solvents include
There are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferred amount is
It is not less than 1 × 10 ⁻⁴ mol and not more than 1 × 10 ⁻² mol per mol.

The silver halide photographic emulsion used in the present invention is
Higher sensitivity and lower fog can be achieved by using sulfur sensitization and / or gold sensitization together in chemical sensitization. Sulfur sensitization is usually performed by adding a sulfur sensitizer,
This is carried out by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Further, gold sensitization is usually performed by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Known sulfur sensitizers can be used for the above sulfur sensitization. For example, thiosulfates, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like can be mentioned. In addition, US Pat.
No. 44, No. 2410689, No. 2278947
No. 2,728,668, No. 350313, No. 3,656,955, German Patent No. 14222869
No., JP-B-56-24937, JP-A-55-4501.
Sulfur sensitizers described in, for example, Japanese Unexamined Patent Publication No. 6 (1994) can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount depends on pH, temperature,
It varies over a considerable range under various conditions such as the size of silver halide grains, but is preferably from 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds usually used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, it is preferably 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.

In order to effectively utilize the effects of the present invention,
During chemical sensitization during the emulsion preparation step as described in JP-A-2-68539, it is preferred that 0.5 mmol or more of a silver halide-adsorbing substance is present per 1 mol of silver halide. This silver halide-adsorbing substance may be added at any time, such as during grain formation, immediately after grain formation, or before or after the start of post-ripening. It is preferably added before the chemical sensitizer is added, or at the same time as the chemical sensitizer, and it must be present at least during the course of chemical sensitization. As a condition for adding the silver halide-adsorbing substance, the temperature may be any temperature in the range of 30 ° C to 80 ° C, but is preferably in the range of 50 ° C to 80 ° C for the purpose of enhancing the adsorptivity. The pH and pAg may be arbitrarily set, but are preferably 5 to 10 and pAg 7 to 9 at the time of chemical sensitization.

Here, the silver halide-adsorbing substance means a sensitizing dye or a photographic performance stabilizer. That is, azoles {eg, benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc .; mercapto compounds {eg, mercaptothiazoles, Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines and the like; Thioketo compounds; azaindenes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) Tiger aza indene), pentaazaindenes such like); known as antifoggants or stabilizers, such as may include many of the compounds as silver halide adsorptive materials. Further, purifying substances or nucleic acids, or high molecular compounds described in JP-B-61-36213, JP-A-59-90844, and the like are also adsorptive substances that can be used.

As a silver halide-adsorbing substance, a sensitizing dye can realize a preferable effect. As sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, and the like can be used. Useful sensitizing dyes for use in the present invention are described, for example, in U.S. Patent Nos. 3,352,052, 3,619,197, 3,713,828 and 36.
15643, 3615632, 3617293, 3628964
No. 3703377, No. 3666480, No. 3667960, No. 36
79428, 3672897, 3769026, 3556800
Nos. 3615613, 3615638, 3615635, 37
05809, 3632349, 3677765, 3770449
Nos. 3770440, 3769025, 3745014, 371
3828, 3567458, 3625698, 2526632
No. 2503776, JP-A-48-76525, Belgian Patent No.
It is described in 691807 and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic characteristics (eg, development acceleration, hardener For various purposes such as sensitization), various surfactants may be contained.

Gelatin is advantageously used as a binder or protective colloid which can be used in the emulsion layer, intermediate layer and surface protective layer of the light-sensitive material used in the present invention, but other hydrophilic colloids are also used. be able to.
For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate, dextran and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and hydrolyzate or enzyme-decomposed product of gelatin can also be used. Among these, it is preferable to use dextran or polyacrylamide having an average molecular weight of 50,000 or less together with gelatin. JP-A-63-68837,
The method described in JP-A-63-149641 is also effective in the present invention.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener.
For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc. Compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid and mucofenoxycyclolic acid), isoxazoles, dialdehyde starch, and 2-chloro-6-hydroxytriazinyl Gelatin and the like can be used alone or in combination. Among them, JP 53-4
No. 1221, No. 53-57257, No. 59-1625
Preferred are the active vinyl compounds described in Nos. 46 and 60-80846 and the active halides described in U.S. Pat. No. 3,325,287.

The hydrophilic colloid layer in the photographic light-sensitive material of the present invention is preferably hardened by these hardeners so that the swelling ratio in water is 250% or less. The swelling ratio in water is measured by a freeze-drying method. That is, the photographic material is 2
The swelling ratio of the hydrophilic colloid layer is measured at the time when 7 days have passed under the conditions of 5 ° C. and 60% RH. The dry thickness (a) is determined by a scanning electron microscope of the section. The swelled film thickness (b) is determined by immersing the photographic material in distilled water at 21 ° C. for 3 minutes, freeze-drying with liquid nitrogen, and then observing it with a scanning electron microscope. The swelling ratio is a value (%) that is 100 times the value of {(b)-(a)} divided by (a). In this case, the lower limit of the swelling ratio is 70%. The preferred swelling ratio is 100
% To 200%. When the swelling ratio is less than 70%, the sensitivity becomes low, and when the swelling ratio exceeds 250%, it is not realistic from the viewpoint of drying properties. This is because the membrane is damaged.

The emulsion layer of the photographic light-sensitive material can contain a plasticizer such as a polymer or an emulsion in order to improve the pressure characteristics. For example, British Patent No. 736618 describes a heterocyclic compound, US Pat. No. 736637 describes an alkyl phthalate, US Pat. No. 7,386,39 describes an alkyl ester, US Pat. No. 2,960,404 describes a polyhydric alcohol, and US Pat.
No. 1060, a carboxyalkyl cellulose, JP-A-49-5017, a paraffin and a carboxylate,
JP-A-53-28086 discloses a method using an alkyl acrylate and an organic acid. Other constitutions of the emulsion layer of the silver halide photographic light-sensitive material of the present invention are not particularly limited, and various additives can be used as needed. For example, binders, surfactants, other dyes, coating aids, thickeners described in Research Disclosure 176, pp. 22-28 (December 1978),
Etc. can be used.

In the silver halide photographic material having a photographic emulsion layer on both sides, there is a problem that the image quality is easily deteriorated by crossover light. The crossover light is emitted from the respective intensifying screens arranged on both sides of the photosensitive material, passes through a support of the photosensitive material (usually a thick one having a thickness of about 170 to 185 μm is used), and is exposed to light on the opposite side. Visible light that reaches the layer and reduces the image quality (especially sharpness).

The smaller the crossover, the sharper the image. Although there are various methods for reducing the crossover, the most preferable method is to fix a decolorable dye between the support and the photosensitive layer by a development treatment. The use of microcrystalline dyes taught in U.S. Pat.
It has good bleaching properties and can contain a large amount of dye, which is very preferable for reducing crossover. According to this method, there is no desensitization due to improper fixation, the dye can be decolorized by rapid processing, and the crossover can be reduced to 15% or less.

The dye layer for reducing crossover is more preferably a layer in which dyes are arranged as densely as possible. It is preferable that the amount of gelatin used as a binder is reduced and the thickness of the dye layer is 0.5 μm or less. However, extreme thinning tends to cause poor adhesion, and the most preferable thickness of the dye layer is 0.05 μm to
0.3 μm.

Emulsions such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide or silver chloroiodobromide emulsions are described in "Photochemistry and Physics" by P. Glafkides (Paul Montell) ,
1967), "The Chemistry of Photographic Emulsions" by GF Duffin (Duffin) (Focal Press, 1966);
It can be prepared by applying the method described in "Preparation and Coating of Photographic Emulsion" by L. Zelikman et al. (Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, but an acidic method and a neutral method are particularly preferable in the present invention in terms of reducing fog. In order to obtain a silver halide emulsion by reacting a soluble silver salt with a soluble halogen salt, any one of a so-called single-sided mixing method, a double-sided mixing method, and a combination thereof may be used. A so-called back-mixing method in which grains are formed under conditions of excess silver ions can also be used. In order to obtain an emulsion of monodisperse grains which is preferable for the present invention, it is preferable to use a double jet method. As one type of the double jet method, it is more preferable to use a method of keeping a silver ion concentration in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method.
By using this method, a silver halide emulsion having a regular silver halide crystal shape and a narrow grain size distribution can be obtained.

To form high silver chloride grains, see JP-A-2
No. -32, No. 3-137632, No. 4-6546,
Methods using bispyridinium compounds described in JP-A-5-127279 and JP-A-5-53231, and
293536, JP-A-1-155332, JP-A-6
Nos. 3-2043 and 63-25643, U.S. Pat.
The methods described in Nos. 400463 and 5061617 can be preferably used.

In the course of such silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt as described above. Alternatively, a complex salt thereof may coexist.

During or after grain formation, a silver halide solvent (for example, as a known solvent, ammonia, thiocyanate, US Pat. No. 3,271,157;
No. 12360, JP-A-53-82408, JP-A-53-82408
-144319, JP-A-54-100717, JP-A-54-155828, and the like) may be used. To obtain a silver halide emulsion having a narrow grain size distribution.

The amount of silver applied is preferably not more than 3.5 g / m ^{2 on} both sides per 1 m ² of the support. The lower limit is not particularly limited, but is about 0.1 g / m ² .

The black-and-white photographic light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styrine dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As a support for a photographic light-sensitive material, 150 to
It must have a thickness of 250 μm. This is indispensable from the viewpoint of handleability when observing on a medical shakasten. The material is preferably a polyethylene terephthalate film, particularly preferably colored blue.

The surface of the support is preferably subjected to a corona discharge treatment, a glow discharge treatment or an ultraviolet irradiation treatment in order to improve the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex, or the like may be provided, and a gelatin layer may be further provided thereon.

Further, an undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided.

The undercoat layer can be further improved in adhesion to the hydrocolloid layer by applying a surface treatment.

As various additives used in the photographic light-sensitive material of the present invention, those described in the following applicable places can be used.

Item The present section 1) Chemical sensitization method JP-A-2-68539, page 10, line 13 from the upper right column to line 16 in the upper left column, JP-A-5-313282 (Japanese Patent Application No. 3-105035) issue). 2) Antifoggants, JP-A-2-68539, page 10, lower left column, line 17 to stabilizer Stabilizer, page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 3) Color tone improver JP-A-62-276439, page 2, lower left column, line 7 to page 10, page 10 lower left column, line 20, JP-A-3-94249, page 6 lower left column, line 15 to line 11 Line 19 in the upper right column of the page. 4) Surfactant, JP-A-2-68539, page 11, upper left column, line 14 to antistatic agent, page 12, upper left column, line 9; 5) Matting agent, sliding From page 12, upper left column, line 10 in JP-A-2-68539, agents and plasticizers: line 10 in the upper right column, line 10 from line 10 in the lower left column, page 14: line 1 in the same column. 6) Hydrophilic colloids JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16; 7) Hardener From page 17, lower left column, line 17 to page 13, upper right column, line 6 of JP-A-2-68539. 8) Polyhydroxyl JP-A-3-39948, page 11, upper left column to page 12, benzenes, lower left column, EP Patent No. 452772A. 9) Layer structure JP-A-3-19841

[0102]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 First, the following photosensitive material was prepared.

Light-sensitive material: having a silver halide emulsion layer containing tabular silver halide grains having an aspect ratio of 3.0 or more at 80% of the projected area of all silver halide grains, and having a swelling ratio of 1
What was 50% was made as follows.

Preparation of emulsion 20 g of gelatin, 5 g of potassium bromide in 1 liter of water,
3 ml of a 5% (mass percentage) aqueous solution of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH was added, and 8.35 g of silver nitrate was stirred into the aqueous solution kept at 75 ° C. An aqueous solution containing an aqueous solution, 3 g of potassium bromide, and 0.4 g of potassium iodide was added by a double jet method in 45 seconds. Subsequently, after adding 2 g of potassium bromide, an aqueous solution containing 5 g of silver nitrate was added over 10 minutes. Subsequently, an aqueous solution of 135 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining the potential at pAg 8.1.
The flow at this time was accelerated so that the flow at the end of the addition was 10 times the flow at the start of the addition. 2mol / l after completion of addition
15 ml of a (2N) potassium thiocyanate solution was added.
Thereafter, the temperature was lowered to 35 ° C., and soluble salts were removed by a sedimentation method. Then, the temperature was raised to 40 ° C., and 35 g of gelatin, 2.5 g of phenoxyethanol and a thickener were added. At pH
It adjusted to 6.1, pAg 8.3. After the temperature was raised to 56 ° C., 735 mg of a sensitizing dye having the following structure was added. 10
After minutes, Ph ₃ P = Se was added at 0.96 × 10 ⁻⁵ mol / mol Ag, sodium thiosulfate was added at 0.64 × 10 ⁻⁵ mol / mol Ag, potassium thiocyanate was added at 110 mg, and chloroauric acid at 2.6 mg was added. And aged for 60 minutes. Thereafter, it was quenched and solidified.

[0105]

Embedded image

In the obtained emulsion, 93% of the total projected area of all grains consisted of grains having an aspect ratio of 3.0 or more, and the average projected area diameter of all grains having an aspect ratio of 3.0 or more was 1 It had a standard deviation of 20% at 0.4 μm, an average thickness of 0.2 μm and an average aspect ratio of 7.

Using the above emulsion, a light-sensitive material as a coating sample having the following form was prepared. The coating amounts shown below are amounts per 1 m ² of the photosensitive material.

Preparation of Coating Sample The following chemicals per mole of silver halide were added to prepare a coating solution. Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 20 g 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg potassium hydroquinone monosulfonate 9 g gelatin (coating amount) There 1.0 g / m ² and comprising an amount added) trimethylolpropane 9g sodium polyacrylate (average molecular weight 41,000) 2.1 g sodium polystyrenesulfonate (average molecular weight 600,000) 1.5 g

Hardening agent 1,2-bis (vinylsulfonylacetamido) ethane (adjusted amount so that swelling ratio becomes a value of 150%) The following compound 34 mg

[0110]

Embedded image

Preparation of Coating Solution for Surface Protective Layer The surface protective layer was prepared and prepared so that each component had the following coating amount. Content of surface protective layer Coating amount Gelatin 0.966 g / m ² Sodium polyacrylate (average molecular weight: 400,000) 0.023 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0 .015 g / m ²

[0112]

Embedded image

Polymethyl methacrylate (average particle size: 3.7 μm) 0.087 g / m ² Proxel (adjusted to pH 7.4 with NaOH) 0.0005 g / m ²

Preparation of Support (1) Preparation of Dye for Undercoat Layer The following dyes were ball-milled by the method described in JP-A-63-197943.

[0115]

Embedded image

434 ml of water and 791 ml of a 6.7% (percent by mass) aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. Dye 2
0 g was added to this solution. Zirconium oxide (ZrO ₂
) Was added and the contents were ground for 4 days. This was followed by the addition of 160 g of 12.5% (mass percent) gelatin. After defoaming, Zr is filtered.
O ₂ beads were removed. Observation of the obtained dye dispersion showed that the particle size of the crushed dye was 0.05 to 1.1 in diameter.
It had a broad distribution down to 5 μm, with an average particle size of 0.30 μm.

Further, by performing the centrifugation operation, 0.9% was obtained.
Dye particles having a size of μm or more were removed. Thus, a dye dispersion was obtained.

(2) Preparation of Support A corona discharge treatment was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoating liquid having the following composition was applied in an amount of 5.1 ml / m ² . And apply it with a wire bar coater.
Dried for minutes.

Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained a dye having the following structure at 0.04% (mass percentage).

[0120]

Embedded image

Butadiene-styrene copolymer latex solution (solid content 40% (mass percentage) butadiene / styrene mass ratio = 31/69) 79 ml 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% ( (Mass percentage) solution 20.5 ml distilled water 900.5 ml

In the latex solution, the following compound as an emulsion dispersant was added in an amount of 0.4% based on the solid content of the latex.
(Mass percentage).

[0123]

Embedded image

A second undercoating layer having the following composition was coated on each of the first undercoating layers on both sides by a wire bar coder method so that the coating amount was as described below. Coated and dried at ℃.

Gelatin 160 mg / m ² Dye dispersion (26 mg / m ² as a dye solid content)

[0126]

Embedded image

Matting agent Preparation of 2.5 mg / m ^{2 of} polymethyl methacrylate having an average particle size of 2.5 μm The above emulsion layer and surface protective layer were coated on both sides of the prepared support by a simultaneous extrusion method. The amount of silver applied per side was 1.30 g / m ² . The amount of gelatin applied and the swelling ratio determined by freeze-drying with liquid nitrogen were set by adjusting the amount of gelatin added to the emulsion layer and the amount of hardener. Thus, a light-sensitive material was prepared.

In addition, as shown in Table 1, a light-sensitive material was prepared in which an auxiliary developing agent was contained in the emulsion layer. The auxiliary developing agent was prepared as a methanol solution and added to the emulsion layer coating solution so that the amount of the photosensitive material shown in Table 1 was added.

Next, the developer formulation used in the present invention will be described.

Developer Replenisher Formulation-A Diethylenetriaminepentaacetic acid 2.0 g Potassium carbonate 96.6 g Sodium sulfite 16.9 g Potassium metabisulfite 7.1 g Erythorbic acid / sodium monohydrate 45.0 g Potassium bromide 2.0 g 5-methylbenztriazole 0.06 g 3,3'-dithiobishydrocinnamic acid 0.4 g 1 liter by adding water (pH 10.40)

Developer Replenisher Formulation-B Developer Replenisher Formulation A was prepared by adding 2.0 g of 1-phenyl-3-pyrazolidone and 40.0 g of triethylene glycol as a solvent for the same (pH 10.40). .

As a starter, a solution of 4.5 g of acetic acid and 4.6 g of potassium bromide in 25 ml per liter of a working solution was added to each formulation of the developer replenisher and added thereto, respectively. Developer mother liquor-A (pH 10.20), developer Mother liquor-B (pH 1
0.20).

Combinations of photosensitive materials and developing solutions (mother liquor and replenisher) were combined as shown in Table 1 and 1.5 m ^{2 /} day using an automatic processor CEPROS-SV manufactured by Fuji Photo Film Co., Ltd. Of the light-sensitive material, and ran for two months.

The replenishment amount of the developing replenisher was 194 ml per m ^{2 of} the photographic material. The fixing solution used was CE-F2 manufactured by Fuji Photo Film Co., Ltd., and the replenishing amount was the same as that of the developing solution. The running water was used for washing. The processing conditions are as follows.

[0135]

The sensitivity at the start of running and after running for two months was evaluated. Table 1 shows the results. The sensitivities in the table are obtained when a photosensitive material containing no auxiliary developing agent was developed as a developing solution mother liquor-B formulation containing the auxiliary developing agent 1-phenyl-3-pyrazolidone (Experiment No. 1).
Are shown as relative values when the reciprocal of the exposure amount necessary to obtain the blackening density of 1.0 is set to 100.

[0137]

[Table 1]

As shown by the results, in the case of Formula B containing the auxiliary developing agent 1-phenyl-3-pyrazolidone in the developing solution mother liquor and the developing solution replenisher, the sensitivity was reduced after two months of running (Experiment No. 1). On the other hand, 1-phenyl-3
-Experiment when pyrazolidone is contained in photosensitive material
No sufficient sensitivity is obtained as the result of No. 3 shows. On the other hand, sufficient sensitivity can be obtained only when the auxiliary developing agent compound according to the present invention is contained in the light-sensitive material, and a stable sensitivity can be obtained without a decrease in sensitivity even during two months of running. I was able to.

[0139]

According to the present invention, even when a long-term running process, particularly a low replenishment process, is performed using a developing solution containing ascorbic acids, which are preferable in terms of environmental protection, as a developing agent, stable processing can be achieved. Photographic performance can be obtained.

Claims (2)

[Claims] 1. A method for processing a black-and-white silver halide photographic material with a developing solution containing ascorbic acids as a developing agent and not containing a dihydroxybenzene type developing agent, wherein the developing solution is 1-phenyl-3. -Processing of a black-and-white silver halide photographic material, wherein the black-and-white silver halide photographic material does not contain pyrazolidones and contains an auxiliary developing agent represented by the following formula (1) or (2): Method. Embedded image [In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group. X represents a substituent capable of substituting on a benzene ring, and m represents an integer of 0 to 5. When m represents an integer of 2 or more, a plurality of Xs may be the same or different. Provided that the total number of carbon atoms of R _{1 to} R ₄ and m groups represented by X is 3 or more and 30
In the following, the groups represented by R _{1 to} R ₄ and X are not substituted with a water-soluble group. In the formula (2), R ₅ ,
R ₆ , R ₇ and R ₈ represent a hydrogen atom, an alkyl group or an aryl group. Y represents a substituent that can be substituted on a benzene ring, and n represents an integer of 0 to 5. When n represents an integer of 2 or more, a plurality of Ys may be the same or different.
R ₉ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group or an arylamino group. However, the total number of carbon atoms of R _{5 to} R ₈ , R ₉ and n groups represented by Y is 2 or more and 30
It is as follows. ] 2. The process is carried out by replenishing the developing solution, wherein the replenishing solution for replenishment contains a carbonate, and the concentration of the carbonate is 0.4 mol / l or more and 1.2 mol / l or less, the developer replenisher black-and-white silver halide photographic light-sensitive material 1 m ² per 50
3. The method for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein 350 ml of the material is replenished.