JPH04128837A - Method for replenishing developer - Google Patents

Abstract

PURPOSE:To stabilize processing with a small replenishing amount over a long period and to enhance image contrast by incorporating in the replenishing solution to be added in proportion to the area of the material to be processed an organic antifoggant higher in concentration than that in the developer and replenishing an alkaline agent in proportion to the blackened area of the material to be processed. CONSTITUTION:The development replenishing solution containing the organic antifoggant higher in concentration than that in the developer to be used in proportion to the area of the silver halide photographic sensitive material to be processed at the time of starting the development is supplied and the alkaline agent is replenished in proportion to the blackened area of the material, and further the development replenishing solution lower in activity than the developer used at the time of starting the development is supplied in an amount corresponding to the minimum necessary replenishing amount per unit time decided by an automatic developing machine.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for developing a silver halide photographic material in high contrast using an automatic developing machine, and in particular, it relates to a photolithography method for printing graphic arcs. The present invention relates to a method of forming a high-contrast negative image suitable for a process using an automatic processor.

[Prior art]

In the graphic arc field, an imaging system is needed that exhibits high contrast photographic characteristics to provide good reproduction of continuous tone images with halftone images or reproduction of line images.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde to keep the concentration of free sulfite ions extremely low so as not to inhibit its infectious development properties. .

Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4,224,401 and U.S. Pat.
．． No. 168.977, same No. 4. No. 166.742, No. 4,311.781, No. 4,272,606,
There is a method using a hydrazine derivative described in 4,211,857, 4,243,739, and the like. According to this method, high contrast and high sensitivity photographic properties are obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. A dramatic improvement in comparison.

However, in the method using this hydrazine derivative, the pH of the developer is set higher than that of a normal lithium developer, so the pH value tends to fluctuate, and this fluctuation in pH value can cause variations in the results of photographic properties. There is a problem of appearance.

In order to solve the above problem, US Pat. It is described that the sensitizing and contrast-increasing effects of hydrazine derivatives can be expressed with a developer having a lower pH value by increasing the pH value of the hydrazine derivative.

Even with this simple method, it is stable over a long period of 1 to 12 months under various processing conditions, such as when the film processing area is large or small, and when the blackening rate of the film to be processed is low or high. It is difficult to obtain high photographic performance.

On the other hand, an attempt was made to stabilize photographic performance by improving the developer replenishment method, as disclosed in JP-A No. 49-68.725.
No. 51-110,329, No. 53-23,631,
No. 53-94,926, No. 53-100,232,
It is described in No. 54-103,349, No. 5B-44,438, etc. Among these, blackening area proportional replenishment, etc. are also described. However, all of these methods are limited to the case of Lith developer, and therefore, the replenishment method also takes into account aging fatigue, processing fatigue, etc., but it is not possible to automatically process silver halide photographic materials containing hydrazine derivatives. There is no disclosure at all of a replenishment method for obtaining high-contrast images through stable processing over a long period of time using a developing machine.

[Problems to be solved by the invention] In general, a high contrast system using hydrazine (T value is 10
In the above system), air oxidation of the developer increases the activity of the developer, resulting in an increase in sensitivity and the occurrence of black spots. To prevent this, in the case of automatic processing, the liquid activity of the replenisher is made lower than the liquid activity of the development starting liquid.

However, as the amount of photosensitive material processed per unit time increases, the amount of low-activity replenisher replenishment also increases accordingly.
The disadvantage is that the liquid activity gradually decreases.

In order to eliminate such drawbacks, a replenishment method for hydrazine high contrast system is described in JP-A No. 61-91939, but furthermore, when a film with a high blackening rate is processed with a smaller replenishment amount, the liquid activity may be decreased. The disadvantage is that the drop is even greater. Therefore, an object of the present invention is to stably process a silver halide photographic material containing a hydrazine derivative using an automatic processor for a long period of time (for example, 1 to 12 months) with a small amount of replenishment, and to obtain a high-contrast image. An object of the present invention is to provide a developer replenishment method.

[Means for solving problems]

An object of the present invention is to develop a silver halide photographic light-sensitive material containing a hydrazine derivative in a method for developing high contrast using an automatic processor. A developer replenisher containing an organic antifoggant at a higher concentration than the developer used is replenished, and an alkaline agent is replenished in proportion to the blackened area of the silver halide photographic light-sensitive material to be processed. Furthermore, the shortage of the required minimum replenishment amount per unit time determined by the automatic developing machine used is achieved by a development processing method characterized by replenishing a developer replenisher with lower activity than the developer used at the start of development. be done.

One of the features of the present invention is that the developer replenisher, which is replenished in proportion to the area of the photosensitive material to be processed, contains a higher concentration of an organic antifoggant than the developer (development start solution) used at the start of development. In the present invention, the amount of organic antifoggant in the development initiating solution is preferably 1.2 times to 2 times (in terms of weight), particularly preferably 1.3 times to 1.7 times the content of the organic antifoggant in the point. The antifoggant is included in a replenisher solution that is replenished in proportion to the treated area. The other composition of the replenisher to be replenished in proportion to the treated area may be the same as that of the development starting solution.

Here, the organic antifoggant refers to an agent that has the function of suppressing fog during development of silver halide photosensitive materials, and
P1365B2, JP-A No. 53-66732, JP-A No. 6
Publicly known documents describing organic antifoggants for developing solutions such as No. 2-4702 can be used as reference.

Specifically, benzimidazole derivatives such as 5-methylbenzimidazole and 2-mercaptobenzimidazole-5-sulfonic acid, benzotriazoles such as 5-methylbenzotriazole=IL 1-phenyl-5-mercaptotetrazole, 3-( Examples include mercaptotetrazole derivatives such as 5-mercaptotetrazole) benzenesulfonic acid, indazole derivatives such as 5-nitroindazole, and thiazole derivatives.

The organic antifoggant added to the replenisher, which is replenished in proportion to the treated area, may be of the same kind as the organic antifoggant used in the development initiation solution, or may be of a different kind.

In the replenishment method of the present invention, the amount of replenisher to be replenished can be reduced in proportion to the treated area. According to the present invention, it is possible to set the replenishment amount of the above-mentioned replenisher to 200 d or less, particularly 150 d or less per rrr of photosensitive material.

Another feature of the present invention is that the alkaline agent is replenished in proportion to the blackened area of the photosensitive material being processed.

As the alkaline agent, an alkaline agent (for example, a water-soluble inorganic alkali metal salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic potassium phosphate, etc.) normally used in a developer can be used.

The amount of alkaline agent replenished in proportion to the blackened area is:
The amount is set in the range of 0.005 to 0.1 mol per blackened area. It is convenient to add the alkaline agent as an aqueous solution, but since such a small amount is sufficient, the amount is negligible compared to the amount of replenisher that is replenished in proportion to the area of the photosensitive material being processed. It only brings about an increase.

A specific example of the developer replenishment method of the present invention will be described below.For ease of explanation, the replenisher containing an organic antifoggant at a higher concentration than the development starting solution will be referred to as replenisher B, and an alkaline agent The replenisher for replenishing the liquid will be referred to as replenisher C.

First, (1) the developing tank of the automatic processor is filled with a developing starting solution and developing is started. (2) Measure the area of the photosensitive material and its blackened area each time the photosensitive material is processed, calculate the replenishment amount of replenisher B based on the area of the photosensitive material, and calculate the replenishment amount of replenisher C based on the blackened area. Calculate the amount of replenishment and replenish with the calculated amounts of replenisher B and replenisher C. (3) After completing the processing on day -, calculate the total amount of replenisher B (ΣB), and (4) when starting the automatic processor operation the next morning, use a developer replenisher with lower activity than the developer starting solution. , Replenish the amount equal to the minimum required replenishment amount minus ΣB (if ΣB exceeds the required minimum replenishment amount, this replenishment will not be performed). From the second day onwards, perform the above (2) to (4). Normally, the replenishment method of the present invention is automatically carried out by incorporating a device for performing the above operations and a sea fence into the automatic processing machine.

In the present invention, a low-activity replenisher means that when a silver halide photographic light-sensitive material containing a hydrazine derivative is developed under certain conditions, the photographic sensitivity is lower than that when developed using a development initiator. It means low. Here, the photographic sensitivity is expressed as the reciprocal of the exposure amount that gives a blackening density of 1.5. In this case, the term "photographic sensitivity is low" means that the sensitivity value is 95% or less.

Specifically, the replenisher having lower activity than the development starting solution used in the present invention includes a solution having a lower pH than the development starting solution, a solution obtained by diluting the development starting solution with water, and a solution containing an organic antifoggant. Examples include a liquid in which the amount of the developing agent is larger than that of the development starting liquid, and a liquid in which the content of a developing agent is smaller than that of the developing starting liquid.

Here, the pHO difference is preferably 0.05 to 0.2
It is. When diluting with water, the ratio of dilution water/development initiator is preferably 0.05 to 0.30. Further, the difference in the content of the organic antifoggant is preferably 20% to 50%.

In the present invention, the total amount of minimum replenishment fluid required per a certain unit time (hereinafter referred to as the minimum required replenishment amount) is approximately determined by the length of the unit time (usually one day is convenient). However, it varies somewhat depending on the activity of the development initiator used, the activity of the replenisher, the type of automatic processor, the amount of developer, the type of photosensitive material, etc. However, once such development conditions are determined, the required minimum replenishment amount suitable for the conditions can be easily determined. For example, if only the developer starter solution is added to the developing bath of an automatic processor at the start, the automatic processor is operated for the average operating time of the day without replenishing the replenisher, and after stopping, the next morning (i.e. (24 hours after the start of development) necessary to bring the solution activity when restarting the automatic processor to the same level as the solution activity at the start.
By determining the amount of low-activity replenisher, the required minimum replenishment amount of low-activity replenisher per certain unit of time (in this case, one day) can be determined.

In the present invention, a dihydroxybenzene-based developing agent is used as the developing agent of the developer, and P-
Although it is preferable to use an aminephenol type developing agent or a 3-pyrazolidone type developing agent, it is not necessary to use an auxiliary developing agent depending on the case.

Examples of dihydroxybenzene-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, and 2.3-dichlorohydroquinone.
-Dibromohydroquinone, 2,5-dimethylhydroquinone and the like, among which hydroquinone is particularly preferred.

Examples of 1-phenyl-3-pyrazolidone or its derivatives as an auxiliary developing agent include l-phenyl-3-pyrazolidone, 1-phenyl-44-dimethyl-3-pyrazolidone, ■-phenyl-4methyl-4-hydroxymethyl-3 -Virapriton, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-virapritone, 1-p-aminophenyl-4
, 4-dimethyl-3-virapritone, 1-P-tolyl-
Examples include 4,4-dimethyl-3-pyrazolidone.

As the p-aminophenol auxiliary developing agent, N-methyl-p-aminophenol, p-aminophenol, N
-(β-hydroxyethyl)-p-aminophenol, N
-(4-hydroxyphenyl)glycine, 2-methyl-
Examples include p-7 minophenol and P-benzylaminophenol, among which N-methyl-p-aminophenol is preferred.

Dihydroxybenzene developing agent is usually 0.05 mol/
It is preferably used in an amount of 1 to 0.8 mol/l, and when a combination of dihydroxybenzenes and 1-phenyl-3-birapritones or p-amino-phenols is used, the former is used in an amount of 0.05 mol/l. mole/f-0.5 mole/!
, the latter at 0°06 mol/l or less! It is preferable to use it in

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite zeta lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is used in an amount of 0.3 mol/p or more, but if it is added in too large a quantity, it will precipitate in the developer and cause contamination of the solution, so the upper limit is preferably 1.2 mol/p.

The pH value of the developer of the present invention is set in the range of 10.5 to 12.3. As the alkaline agent used for setting the pH value, ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, sodium carbonate, tribasic potassium phosphate, etc.) can be used.

In addition, the developer of the present invention includes pH buffering agents such as boric acid, borax, tribasic sodium phosphate, and tribasic potassium phosphate;
Development inhibitors such as potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol, and methanol may also be included.

In particular, when using a compound such as 5-nitroindazole, it should be pre-dissolved in a separate area from the area containing the dihydroxybenzene developing agent or sulfite preservative, and when used, mix the image area and add water. etc. are common. Furthermore, if the part where 5-nitroindazole is dissolved is made alkaline, it will be colored yellow and will be convenient for handling.

Furthermore, U.S. Patent No. 4,269.929, JP-A-60-2
No. 58537, No. 61-267759, Patent Application No. 1-2
It can contain amino compounds described in No. 9418 and the like. By using an amino compound, the pH of the liquid can be lowered and the stability of the liquid itself can be improved.

Furthermore, it may contain a toning agent, a surfactant, a water softener, a hardening agent, etc., if necessary.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. Moreover, as an oxidizing agent, ethylenediaminetetraacetic acid Fe(I[I)1! Salt may also be used.

The treatment temperature is usually chosen between 18°C and 50°C, but it may also be below 18°C or above 50°C.

The method of the invention is particularly suitable for rapid processing using automatic processors. The automatic developing machine is one with roller conveyance, Bell) Il! You can use any of the following. The processing time may be short, within 2 minutes in total, especially 100 seconds or less, within which the time allotted for development is 15 to 60 minutes.
It is fully effective even for rapid development in seconds.

The hydrazine derivative used in the present invention has the following general formula (
1) Preferred are compounds represented by the general formula N) R, -N-N-G, -R.

A, A.

In the formula, R1 represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and C1 represents a -C- group, -S O, -II 1
111 group, -5O- group, -P- group, -C-C- group, ThioR.

Represents a carbonyl group or iminomethylene group, A, ,
Both Ats represent a hydrogen atom, one of which is a hydrogen atom, and the other of which is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula (1), the aliphatic group represented by R preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

The aromatic group represented by R3 in general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be fused with an aryl group.

Preferred R3 is an aryl group, particularly preferably one containing a Hensen ring.

The aliphatic group or aromatic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group , carboxyl group, phosphoric acid amide group, diacylamino group, imide group, Rz N HCN CI
't Toka Kyo Lt Rare, good R.

Preferred substituents include alkyl groups (preferably those having 1 carbon number)
~20 carbon atoms), aralkyl groups (preferably 7~20 carbon atoms),
3o), alkoxy group (preferably 1 to 2 carbon atoms),
o), a substituted amino group (preferably 1 to 20 carbon atoms)
(an amino group substituted with an alkyl group), an acylamino group (preferably one having 2 to 30 carbon atoms), a sulfonamide group (preferably one having 1 to 30 carbon atoms), a ureido group (preferably one having 1 carbon number) 30 carbon atoms), a phosphoric acid amide group (preferably one having 1 to 3 carbon atoms), and the like.

The alkyl group represented by R2 in general formula (1) 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, one containing a Hensen ring). .

When G is a -C- group, preferred among the groups represented by R1 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxyhensyl group, etc.), aryl group (e.g., phenyl group, 35-dichlorophenyl group, o-methanesulfonamidophenyl group) , 4-methanesulfonylphenyl group,
(2-hydroxymethylphenyl group, etc.), and a hydrogen atom is particularly preferred.

R, may be substituted, and Ill! ! Basically,
The substituents listed for R1 are applicable.

G in general formula (+) is most preferably a -C- group.

Further, R2 may be one that causes a cyclization reaction in which the Cz Rz part is split from the remaining molecules and a cyclic structure containing the atoms of the GI R1 part is generated; examples thereof include: For example, those described in Japanese Patent Application Laid-Open No. 63-29751 can be mentioned.

Hydrogen atoms are most preferable as A, , At.

R3 or R2 in the general formula (1) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group,
It can be selected from phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, etc. Examples of the polymer include those described in JP-A-1-100530.

-JIG R or R in formula (1) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include a thiourea group,
U.S. Pat. Nos. 4,385.108 and 4,45 for heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
9.347, JP-A-59-195,233, JP-A No. 59
-200231, 59-201.045, 59
No. 201.046, No. 59-201.047, No. 59
-201,048, 59-201049, 61-170.733, 61-270,744, 62-'948, 63234.244, 6
Examples include the groups described in No. 3-234,246.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ R N = N ■-17 O N = N ■-18 ■-19 N = N ■-20 ■-21 ■-22 ■ ■-23 ■-24 ■-25 ■-26 H In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO3URE
Item23516 (November 1983 issue, P, 34
6) and the documents cited therein, as well as U.S. Pat.
80.207, 4,269.929, 4.27
No. 6.364, No. 4,278,748, No. 4.385
, No. 108, No. 4,459,347, No. 4,560,
No. 638, No. 4,478,928, British Patent No. 2,01
1.391B, JP-A-60-179734, JP-A No. 62-
No. 270,948, No. 63-29,751, No. 61-
No. 170733, No. 61-270,744, No. 62-
No. 948, EP 217,310, or US 4°68
6.167, JP-A No. 62-178.246, JP-A No. 63
-32,538, 63-104゜047, 63
-121,838, 63-129.337, 6
3-γ23,744, 63-234,244, 63-234,245, 63-234,246,
63-294.552, 63-306,438, JP-A-1-100.530, JP-A-1-105.941
No. 1-105.943, JP-A-64-10.23
No. 3, JP-A No. 1-90,439, JP-A-1-276,12
No. 8, No. 1-283,548, No. 1-280,747
No. 1-283,549, No. 1-285,940, Patent Application No. 147.339/1983, No. 63-179.7
No. 60, No. 63-229, 163, Patent Application Hei 1-18,
No. 377, No. 1-18, 378, No. 1-18.379
No. 1-15.755, No. 1-16,814, No. 1-40.792, No. 1-'42,615, No. 1-
No. 42,616, No. 1-123.693, No. 1-12
Those described in No. 6,284 can be used.

The amount of the hydrazine derivative added in the present invention is 1X10-6 mol to 5X10 per 1 mol of silver halide.
-" mole is preferable, and the addition amount is particularly preferably in the range of 1X10-' mole to 2X10-" mole.

The silver halide emulsion used in the present invention is a negative emulsion, and its halogen composition is not particularly limited. The composition may be different, but the content of silver iodide is 5 mol% or less,
In particular, the silver halide grains in the photographic emulsion used in the present invention preferably have a relatively wide grain size distribution, but preferably have a narrow grain size distribution, particularly It is preferable that the size of grains that account for 90% of the total weight or number of silver halide grains is within ±40% of the average grain size (
Generally, such emulsions are called monodisperse emulsions).

The silver halide grains used in the present invention are fine grains (for example, 0
．． 7μ or less) is more preferable, and particularly preferably 0°4μ or less.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Two or more silver halide emulsions formed separately may be used in combination.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

As the silver halide emulsion, a so-called primitive emulsion without chemical sensitization can be used, but it may also be chemically sensitized. "Lagen der Fotografisien Brosetsse Mitsuzilberhalogeniden", Akademissie Förlagesgesgeschaft, 1968 (H, Fr1eser, Die Gr.
und-1agen derPhotography
chen Prozesse +mit Silver
halogeniden, Akademische
Verlaggesselschaft.

1968) can be used.

In other words, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g. thioic acid salts, thioureas, mercapto compounds, rhodanines), reducing substances (
For example, reduction sensitization using stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (for example, gold compounds, and metals from group Ⅰ of the periodic table such as platinum, iridium, palladium, etc.) A noble metal sensitization method using complex salts of 1 to 4 can be carried out alone or in combination.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroquine ethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; Vinyl alcohol, polyvinyl alcohol partial acetal, bo1゜-N~ruvinylpyrrolidone polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as monopolymers or copolymers of polymethacrylic acid, polyacrylamide, borivinino-imidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, process-resistant gelatin, platen of the Society of Scientific Photography, Inc. Japan (B
ull, Soc, Sci, Phot, Japan) Floor 1
Enzyme-treated gelatin such as that described on page 6.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or other dyes. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes may be used in combination to obtain a hyperchromic enhancement effect.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
Substances exhibiting supersensitization may be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
35,721), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743,510)
may contain cadmium salts, azaindene compounds, etc. U.S. Patent Nos. 3,615.613, 3,615,641, 3.617.295,
The combination described in No. 3,635,721 is particularly useful.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds niazaindenes, such as oxazolinthione;
For example, triazaindenes, tetraazaindenes (
In particular, 4-hydroxy substituted (1,3,3a,7)tetraazaindenes (1 g), pentaazaindenes, etc.; anti-capri agents or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known as can be added.

Among these, particularly preferred are benzotriazoles (e.g., 5-methylbenzotriazole) and nitroindazoles (e.g., 5-nitroindazole); however, these compounds may be included in the treatment liquid. .

The photographic light-sensitive material used in the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (23-dihydroxydioxane), activated vinyl compounds (1°3.5-
) Liacryloyl-hexahydro-S triazine, 1.
3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (24-dichloro-6-hydroxy-s
-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention may be used as a coating aid, or to prevent static electricity, improve slipperiness, emulsion dispersion, prevent adhesion, and improve photographic properties (e.g., development acceleration, high contrast). for various purposes such as sensitization, sensitization), etc.
Various surfactants may be included.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfone M salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyester alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkylhetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts! Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 58-9412.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid. , methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used.

In the photographic light-sensitive material used in the present invention, dyes, desensitizers, plasticizers, lubricants and the like are used in the photographic emulsion layer and other hydrophilic colloid layers as necessary.

Regarding these additives and the aforementioned additives, please refer to the Research Disclosure (RESEARCH DISC).
O511RE) Volume 176, 17643 (197
Those described in P, 22 to P, 28 of December 2008) can be used.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 Development starting solution, replenisher A, replenisher B, and replenisher C with the following compositions
was prepared.

As the surface fixer, fixer 0R manufactured by Fuji Photo Film Co., Ltd.
-F1, then washed with water and dried.

For this process, use automatic development 11 manufactured by Fuji Photo Film Co., Ltd.
FG680A was used. As a result of preliminary experiments, this automatic processor 1
The minimum required daily replenishment amount is 2.41. Fuji camera contact film GA-10 as a photosensitive material for photo shoots
0 was used. Development time was 30 seconds at 34°C. Table 2 shows the experimental conditions and the results obtained.

As the results in Table 2 show, in the conventional method, the sensitivity changes depending on the blackening rate of the processed film, and in addition, experiment number 3
．． When the amount of replenisher is as small as 120d/rrT as shown in 4, the change in sensitivity becomes large. According to the method of the present invention, the blackening rate of the film processed even with a small amount of replenisher as shown in Experiment No. 5.6 Sensitivity remains stable even if the value changes.

Example 2 The development starting solution used, replenisher A, replenisher B, replenisher C1, fixer, automatic processor, film, development time, and temperature were all the same experimental conditions as in Example 1, and the amount of film processed per day was I gave it a 5-bo. The results obtained are shown in Table 3.

As shown in the results in Table 3, in the conventional replenishment method, the sensitivity changes depending on the blackening rate of the film to be processed. Even if the blackening rate of the film changes, the sensitivity remains constant and stable.

Claims (5)

[Claims] (1) In a method of developing a silver halide photographic light-sensitive material containing a hydrazine derivative to high contrast using an automatic processor, a developer replenisher that is replenished in proportion to the area of the silver halide photographic light-sensitive material to be processed starts development. A developer is characterized in that it contains an organic antifoggant at a higher concentration than the developer sometimes used, and that an alkaline agent is replenished in proportion to the blackened area of the silver halide photographic light-sensitive material being processed. How to replenish. (2) A replenisher with lower activity than the developer used at the start of development is used to replenish the amount that is insufficient for the minimum replenishment amount per unit time determined for the automatic developing machine used. The method for replenishing a developer according to claim (1). (3) To make up for the shortage of the required minimum replenishment amount per unit time, add 5% to 30% water to the development start solution as a replenisher with lower activity than the developer used at the start of development. 2. The method for replenishing a developer according to claim 1, wherein the developer contains a higher concentration of an organic antifoggant than the replenisher or the development initiator, which has been made to have a lower activity. (4) The replenishment amount of developer replenisher, which is replenished in proportion to the area of the silver halide photographic light-sensitive material to be processed, is 65 m/m^2.
2. The method of replenishing a developer according to claim 1, wherein the amount is 1 to 200 ml. (5) The amount of alkaline agent to be replenished is 0.005 per m^2 in proportion to the blackened area of the silver halide photographic light-sensitive material being processed.
Claim (1) characterized in that the amount is ~0.100 mol.
How to replenish the developer.