JPS62269956A - Image forming method - Google Patents

Abstract

PURPOSE:To stabilize characteristics of forming a photosensitive material ultrahigh in contrast containing a hydrazine derivative by using a developing replenishing solution as a processing solution at the beginning of development, containing a developing agent, >=0.25mol/l sulfite, an amino compound, and a buffer, and in addition to these, a development activator. CONSTITUTION:In the process for developing the silver halide photographic sensitive material containing the hydrazine derivative and forming an ultrahigh contrast image, the developing replenishing solution to be used as the processing solution at the beginning of the processing contains the developing agent, the >=0.25mol/l sulfite, the amino compound, and the buffer, and in addition to them, the development activator in an amount of <=200ml, especially, <=100ml per l of the developing replenishing solution, thus permitting the ultrahigh contrast characteristics of the photosensitive material containing the hydrazine derivative to be stably obtained by easy and simple operation, fluctuation of composition during running processes to be reduced, and fluctuation of the obtained photographic characteristics also to be reduced.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for forming an image using a silver halide photographic material containing a hydrazine derivative, and in particular to a photolithography method for printing. The present invention relates to an image forming method of a silver halide photographic light-sensitive material for plate making, which can stably obtain ultra-high contrast negative images suitable for printing.

(Prior Art) In the photoengraving process, in order to improve the reproduction of continuous tone images or line images using halftone images,
What is needed is a system for producing images 1 exhibiting ultra-high contrast photographic characteristics.

Traditionally, a special developer called a Lith developer has been used for this purpose.

Lith developer contains only no-hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde to extremely low the concentration of free sulfite ions so as not to inhibit its infectious development properties. There is. Therefore, Lith developer is extremely susceptible to air oxidation and has the serious drawback of not being able to withstand storage for more than 3 days.

A method for obtaining ultra-high contrast 7c% image quality using a stable developer that solves the above problems is disclosed in U.S. Patent No. 4122414.
No. 01, No. 416a977, No. 416fi742,
4311.781, 4272.606, 42
There is a method using a hydrazine derivative described in No. 21.857 and No. 4243739. According to this method, photographic properties with ultra-high contrast and high sensitivity can be 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, the effects of ultra-high contrast and increased sensitivity due to this hydrazine derivative are manifested in a region where the pH of the developer is high. To stably obtain this effect, it is necessary to use a buffer to reduce pH fluctuations at high pH. however,
Even if it contains a buffering agent, since it is a high-pH developer, its pH tends to rise due to air oxidation.Also, if the developer continues to operate at high temperatures for a long time in an automatic processor, evaporation and concentration will occur, resulting in a decrease in salt concentration. goes up. Both of these fluctuations increase the liquid activity, leading to an increase in sensitivity and a sharp increase in black spots, and making it impossible to stably obtain the ultra-high contrast characteristics of the photosensitive material. Therefore, in a system using such a hydrazine derivative, automatic processing is performed; the developer replenisher used is a developer (hereinafter referred to as
In this specification, the developer solution refers to a processing solution at the start of development, and it is necessary to make the solution activity lower than that of the developer replenisher.

Therefore, the developer replenisher is usually used after diluting the developer. Dilution lowers the pH and developer concentration, resulting in lower solution activity. The developer replenisher used in normal developer systems such as Lith developer has a pH higher than that of the developer.
The developer has a high concentration, a high developer concentration, and therefore a high solution activity, which is completely opposite to the developer system using such a hydrazine derivative.

(Problems to be Solved by the Invention) However, as described above, in a developer system in which a hydrazine derivative is applied, the developer and developer replenisher are the same solution, and only the dilution ratio is changed. In the case of only one drug, the advantage is that storage and management are easy because only the -agent needs to be used, but there are disadvantages as described below.

1) The developer replenisher composition is completely regulated by the developer composition.

2) Since all components are diluted equally, it is prudent to include a large amount of a specific composition to compensate for the components that fluctuate during running.

3) Dilution of developer and developer replenisher The dilution ratios are different, making it complicated and prone to mistakes.

On the other hand, there is a method of completely separating the developer and developer replenisher and using them as separate processing agents, but it is complicated and uneconomical to store and manage a developer that is rarely used for a long period of time.

Accordingly, the first object of the present invention is to provide an image forming method that can stably obtain ultra-high contrast characteristics of a photosensitive material containing a hydrazine derivative using a simple and easy-to-handle method. A second object of the present invention is to provide an image forming method that can reduce compositional fluctuations during processing runs and reduce fluctuations in photographic characteristics.

(Another means to solve the problem) The above object is to develop a silver halide photographic light-sensitive material containing a hydrazine derivative to form an ultra-high contrast image. Image formation characterized by using a developer replenisher containing a, a developing agent b, 0.25 mol 1 liter or more of sulfite C, an amino compound d, and a buffer, to which a developer activity enhancer is added. method).

The term "processing solution at the start of development" as used herein refers to a developer used only at the start of running processing, and is hereinafter simply referred to as a "developer" to distinguish it from a "developer replenisher."'The term "developing replenisher" as used herein refers to a replenishing processing solution that is used exclusively when replenishment is required during the processing of light-sensitive materials after the start of development (after the start of running processing).

The development auxiliary solution contains the above α to d, and may be used as an undiluted solution, or the concentrated S solution may be diluted with water to obtain a desired concentration. Although it depends on the developer replenisher, it is carried out at an amount of 300 to 2000 mA' per day, regardless of the processing amount.

1' The "development activity increasing agent" used in the present invention refers to a processing agent containing a compound that increases development activity. The developing activity increasing agent includes an alkaline agent, an amine compound, a dihydroxybenzene developing agent, 1-phenyl-3-
It is sufficient if it contains one or more of pyrazolidones, P-aminephenols, and the like. Especially alkaline agents and/or
Or it is preferable to contain an amine compound. Further, the components contained in the developer activity increasing agent may be the same type as the components contained in the developer replenisher, or may be of a different type.

, 1 The developer activity increasing agent may be used as a stock solution, or its concentrated solution may be diluted with a solvent (for example, water) to obtain a desired concentration.

Development activity enhancers include compositions for compensating for compositional fluctuations associated with processing runs, development inhibitors (potassium bromide, etc.),
Anti-fouling agents and the like may be added as appropriate.

The present invention is characterized in that a developer is prepared by adding a developer activity enhancer to the developer replenisher, and the amount of additive added is 200. v/ or less, particularly preferably 100 m# or less.

While conventional developer replenishers dilute the developer to make the solution activity relatively low, the present invention takes a completely different perspective and adds the above developer activity increasing agent to the developer replenisher. We have newly discovered that by preparing a developer replenisher with similar activity to that of the developer, it is possible to stably obtain ultra-high contrast characteristics of photosensitive materials containing hydrazine derivatives. It is something that

According to the present invention, the composition components of the developer replenisher and the developer can be made to depend on each other by appropriately selecting and adjusting the type and amount of the compound that increases the developer activity in the developer activity enhancer and the local additives. It is possible to use different components as desired without any problems. For example, by including a component that increases during running processing as a component in a developer activity enhancer and adding it at the start of development, it is possible to reduce compositional fluctuations in the processing solution during running, and photosensitive characteristics with small performance fluctuations. can be obtained.

Moreover, unlike using the developer imw itself as a separate processing agent, the present invention basically involves adding a developer activity enhancer to the developer replenisher, which is a very simple operation, so that the developer solution that is used infrequently can be used each time. It can be prepared easily, and since the developer activity increasing agent itself is used in a small amount, it is easy to store.
And there are fewer mistakes.

The method of using the development activity increasing agent of the present invention is particularly suitable for processing in which the amount of photosensitive material to be processed is small, and has the advantage that the developer and developer replenisher are separate, making it easy to use.

According to the image forming method of the present invention, there is no need for complicated liquid management, and photographic characteristics of constant ultra-high contrast and high sensitivity can be obtained simply by replenishing the developer replenisher.

The developing agent that can be used in the developer activity enhancer and developer replenisher used in the present invention preferably contains dihydroxybenzenes because it facilitates obtaining good dot quality, and furthermore, from the viewpoint of developing ability, dihydroxybenzenes are preferably included. Benzene and 1-phenyl-
A combination of 3-pyrazolibins or a combination of dihydroxybenzenes and p-aminephenols is preferred.

Examples of the dihydrox-7benzene development main material that can be used in the present invention include hydroquinone, chlorohydroquinone, fromhyhydroquinone, inpropylhydroquinone, methylhydroquinone, 2.3-"'chlorohydroquinone, Z:l)-U chloro Hydroquinone S Examples include 23-zineromhydroquinone and 25-dimethylhydroquinone, with hydroquinone being particularly preferred.

Examples of developing agents for 1-phenyl-3-pyrazolidone or its derivatives that can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl −
4-Hydroxymethyl-3-vilasoribine, 1-phenyl-44-dihydroxymethyl-3-pyrazolidone, 1
-phenyl-5-methyl-3-pyrazolidone, 1-p-
aminophenyl-44-dimethyl-3-pyrazolidone,
Examples include 1-p-tolyl-44-dimethyl-3-pyrazolidone. Examples of p-aminophenol-based developing agents that can be used in the present invention include N-methyl-p-aminophenol, p-aminephenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4- hydroxymethyl)glycine, 2-methyl-p-azunophenol, p-benzylaminophenol, etc.
Among them, N-methyl-p-aminephenol is preferred.

The developing agent in the developer replenisher is usually 0.05 mol/l to 0.05 mol/l.
Preferably it is used in an amount of 8 mol/l.

In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols, the former 'io, 05 mol/l to 0.5 mol 1
Preferably, the latter is used in an amount of 0.06 mol/l or less.

The concentration of the developing agent in the development activity enhancer is 0.5 to 3.0 mol/l of dihydroxybenzenes, preferably 0.8
~1.2 mol/! Acid, 1-phenyl-3-pyrazolidones or p-aminephenols are 0.01 to 0.1
mol/l, preferably 0.02 to 0.08 mol/l. The former and the latter may be used in combination.

When a developing agent is used as the development activity enhancer, necessary additives (for example, preservatives such as sulfites, solvents such as ethylene glycols, etc.) may be used in combination.

Preservatives that can be used in the developer activity enhancer and developer replenisher of the present invention include sodium intersulfate, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde 9.
Examples include sodium bisulfite. Sulfite is used at least 0.25 mol/l, especially at least 0.3 mol/l, but if too large a quantity is added, it precipitates in the developer and causes solution contamination, so the upper limit is 1.2 mol/l. It is desirable to do so.

The amine compound that can be used in the developer activity increasing agent and developer replenisher of the present invention has an effect of promoting high contrast in the presence of a hivirazine compound.

Useful amine compounds are those having a variety of structures and properties. For example, useful amine compounds include both inorganic and organic amines, such as hydroxylamine.

The organic amine can be an aliphatic amine, an aromatic amine, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine. Primary, secondary and tertiary amines as well as quaternary ammonium compounds are all effective.

A preferred class of amine compounds are alkanolamines, and the term also refers to amines in which the nitrogen atom is directly bonded to the hydroxyalkyl group, i.e., N
-X -OE M (wherein X is an alkylene group) is used in the present application. N-
The group attached to the free bond in the X--OH group can be a hydrogen atom or an organic group, such as an unsubstituted or substituted hydrocarbon group. These groups are preferably hydrogen atoms or hydrocarpyl groups having 1 to 12 carbon atoms, ? ILt is an alkyl group, an aryl group, an alkaryl group or an aralkyl group.

Particularly preferred alkanolamines for the purposes of the present invention are compounds represented by the following formula: in which R is a hydroxyalkyl group having 2 to 10 carbon atoms, and R and R are each hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 2 to 104i='l carbon atoms, a benzyl group, or a group of the following formula: where n is 1 to 10 and X and Y are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 2 to 10 carbon atoms).

Another preferred class of amine compounds is the alkyl amines, especially those represented by the formula: (wherein is an alkyl group having from 1 to 10 carbon atoms)
, and R5 and R are each a hydrogen atom or 1
is an alkyl group having ~10 carbon atoms).

Among the many amine compounds that can be used in carrying out the present invention, representative examples are listed below.

(A-1) 2-(2-7minoethylamino)ethanol (A-2) Ethanolamine (A-3) 2-diethylamino-1-ethanol (
A-4) 2-methylamino-1-ethanol (A-
5) 3-dimethylamine-L2-pronogundiol (A-6) 3-diethylamino-1-propatol (A-7) s-amino-1-4butanol (A-8
) Dipropylamine (A-9) Di-isopropylamine (A-10)
33'-diaminodipropylamine (A-11)
3-dimethylamino-1-pronognol (A-12)
2-dimethylaminoethanol (A-13) 2
-Ethylamine ethanol (A-14) Diethylamino-L2--10 nocundiol (A-15)''n
-Butylgetanolamine (A-16) 3-amino-1-propatol (A-17) 1-dimethylamino-2-propatol (A-18) Benzylamine (A-19) 2-amino-1- Ethanol (A-2
0) 4-amino-1-butanol (A-21)
6-amino-1-hexanol (A-22) O-aminobenzyl alcohol The amount of these amine compounds added to the developer replenisher may be an amount that promotes high contrast, but generally it is 0.01 to 0. It can be used in an amount of 0.9 mol/lf, more preferably 0.01 to 0.4 mol/lf. When used as a developer activity enhancer, the concentration is 0.1 to 1.5 mol/j
More preferably, it is used in an amount of 0.12 to 0.6 mol/l.

Buffers used in the developer replenisher of the present invention include 1)
Hlo, O~12. ．． 8, those having a buffering capacity are preferable, such as the borate described in Japanese Patent Application No. 61-28708,
Sugars (e.g., sucrose), oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalcylic acid), tertiary phosphates (e.g., sodium salt, Potassium salt), carbonate, etc. are used.

The pi of the developer g or developer replenisher of the present invention is 11.0~
12.3. As the developer activity increasing agent and the alkaline agent used in the developer replenisher for setting the pH, common water-soluble inorganic alkali metal salts (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) can be used. When an alkaline agent is used as a developer activity increasing agent, the concentration is 0.2 to 3.0 mol/l, preferably 0.
．． It can be used at 3 to 1.0 mol/l.

In addition to the above-mentioned components, additives used in development activity enhancers and developer replenishers include, for example, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, and triethylene glycol; Axial bath additives such as mercapto compounds such as pepper) prevention 4] may contain a toning agent, a surfactant, an antifoaming agent, a water softener, a film hardening agent, etc. as necessary.

The developer used in the present invention is disclosed in Japanese Patent Application No. 59-19620.
[It is preferable to store the product in a packaging material with low cumulative permeability.

As the fixing agent, those having commonly used compositions can be used.

The fixing agent is a fixing agent such as ammonium thiosulfate or ammonium thiosulfate, which contains thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to about 5 mol/l.

In addition to the above-mentioned thiosulfate, the fixing solution usually contains sulfite as a preservative, sulfuric acid, acetic acid, etc. as a pH adjustment and buffering agent, and in the case of a hardening fixer, it usually also contains a water-soluble hardening agent. (2) Contains aluminum salts and dibasic acid salts as stabilizers.

Usually the pH of the fixer is 4.0 to 5.4, more preferably 4.
．． 6~5.0''C. Furthermore, a trivalent iron compound can also be used as an oxidizing agent in the form of a complex with ethylenediamine tetraacetate.

As the water-soluble aluminum salt, aluminum sulfate, aluminum chloride, light bread, etc. are used. The amount added is usually 0.3 to 1.79 A11).

As the aforementioned dibasic acid, tartaric acid or a derivative thereof, citric acid r:l or a derivative thereof can be used alone or in combination of two or more kinds. It is effective to use these compounds in an amount of 5 mol or more of O, OO per fixer 11, and particularly 0.01 mol/l to 0.03 mol/l.

A stopping process may be included between the developing process and the fixing process. The stop solution usually contains acetic acid, sulfuric acid, sulfite, and the like.

The development temperature is usually selected between 18°C and 50°C, preferably between 25°C and 43°C.

The developing method of the present invention is particularly suitable for rapid processing using an automatic WJ developing machine. Automatic developing machines include those with roller feed,
Can be used with belt conveyance or any other type. The processing time may be short, and is sufficiently effective for rapid processing, within 2 minutes in total, 100 seconds or less, within which the time allotted for development is 15 to 60 seconds.

The water washing may be performed with running water or with standing water, or may be a countercurrent washing method. The washing water may contain compounds described in Japanese Patent Application No. 60-253807.

Examples of the hydrazine derivatives used in the present invention include RESERCHI) ISCLO8URE engineering tem 2
3516 (November 1983, P, 346) and the documents cited therein, as well as U.S. Pat.
No. 273748, No. 108 to No. 438, No. 445
a347, 456Q638, 447a928, British Patent No. 2,011,391B, JP-A-60-179
Those described in No. 734 can be used.

Preferred examples of the hydrazine derivatives used in the present invention include aryl hydrazides in which a sulfinic acid residue is bonded to a hydrazo moiety as described in U.S. Pat. Examples include compounds coated with

General formula (I) R-Nl(NH-G-R8 where R7 represents an aliphatic group or an aromatic group, R8 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, It represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a sulfolyl group, or an N-substituted or unsubstituted iminomethylene group.

In general formula (1), the aliphatic group represented by R7 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
~20 straight chain, branched or cyclic alkyl groups.

The aromatic group represented by R7 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Particularly preferred as R7 is an aryl group. R7
The aryl group or unsaturated heterocyclic group may be substituted, and typical substituents include a straight chain, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms),
Aralkyl group (preferably the alkyl moiety has 1 to 1 carbon atoms)
3), an alkoxy group (preferably one having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Examples thereof include an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), and a ureido group (preferably having 1 to 30 carbon atoms).

Among the groups represented by R8, when G is a carbonyl group, preferred are a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, and a substituted or unsubstituted phenyl group, with a hydrogen atom being particularly preferred.

When G is a sulfonyl group, R8 is a methyl group,
Ethyl group, phenyl group, and 4-methylphenyl group are preferred, and methyl group is particularly preferred.

When G is a sulfolyl group, R8 is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, with a phenyl group being particularly preferred.

When G is a sulfoxy group, preferred RB is a cyanobenzyl group, methylthiobenzyl group, etc., and when G is an N-substituted or unsubstituted iminomethylene group, preferred R8
is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

R7 or R8 may have incorporated therein a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms that is relatively inert to photography.

R7 or R8 may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include groups described in US Pat. No. 438a108, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.

G in general formula (1) is most preferably a carbonyl group.

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

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

knee 3 knee 5 knee 7 2H5 1-i.

O The synthesis method of these compounds is described in JP-A No. 53-20921,
No. 53-20922, No. 53-66732, No. 53
-20318 etc.

The compound represented by general formula (1) is preferably contained in an amount of p I
A preferable addition amount is in the range of 10 moles.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
4μ to 0.15μ is preferred. There are no restrictions on particle size distribution for basic fishing, but eastern dispersion is preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles is composed of particles having a size within ±40% of the average particle size.

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

A mixed silver halide emulsion of two or more separately formed silver halide emulsions may be introduced into separate layers as disclosed in Japanese Patent Application No. 60-64199.

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

In the present invention, the silver halide emulsion which is particularly suitable as a light-sensitive material for line drawing and halftone dot creation is
Preferably, silver halide is produced in the presence of 0 to 10 moles of iridium salt or a complex salt thereof, and 70 moles or more, particularly 90 moles or more of silver bromide. Moreover, the content of iodized steel is less than 10 mole, especially from 0.1 to 5 mole.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized.

As methods of chemical sensitization, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic properties during the manufacturing process, storage, or photographic processing of the light-sensitive material. Namely, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. mercapto'pyrimidines;mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes, especially 4-hydroxyW (Lλ3a, 7) tetrazaindenes; A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, henzenesulfonic acid, benzenesulfonic acid amide and the like;

Among these, preferred are benzotriazoles (e.g. 5-methyl-benzotriazole) and nitroindazoles (e.g. 5-nitroindazole).
It is. Further, these compounds may be included in the treatment liquid.

The sensitizing dyes used in the present invention include various sensitizing dyes known in the field of photographic materials, such as cyanine dyes and merocyanine dyes. A preferred dye is JP-A-55-52
These include dyes described in No. 050.

In the photographic light-sensitive material of the present invention, an inorganic or organic hardening agent may be included in the photographic emulsion layer and other hydrophilic colloid layers.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used. Specifically, research
Disclosure (isWARcHD Engineering5CLO8U
It is described in section ■ of R.J. No. 176, A17643 (December 1978).

The photosensitive materials used in the image forming method of the present invention include:
Patent application No. 60-80026, No. 60-206258,
Photosensitive materials described in JP-A No. 60-66179, JP-A No. 6O-s4xci9, etc. can be used.

(Example) The present invention will be explained in detail with reference to the following examples.
In the presence of moles of potassium iridium (III) hexachloride and ammonia, a silver nitrate aqueous solution, potassium iodide, and a potassium bromide aqueous solution were added simultaneously over 60 minutes, and the pAg was maintained at 78 during that time (so that the average particle size was 0°25μ). A cubic monodisperse emulsion with an average silver iodide content of fi 1 mol was prepared.

3-ethyl- as a sensitizing dye was added to these silver iodobromide emulsions.
5-(2-(3-ethyl-2(3H)-thiazolinidene-etheridene) rhodanine'k fK5 added, S5'
- dikuoo-g-ethyl-h 3/-his(3-sulfopropyl)oxacarbocyanine sodium salt,
4-hydroxy-6-methyl-1,3,3 as stabilizer
a, 7-chitrazaingen, dispersion of polyethyl acrylate! 1L L3-1 Vinylsulfonyl-2-pronominol and compound 1-7 of the general formula (11) were added at a concentration of 93×10 mol per mol of silver, and the mixture was deposited on a polyethylene terephthalate film with a Mi of 3.49/m”K.
I applied it completely.

After exposing this film to light using a 150-line magenta contact screen through the entire sensitometric exposure wedge, a developer having the composition shown in Table 1 was applied to an automatic processor FG360.
First, the photographic performance of the new solution was tested using U (Fuji Photo Film Co., Ltd.), and then 20 sheets of Nishimei size (254an x 30.5 cm), which were fully exposed to light, were developed. A developer replenisher having the composition shown in Table 1 was added to the photosensitive material 1.
20ml was replenished every time a sheet was processed, and running was carried out in the same manner for one week.

Afterwards, the photographic performance was tested in the same way as the new solution.

The development conditions were 34° C. for 50 seconds. The fixer is dural fixer LF'-605 (Fuji Film Co., Ltd. jl!!)
I used k.

No.1 expression developing solution: developer activity increasing agent hydroxide) IJum 2.
29 Potassium Bromide 259 Add water and add 50ml to the developer replenishment g (1/) below.

Developer replenisher: Hydroquinone 45.0
9N・Methyl P・Aminephenol 2mn1
o, sg sodium hydroxide 1
509 Potassium hydroxide 55
．． Q95-Sulfosalicylic acid 45.
09 Boric acid 25.09 Potassium sulfite 110.09
Ethylenediaminetetraacetic acid disodium salt 1.
09 Potassium Bromide 3.
51+5 methylbenzotriazole 0.
69n-butyl jetanolamine 15.
Add 0g water (adjust pH to 11.5)
The Il treatment results are shown in Table 1.

Evaluation method Relative sensitivity: Density 1 when developed at 34°C for 50 seconds
．． It is expressed as a relative value of the reciprocal of the exposure amount giving a value of 5, and the new solution is taken as 100.

Kurobo: Evaluated in 5 stages by microscopic observation. [5] is the least, and [l is the most. [3] is the practical limit.

It can be seen that stable performance can be obtained by running with the method of the present invention. Furthermore, since the replenisher is a working solution, dilution is not necessary and daily replenishment is simple.

Example 2 The same photosensitive material as in Example 1 was processed using a developer and a developer replenisher having the composition shown in Table 8.

Two to four pieces of Nishimei size were treated every day, with the entire surface exposed to light. 500 d of replenisher was added every morning at the start of operation, regardless of the amount of treatment, and running treatment was carried out for two weeks.

2nd expression liquid: developer activity increasing agent '3-diethyluaminopropanonyl 3.0g5
-Methylbenzotriazole Add 0.05g water
Add 60 d to the developer replenisher (11) below.

Developer replenisher: Hydroquinone 35.0
gN・Methyl P・Aminophenol sulfate 0.
89 Sodium hydroxide 9.
09 Potassium triphosphate 74
．． 09 Potassium sulfite 90
．． 09 Ethylenediaminetetraacetic acid disodium
1.093-diethyl-amino-1-pronol 11.095-methylbenzotriazole
0.59 Sodium Bromide
3. Q9 Add water (PHill, 7
11) The processing results 't- are shown in Table 2.

Table 2 shows that stable performance can be obtained by simple usage.

(Effects of the Invention) From the above, according to the present invention, it is possible to stably obtain ultra-high contrast characteristics of a photosensitive material containing a hydrazine derivative with a very simple operation that is easy to handle7. It would be possible to reduce compositional fluctuations and to reduce fluctuations in the photographic properties of the resulting light-sensitive materials (and two others) ゛-11~' Director General of the Japan Patent Office U24 Kitachi nβ 6. Number of inventions increased by amendment 207, Subject of amendment - ``Detailed explanation of the invention after the specification'' column
/Ko\

Claims (1)

[Scope of Claims] In a method of developing a silver halide photographic light-sensitive material containing a hydrazine derivative to form an ultra-high contrast image, the processing solution at the start of development includes the following a to d a, developing agent b, 0 An image forming method characterized by using a developer replenisher containing a sulfite c, an amino compound d, and a buffer in an amount of 25 moles or more per liter, to which a developer activity enhancer is added.