JPS6323149A - Image forming method - Google Patents

Abstract

PURPOSE:To improve the stability of a liquid replenisher with lapse of time and to enable stable processing by subjecting a silver halide photosensitive material contg. a hardly soluble metallic compd. to a developing process with a liquid developer replenished with a liquid contg. a compd. which can make complex forming reaction with the metallic ions constituting the hardly soluble base metallic compd. and release a base. CONSTITUTION:The hardly soluble basic metallic compd. is incorporated into the photosensitive material and the compd. which can make complex forming reaction with the metallic ions constituting the basic metallic compd. hardly soluble in water is incorporated into the liquid replenisher of the liquid developer. Both the compds. effect the complex forming reaction during the development to generate the base in the film of the photosensitive material. The basic metallic compd. hardly soluble in the water to be incorporated into the photosensitive material is exemplified preferably by the compd. which has <=0.5 solubility (number of gram of the material dissolving in 100g water) with 20 deg.C water and is expressed by the formula TmXn, where T denotes a transition metal or alkaline earth metal, X denotes the metal which can make an ion pair of M in water and exhibits alkalinity. m and n denote such integers at which the respective valencies of T and X maintain the equal.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to an image forming method in which continuous processing is performed using a silver halide photosensitive material.

Prior art and its problems When developing silver halide photographic materials, reduction of silver halide in the developing solution causes release of halide ions and oxidation of the developing agent, resulting in a decrease in pH, etc. A change occurs in the composition. Further, even during storage during development, the developer is gradually oxidized by air in the tank, causing changes in pl+, developer concentration, preservative concentration, etc.

For this reason, when developing photographic materials continuously or in large quantities, in order to maintain a constant developer composition or developer activity to ensure stable development quality.
The developer tank is refilled with replenisher. Since replenishment of replenisher is an economical and efficient use of developer, apart from some hobby applications and instant photography,
This is done in most processing facilities, such as film labs, general photo labs, plate-making and printing factories, and hospitals.

In this case, the replenisher is used depending on the processing star of the photographic material.
Also, sometimes it is added at a rate depending on the elapsed time. The replenisher has the function of replenishing components that are consumed or taken out from the bath during development processing or over time, and also has the function of adjusting the concentration of generated reaction products (halide ions, etc.) by dilution. Needless to say, the depleted amount of developer is also replenished at the same time.

However, similar to the developing mother solution, the replenisher contains a developing agent and a thickening compound such as hydroxylamine in the alkaline aqueous solution, so special care must be taken when preparing the solution.
Furthermore, since the solution tends to change during storage, it is difficult to prepare a large amount of the solution at one time.

(2) Purpose of the Invention An object of the present invention is to provide an image forming method that can improve the stability of a replenisher over time and enable stable processing.

■Disclosure of invention These objects are achieved by the invention described below.

That is, in the present invention, a halogenated SFi photosensitive material containing a sparingly soluble metal compound is replenished with a replenisher containing a compound that causes a complex formation reaction with metal ions constituting the sparingly soluble metal compound to release a base. This is an image forming method characterized by carrying out a development process using a developing solution.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

In the image forming method of the present invention, the silver halide photographic light-sensitive material is normally processed continuously while being replenished with a replenisher. A compound (hereinafter referred to as a complex-forming compound) that can undergo a complex-forming reaction with the metal ion constituting the basic metal compound that is sparingly soluble in water is contained in the replenisher of the developing solution, and A complex formation reaction between the two generates a base in the film of the photosensitive material.

Examples of basic metal compounds that are sparingly soluble in water to be included in the photosensitive material in the present invention include the solubility in water at 20°C (
If the number of grams of a substance that dissolves in 100 g of water is 0.5 or less, the formula TI! The one represented by l xn is preferred.

Here, T is a transition metal such as Zn, Ni, Co, Fe,
Represents an alkaline earth metal such as Mn, such as Ca, Ba, Mg, etc., and X can serve as a counter ion for M, which will appear in the explanation of complex-forming compounds described later in water, and exhibits alkalinity. For example, carbonate ion, phosphate ion, silicate ion, borate ion, aluminate ion, hydroxyl ion, oxygen atom. m and n represent integers such that the valences of T and X are balanced, respectively.

Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate ((:aMg((:O:l) 2 ), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, hydroxide Aluminum, magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, aluminic acid Zinc, calcium aluminate, basic zinc carbonate (2ZnC03.3
7, n(Oll) 2 ・If 20), basic magnesium carbonate (:1MgCO3 ・Mg(011) 2
・:]OH0), basic nickel carbonate (NiC03・2
Ni(Oll) 2 ), basic bismuth carbonate (Bi
2 (GO3)02 ・H20), basic cobalt carbonate (2GO(:03 ・3Co(OH) 2 ),
Aluminum Magnesium Oxide Among these compounds, those that are not blue in color are particularly preferred.

In the present invention, the complex-forming compound contained in the replenisher of the developer includes a metal ion constituting the basic metal compound,
A complex salt having a stability constant of 1 or more in ILog is produced.

These complex-forming compounds are described, for example, by N.E. Martill and R.M. Smith.
ell, R.M., Sm1th), “Critical
Stadriti Constance (CriticalSLa)
"Bility Con5tants), Volumes 1-5",
Plenum Press.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, aniline carboxylic acids, pyridine carboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri,
Tetracarboxylic acids and compounds with further substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthi, phosphino, etc.), alkali metals such as hydroxamic acids, polyacrylates, and polyphosphoric acids, guanidines, amidine and quaternary ammonium salts.

Preferred specific examples include picolinic acid, 2゜6-pyridinedicarboxylic acid, 2.5- and lysinedicarboxylic acid, 4-
Dimethylaminopyridine = 2.6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, oxalic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA, NTA, CDTA, hexametaphosphoric acid,
Tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, 1102 CCH20CI(2(:l辷0C112CO
211.

1102 CC1120CI 2 CO2H.

Examples include alkali metal salts such as l13 H203P-C1 (-PO3112), guanidine salts, amidine salts, and quaternary ammonium salts.

Among these, aromatic heterocyclic compounds having at least one -C02M and one nitrogen atom in the ring are preferred. The ring may be a monocyclic ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -C
The position where O2M is bonded to the ring is particularly preferably α-position with respect to the N atom. M is any one of an alkali metal, guanidine, amidine and quaternary ammonium ion.

More preferable compounds include those represented by the following formula.

Formula In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -co2M, a hydroxycarbonyl group, and an electron-donating group such as an amine group, a substituted amino group, and an alkyl group. Two R's may be the same or different.

Zl and 22 each have the same definition as in R, and Zl and 22 may be combined to form a ring fused to the pyridine ring.

Next, the most preferred examples of combinations of slightly water-soluble basic metal compounds and complex-forming compounds are listed (here, M is an alkali metal ion, a substituted or unsubstituted guanidinium ion, an amidinium ion, or a quaternary (represents ammonium ion).

Basic magnesium carbonate - Basic zinc carbonate - Basic magnesium carbonate - Calcium carbonate - Zinc oxide - Calcium carbonate - Calcium carbonate - Magnesium oxide - Zinc hydroxide - +13 CCI+3 ~ Magnesium hydroxide - M salt of hexametaphosphoric acid Calcium carbonate - Base Basic magnesium carbonate - Calcium carbonate - Basic zinc carbonate - These combinations can be used alone or in combination of two or more.

Here, the mechanism of generating a base in the developer in the present invention will be explained using a combination of potassium picolinate and zinc hydroxide as an example.

The reaction between the two is shown, for example, by the following formula.

That is, when water in the developer is involved, picolinate ions cause a complex-forming reaction with zinc ions, and as a result of the reaction represented by the above formula proceeding, a base is generated.

The progress of this reaction is due to the stability of the complex formed, but the progress of this reaction is due to the stability of the complex formed, and
ML generated from ML2. The stability number of the complex, expressed as ML3, is very large as shown below and explains the progress of this reaction well.

ML ML2 ML3J2ogK
5.30 9.62 12.92 Slightly soluble metal compounds are described in JP-A-59-174830 and JP-A-53-10.
It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 2733, etc., and the average particle size is 50.
It is preferably 5 μ or less, particularly 5 μ or less.

The basic metal compound in the present invention may be added to any layer such as an emulsion layer, an intermediate layer, a protective layer, an antihalation layer, a white pigment layer, and a back layer. Moreover, it may be contained in one layer or in two or more layers.

The amount added varies depending on the method of replenishing the replenisher, the complex-forming compound pillars, the compound pillars of the base-soluble metal compound, the particle size, the treatment temperature, etc., and may be an amount sufficient to compensate for the alkali consumed in the treatment. 01-20 g/rn', preferably 0
, 1 to 5 g/rn'.

The amount of the complex-forming compound to be added to the replenisher varies depending on the method of replenishing the replenisher, the pH of the developer, the type of complex-forming compound, etc.
It is preferable to set it to 10 or more. Generally 0.01-10
It is preferable to set it to about mol/ffi.

In the present invention, a common developer is used for developing the photosensitive material.

The developer contains hydroquinone, dihydroxybenzenes such as hydroquinone monosulfonate, and 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known developers such as aminophenols such as methyl-p-aminophenol and P-phenylene diamines such as 3-methyl-4-amino-N, N-diethylaniline can be used alone or in combination.

The developer contains pH buffers such as alkaline carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. agent; hydroxylamine, triethanolamine, West German patent application (
OLS) No. 2622950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, 3. Development accelerators such as 6-thiaoctane-1,8-diol; nucleating agents such as sodium poron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid; Aminopolycarboxylic acids such as acetic acid, cyclohexanediaminetetraacetic acid, iminoniacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the compounds described in JP-A-58-195845, etc. -Hydroxyethylidene-1,1'-diphosphonic acid, Research Disclosure 18170 (May 1979)
The organic phosphonic acids described, aminotris (methylenephosphonic acid), ethylenediamine-N.

Aminophosphonic acids such as N, N', N'-tetramethylenephosphonic acid, JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55
-4024, 55-4025, 55-1262
No. 41, No. 55-65955, No. 55-65956, and Research Disclosure No. 18170 (
chelating agents such as phosphonocarboxylic acids described in May 1979).

The developing agent is generally in a concentration of about 0.1 g to about 30 g per developer inlet, more preferably in a concentration of about 0.1 g to about 30 g per developer inlet.
Use a concentration of about 1 g to about 15 g per 2. The pH of the developer is usually 7 or higher, most commonly about 9.
~ used in about 13.

The replenisher contains the same components as the developer, i.e., a developing agent, an antifoggant,
Add preservatives, etc.

According to the present invention, it is possible to lower the pl+ of the developer replenisher.

For this reason, it is possible to increase the concentration of the type of developing agent whose solubility increases when the PL+ is lowered, which not only extends the life of the processing solution, but also allows for high concentration and low replenishment of the developer replenisher. is measured.

In addition, when a complex forming compound is present in the developer replenisher, conventional alkaline agents (2C03, Na2Co3, 3PO
, etc.), the ionic strength in the solution can be lowered, the solubility of the developing agent can be increased, and the developer replenisher can be refilled at a high concentration and at a low replenishment level.

Therefore, the present invention is particularly suitable for a replenishment method that eliminates overflow and replenishes only the decreased amount (volume) of the processing liquid in the processing tank, so-called "reduced replenishment".

In order to allow for reduced replenishment, high concentrations of developer and the like are required, which is generally accompanied by considerable difficulty in aqueous solutions of high ionic strength. However, as mentioned above, the method of the present invention is very advantageous because the constraints on the pl+ and ionic strength of the replenisher are greatly reduced and the concentration of the developing agent is increased. In addition, in the method of the present invention, a low pH can be selected at which the air oxidation of the developing agent does not proceed, which is particularly advantageous for the reduced amount replenishment method.

The amount of the developer replenisher and the complex-forming compound contained in the developer depending on the developer replenishment method and the pH of the developer
The average concentration in the swollen film of the number of moles of basic metal compounds to be reacted in total is preferably 1710 or more when it is also added to the developer, although it varies depending on the type of complex-forming compound. Generally, the developer replenisher contains 0.01 to 5 mol/J!
It is better to set it as a degree. Also, when added to the developer, the amount is about 0.01 to 5 mol/J2.

Further, it is desirable that the solution contains a larger amount of the complex-forming compound than the number of moles of the basic metal compound that is sparingly soluble in water contained in the photosensitive material to be processed with the solution. This is because the amount of liquid generated can be made proportional to the processing amount of the photosensitive material, more precisely, the amount of development reaction, and even more precisely, the amount of development reaction.

The amount and method of replenishing the replenishing fluid follow the usual methods.

In addition, the replenisher may contain a water softener, a solubilizing agent, a base for adjusting ionic strength, and the like. Moreover, it can also be used in combination with the above-mentioned pH buffering agent, if necessary.

Examples of water softeners include polyphosphoric acid compounds such as sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, or potassium salts of the above polyphosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Examples include aminopolycarboxylic acids represented by dichlorohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and the like.

The amount added varies depending on the hardness of the water, but it is usually used at around 0.5 to 10 g/fi.

Organic solvents may be used as solubilizing agents, ie, those that improve the solubility of developer components, especially the developing agent.

These include ethylene glycol, hexylene glycol, diethylene glycol, methyl cellosolve, methanol, ethanol, acetone, triethylene glycol,
Dimethylformamide, dimethyl sulfoxide, etc. Special Publication No. 1983-33378, Special Publication No. 44-9509
This includes the compounds described in No.

The amount added can vary widely depending on the component composition of the liquid, but is usually 50% or less, often 10% or less of the liquid used. However, the solvent constituting the treatment liquid may be anhydrous.

Salts include NaNO3, No, Na25O-,
NaC1,KC! l, borax, NaHCO3, HCO
3. Boric acid, etc. can be mentioned.

The fixing agent used for fixing is a known fixing agent, namely, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid, 3.6- These are water-soluble silver halide solubilizing agents such as thioether compounds such as cythio-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more.

In the case of fixing treatment, the concentration of the fixing agent is preferably 0.2 to 4 mol/〃.

Further, the pH of the fixer is generally preferably 4.0 to 9.0, particularly preferably 5.0 to 8.0.

In addition to the above-mentioned additives, the fixer may contain preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine, and bisulfite compounds of aldehyde compounds (e.g., acetaldehyde bisulfite). (sodium sulfite), etc. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained.

After the fixing step, processing steps such as water washing and stabilization are performed.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 25°C to 40°C is standard, but higher temperatures can be used to accelerate the processing and shorten the processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Furthermore, each processing time can be made shorter than the standard time within a range that does not cause any problems, if necessary, in order to speed up the process.

In addition, during continuous processing, not only the developer in the development process but also the replenisher of each processing solution in each process,
By preventing fluctuations in the liquid composition, a consistent finish can be achieved. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, etc., as necessary.

The light-sensitive material of the present invention may contain not only the above-mentioned developing agent but also a precursor thereof for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Specific examples of developer precursors include, for example, U.S. Patent No. 3.3.
Indoaniline compounds described in No. 42.597, No. 3 of the same
, No. 342, 599, Research Disclosure 1
No. 4850 (August 1976) and No. 15159 (August 1976)
Schiff base-type compound described in November 1976), 13
Aldol compounds described in No. 924, U.S. Pat. No. 3.71
Metal salt complex described in No. 9.492, JP-A-53-1356
There is a urethane compound described in No. 28, published in JP-A-56-6
No. 235, No. 56-16133, No. 56-59232
No. 56-67842, No. 56-83734, No. 56-83735, No. 56-83736, No. 56-
No. 89735, No. 56-81837, No. 56-544
No. 30, No. 56-106241, No. 56-10723
No. 6, No. 57-97531 and No. 57-83565
Various salt-type precursors described in No. 1, etc. can also be used in the present invention.

In addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used as the silver halide used in the light-sensitive material in the present invention. The average grain size of the silver halide grains (in the case of spherical or approximately spherical grains, the grain size is taken as the grain diameter, in the case of cubic grains, the principal is taken as the grain size, and expressed as an average based on the projected area) is preferably 10 μ or less, but it is particularly preferred. is less than 4μ. The particle size distribution may be narrow or wide.

The shape of these silver halide grains may be any cubic crystal shape, octahedral shape, tabular shape, or a mixed crystal shape thereof.

Silver halide emulsions are usually made from water-soluble root salts (e.g. silver nitrate).
The solution is prepared by mixing the solution with a water-soluble halide salt (e.g. potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin.

Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is similar up to the inside, there are also grains with a layered structure with different interior and exterior structures, and those with a layered structure in which the inside and outside are different.
It may also be of the so-called conversion type as described in US Pat. No. 3,622,318.

Further, either a type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions.

Mees, “The Theory of Photographic Processes,”
Photographic Process), Macmillan: Written by Bea Grafkides, (P, Grafkides) Chin+ie Photograph
Paul Montell
Mantel) Company Use (1957) and other books, and is generally accepted as B. Grafkide (P, G.
Iafkides), Chimic eL Physi
que PhoLographique ) Paul Montel Company F, (19
1967), G.F. Dufin
fin), Photographic Emulsion Chemistry
Chemistry) The Focal Press (T
Published by Focal Press, (1966)
, V4" El Zelikman (V, L, Zelikma
“Making and Coating Photographic Emulsions” by N etal et al.
and Coating Photography
c Emulsion), published by The Focal Press, (19
64). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a type of simultaneous mixing method, P in the liquid phase in which silver halide is produced is
It is also possible to use a method in which Ag is kept constant, ie, the so-called Chondrold double jet method.

According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Tardel water washing method, which involves gelatinization of gelatin, may be used for this purpose. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used.

The process of removing soluble salts may be omitted.

As the silver halide emulsion, a so-called "primitive" emulsion which is not chemically sensitized may be used, but it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Ze!
ikman) et al. or Bar Freezer (I
Die Grundlagen der Photografschenprozesse Mid Silver Silver Halide
Grundlagen dcr r'hotogra
phischenProzcsse miL Silb
erhalogcniden), Akademische Verlagsgesellschaft (Akademische
VerlagsgescllschafL ), (1
968) can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to.

In the present invention, the amount of coated silver is approximately 0,601 to 10 g/.

In order to obtain desired development characteristics, image characteristics, film properties, etc., it may be preferable for the photosensitive material to further contain various additives. These additives include organic compounds with iodide or mercapto free radicals in salt form, such as quenylmercabutotetrazole, alkali metal iodide salts, etc.
However, it is desirable to avoid using large amounts of these.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, photosensitive materials may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, and urea. It may also include derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, U.S. Patent Nos. 2,400,532 and 2,42
No. 3,549, No. 2,716゜062, No. 3,6
No. 17,280, No. 3.772,021, No. 3,
808°003, British Patent No. 1,488,991, etc. can be used.

Preferred examples of antifoggants generally added to the light-sensitive silver halide emulsion layer and non-light-sensitive auxiliary layer of light-sensitive materials include heterocyclic organic compounds such as tetrazole, azaindene, and triazole aminopurines.

Other additives that may be included in the photosensitive material include hardeners, plasticizers, lubricants, surface agents, brighteners, and other additives known in the photographic art.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and pre-treated gelatin.
Scientific Photography of Japan (Bull, Soc, Sci.

Photo, Japan) Number (No,) 16, 3
Enzyme-treated gelatin such as that described on page 0 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used.

As the gelatin graft polymer, gelatin is grafted with a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. Particularly preferred are graft polymers with polymers that are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate, and the like. Examples of these are U.S. Pat. No. 2,763,625;
It is described in No. 1.767, No. 2,956,884, etc.

If necessary, the photographic emulsion can be spectral sensitized by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or by using them in combination with styryl dye or the like.

In photosensitive materials, it is used as a filter dye in the hydrophilic colloid layer, to prevent irradiation, and for various other purposes.
May contain water-soluble dyes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes,
Included are merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The photosensitive material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, an acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

In the photographic material, the photographic emulsion layer and other hydrophilic colloid layers may contain brighteners such as stilbene-based, triazine-based, oxazole-based, or coumarin-based brighteners. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion.

In a photosensitive material, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

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

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 alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl poly Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, and phosphoric acid ester groups, such as oxyethylene alkylphenyl ethers and polyoxyethylene alkyl phosphoric acid esters; amino acids, Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, and heterocycles such as pyridinium and imidazolium. Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic material may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) Such),
Active vinyl compounds (1,3゜5-triacryloyl-hexahydro-5-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2
, 4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

The photosensitive 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)
Acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acids, hydroxyalkyl (meth) Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used.

The present invention is applicable to silver halide photographic materials having at least one silver halide emulsion layer on a support. Specifically, there are black and white negative photosensitive materials for photography, black and white photosensitive materials for printing, photosensitive materials for printing, and photosensitive materials for X-ray.

■Specific effects of the invention According to the present invention, a basic metal compound that is sparingly soluble in water is contained in a light-sensitive material, and a complex-forming compound is contained in a developer replenisher, so that both of them form a complex during development. Since we apply an image forming method in which a base is generated in the film of the photosensitive material through a reaction, the p)l of the replenisher can be lowered, significantly improving the stability of the replenisher over time. be able to. Furthermore, since a base is generated in accordance with the amount of photosensitive material processed, the pH of the developer can be kept constant and stable processing becomes possible.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in detail.

Example 1 Typical X-ray silver iodobromide emulsion (AgBr 98 mol%
, Ag 12 mol%, octahedral system, average particle size 1.3#
IM, gold/sulfur sensitized type), zinc hydroxide was added together with ortho-sensitized type spectral sensitizer, hardener, tetraazaindene, coating aid, etc., and the coating amount was Ag; 8.0 g/rn.
2 (Both sides of support) Zn (OH)2; 1.
Coat on the polyethylene terephthalate base at 7X10' mol/m2 (both sides of the support are placed)! Photographic material 101 was prepared for iL/X-ray.

On the other hand, for comparison, photographic material 102, which was the same as sample 101, was prepared except that zinc hydroxide was removed.

On the other hand, the following ID19 formulation was used as a developer, and a comparative replenisher A and a replenisher B to which sodium picolinate of the present invention was added instead of Na2Co were prepared as replenishers.

Developer solution Replenisher A Replenisher B N-methyl-p-aminophenol・2.25g 2.8g
2.8g! /2 sulfate hydroquinone 8.75g 18g 18g
Na2SO371g 71g 71gNa2 C0
3 (anhydrous) 49g 50g - to Br
4g --Sodium picolinate
- -26,5gH2O1j2 in
1Il pH 10,210,58,0 No precipitation was observed in replenisher B after preparation, but precipitation was observed in replenisher A.

A fan dome is baked on the coated sample, and the liquid level in the developing tank is approximately 6I1. Developing was performed using a roller conveyance type developing machine. At that time, replenisher fj, B was used for sample 10"l, and replenisher A was used for sample 102, each at 9200 ml/
The addition was carried out at a rate of rn2 (215 to 1/3 of the normal replenishment amount).

The photographic results obtained when a 5 m2 sample was processed are shown below.

Table 1 Next, replenishers A and B were placed in a plastic tank and left open for one month, and the above-mentioned treatment was performed using a time-lapse replenisher whose evaporated components were corrected with water. The results after 5m2 treatment are shown below.

Table 2 From the above, it can be seen that when using the method of the present invention, the replenisher has higher stability over time than replenisher A, and high-quality photographic images can be obtained even after time.

Example 2 A fan dome was baked onto the sample 101 of Example 1, and the same treatment as in Example 1 was performed. However, as a replenisher, use the following composition of weight loss replenisher C at a rate of 90 ml/rn" (4
0% reduction).

Replenisher C N-methyl-p-aminophenol 2.8g 172 sulfate hydroquinone 22g Na2SO371g Na2Co, (anhydrous) - KBr
- Sodium picolinate 26.5gH2
O1i pH Adjustment There was no significant difference in photographic performance when the 8.05 m2 sample was processed compared to the beginning of the run.

Claims (1)

[Claims] Replenishment of a silver halide photosensitive material containing a basic metal compound that is sparingly soluble in water with a compound that causes a complex formation reaction with the metal ions constituting the basic metal compound that is sparingly soluble in water and releases a base. An image forming method characterized by carrying out a development process using a developer supplemented with a liquid.