JP2727120B2 - Silver halide photographic material and processing method thereof - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for forming an image of a silver halide photographic light-sensitive material, and more particularly to a method of forming an image of a printing light-sensitive material having rapid processing suitability.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has been steadily increasing. For this reason, the number of developed silver halide photographic materials has been increased, and it has been required to speed up the development processing, that is, to increase the processing amount within the same time.

The above tendency is also seen in the printing plate making field. That is,
Due to the rapid increase in the immediacy and the number of times of information, it is necessary to carry out printing plate making operations in a short delivery time and in a larger amount. In order to satisfy the demands of the printing plate making industry, it is necessary to promote simplification of the printing process and to process the printing plate making film more quickly.

However, shortening the processing time is not preferable because deterioration of residual colors and residual color unevenness occur.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide, for example, a processing time in development, fixing, washing, and / or stabilizing solution processing.
It is an object of the present invention to provide a silver halide photographic light-sensitive material having less residual color and having no residual color unevenness even when ultra-rapid processing of 45 seconds or less is performed, and a processing method therefor.

[Configuration of the invention]

The object of the present invention is to provide a silver halide photographic material having a support and a hydrophilic colloid layer including at least one silver halide emulsion layer coated on the support, wherein the hydrophilic colloid layer is The silver halide grains contained are spectrally sensitized by a compound represented by any one of the general formulas (Ia) and (Ib), and the at least one
A silver halide photographic light-sensitive material characterized in that two hydrophilic colloid layers contain a polymer compound having a heterocycle substituted with a sulfonic acid group, and developing, fixing, washing and And / or a processing method for a silver halide photographic light-sensitive material, characterized in that processing is performed within a processing time of 45 seconds to a stabilizing solution.

[Wherein Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ are each a 5-member or 6-member
Represents a group of non-metallic atoms necessary for completing the membered nitrogen-containing heterocyclic ring, and R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted aralkyl group, an alkoxy group, a phenyl group, a benzyl group, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ and X ₂₁
Represents an anion. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ are 0 or 1
Represents Hereinafter, the present invention will be described in detail.

The processing time of less than 45 seconds in the developing, fixing, washing and / or stabilizing solution of the present invention means that the film comes out of the fixing solution, washing solution and / or stabilizing solution after the leading edge of the film enters the developing solution. The time until the transfer is less than 45 seconds, and includes the time for the transfer from the developing solution to the fixing solution and the time for the transfer from the fixing solution to the washing solution.

First, the general formulas [Ia] and [Ib] will be described.

[Wherein Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ are each a 5-member or 6-member
Represents a group of non-metallic atoms necessary to complete the membered nitrogen-containing heterocyclic ring, for example, a benzothiazole ring, a naphthothiazole ring,
Benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring, quinoline ring,
Examples include a 3,3-dialkylindolenin ring, a benzimidazole nucleus, and a pyridine ring.

These heterocycles are a lower alkyl group, an alkoxy group,
It may be substituted with a hydroxyl group, an aryl group, an alkoxycarbonyl group, or a halogen atom.

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted aralkyl group, an alkoxy group, a phenyl group, a benzyl group, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. Y ₁₁ , Y ₁₂ , Y ₂₁ ,
One of Y ₂₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , and R ₂₆ is an acid group (for example, carbonyl group, sulfonyl group Etc.) or a group substituted with an acid group. X ₁₁ and X ₂₁ represent anions. When there is an acid group, m ₁₁ and m ₂₁ represent 0, and when there is no acid group, m ₁₁ and m ₂₁ represent 1. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ represent 0 or 1.

Next, specific examples of the sensitizing dye used in the present invention (hereinafter, referred to as the sensitizing dye of the present invention) are shown, but the present invention is not limited thereto.

The sensitizing dye of the present invention is contained in a silver halide photographic emulsion in an amount of preferably from 1 mg to 2 g, more preferably from 5 mg to 1 g, per mol of silver halide.

The sensitizing dye of the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Further, sensitizing dyes other than the present invention can be used in combination. When a sensitizing dye is used in combination, it is preferable that the total content is the above content.

The sensitizing dyes of the present invention are described in U.S. Patent No. 2503776, British Patent No. 742112, French Patent No. 2065662, Japanese Patent Publication No. 40-2346.
Can be easily synthesized with reference to the reference numbers.

The polymer compound having a heterocyclic ring substituted by a sulfonic acid group (hereinafter referred to as the polymer of the present invention) used in the present invention preferably has a molecular weight of 2 to 2,000,000. Preferred examples of the hetero ring of the polymer of the present invention include a pyridine ring, a pyrrolidine ring, a carbazole ring, a pyrrole ring, a thiophene ring, a furan feeling, and an indole ring. Examples of the sulfonic acid group include an alkylsulfonic acid group having 1 to 16 carbon atoms or a substituted alkylsulfonic acid group.

In addition, the bonding group of these sulfonic acid groups and hetero acid groups is
Composed of carbon, nitrogen, sulfur, oxygen and phosphorus atoms 2
Any valence bonding group may be used.

As specific examples of the polymer compound of the present invention, homopolymers, copolymers, and terpolymers are listed below, but are not limited thereto.

As a medium for polymerizing the monomer capable of forming the polymer compound of the present invention, in addition to an aqueous solution, an alcohol such as methanol or ethanol, a hydrophilic colloid solution matrix such as an aqueous gelatin solution or tricresyl phosphate sodium salt, The polymer can be formed using the above polymerization initiator in a high boiling point solvent such as paraffin.

The addition amount of these compounds is preferably from 10 ^-9 to 10 ⁵ mg / m ² , particularly preferably from 10 ^-2 to 10 ⁴ mg.

The polymer compound of the present invention can be easily synthesized by obtaining a monomer capable of forming a polymer as a commercial chemical product.

The silver halide photographic light-sensitive material of the present invention has a support and a hydrophilic colloid layer including at least one silver halide emulsion layer provided on the support, and this silver halide emulsion is directly coated on the support. It may be coated or it may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer may be further coated as a protective layer on the silver halide emulsion layer. Also, the silver halide emulsion layers may be divided into silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, the silver halide emulsion layer
An intermediate layer of a hydrophilic colloid layer may be provided between these layers, or an intermediate layer may be provided between a silver halide emulsion layer and a protective layer. The layer containing the compound of the formula [I] according to the present invention and the polymer of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and / or a hydrophilic colloid adjacent to the silver halide emulsion layer. Layer.

To incorporate the polymer of the present invention into the hydrophilic colloid layer, a method of dissolving the polymer of the present invention in an appropriate water and / or organic solvent or adding the solution dissolved in the organic solvent to gelatin or a gelatin derivative is used. A method of adding the compound after dispersing it in the lipophilic colloid matrix or a method of adding the compound dispersed in a latex.

The silver halide emulsion used in the light-sensitive material of the present invention may be a silver halide emulsion such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or silver chloroiodobromide. Any used one can be used, but silver chloride is 50 mol%
Preferably, the particle size is 0.2 μm or more, 0.5 μm
The following is preferred. The amount of gelatin on the emulsion layer side was 2.8 g / m ²
Or less, preferably 2.5 g / m ² or less.

The silver halide grains may be obtained by any of an acidic method, a neutral method and an ammonia method.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. The particles may be particles formed mainly in the particles or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Patent 4,
183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, etc., and the Journal of
Photographic Science (J. Photgr, Sci). Two
By the method described in 1.39 (1973) documents, such as octahedral, tetradecahedral, create a particle having a shape such as dodecahedral, it can also be used this. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

Further, any emulsion having any grain size distribution may be used, and an emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion). May be used alone or in combination. Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

In the present invention, a monodisperse emulsion is preferred. The monodispersed silver halide grains in the monodispersed emulsion are those in which the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. Some are preferred, particularly preferably 70% or more, more preferably 80%
That is all.

Here, the average particle size is the frequency ni of the particles having the particle size ri and
ni × ni ³ with ni ³ defines a grain size ri when the maximum.

(Three significant digits and the least significant digit are rounded off.) The particle size referred to here is the diameter of spherical silver halide grains, or the projected image of grains other than spherical. It is the diameter when converted to a circular image of the peripheral area.

The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection. (The number of particles to be measured is 1000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention are: Is less than or equal to 20, more preferably less than or equal to 15.

Here, the average particle diameter and the standard deviation of the particle diameter are determined from ri defined above. Monodispersed emulsions are described in JP-A-54-48521,
Reference can be made to JP-A-58-49938 and JP-A-60-122935, and the like.

Since the photosensitive silver halide emulsion is not subjected to chemical sensitization, it can be used as a so-called unprimed (Primitive) emulsion, but is usually chemically sensitized. For chemical sensitization, the Glafkides or Zelikman et al., Or
H. Frieser ed. Die Grundlagen der Photographischen Prozesse m
it Silberhalogeniden, Akademicche Verlagsgesellsch
aft, 1968).

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, gold or another noble metal compound can be used.

The conditions such as pH, pAg, and temperature during chemical sensitization are not particularly limited, but the ph value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11, particularly 7 to 9. It is preferable to keep. The temperature is preferably from 40 to 90 ° C, particularly preferably from 45 to 75 ° C.

The photographic emulsion used in the present invention is the above-described sulfur sensitized,
In addition to sulfur sensitization, a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound or the like can also be used in combination.

As the photosensitive emulsion, the above-mentioned emulsions may be used alone, or two or more kinds of emulsions may be mixed.

In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3
Various stabilizers such as a, 7-tetrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole and the like can also be used. If necessary, a silver halide solvent such as thioether or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention may be formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt during the process of forming and / or growing the grains. Alternatively, a metal ion can be added using a complex salt, and the metal ion can be contained inside the particle and / or on the particle surface.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. The removal of the salts can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention,
Further, a sensitizing dye may be added and used in combination. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like.

The sensitizing dye used in the present invention is used at the same concentration as that used for ordinary negative-working silver halide. In particular, it is advantageous to use a silver halide emulsion at a dye concentration that does not substantially lower the intrinsic sensitivity of the emulsion. The sensitizing dye is preferably about 1.0 × 10 ^-5 to about 5 × 10 ^-4 mole per mole of silver halide, and more preferably about 4 × 10 ^-5 mole of sensitizing dye per mole of silver halide.
It is preferable to use a concentration of about 2 × 10 ⁻⁴ mol.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. The sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization.

The silver halide photographic light-sensitive material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a reduction in sensitivity and generation of fog during the production process, storage or processing of the silver halide photographic light-sensitive material.

The silver halide photographic light-sensitive material of the present invention contains, in the photographic constituting layer, U.S. Pat.Nos. 3,411,911 and 3,411,912,
And an alkyl acrylate-based latex described in US Pat.

In the light-sensitive material of the present invention, various additives can be further used according to the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item 17643.
(December 1978) and Volume 187, Item 18716 (November 1979)
The relevant locations are summarized in the table below.

In the implementation of the silver halide photographic light-sensitive material of the present invention,
For example, the emulsion layer and other layers can be formed by coating one or both sides of a flexible support generally used for photographic light-sensitive materials. Useful as a flexible support are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (Eg, polyethylene, polypropylene, ethylene / butene copolymer) or the like coated or laminated. The support may be colored using a dye or a pigment.
It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with an emulsion layer or the like. Undercoating treatment is described in JP-A-52-104913 and JP-A-59-1894.
No. 9, No. 59-19940, and No. 59-11941 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, a photographic emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like can be used.

The developing / fixing / washing / drying steps performed in the present invention for a development time of 20 seconds or less, preferably 15 seconds or less, will be described.

The developing agent used in the black-and-white developing solution used in the present invention has a dihydroxybenzene chain and 1
Most preferred are combinations of -phenyl-3-pyrazolidones. Needless to say, a p-aminophenol-based developing agent may also be contained.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

Examples of the developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine , 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p
-Aminophenol is preferred.

The developing agent is preferably used usually in an amount of 0.01 mol / to 1.2 mol /.

Examples of the preservative of the sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The amount of the sulfite is preferably 0.2 mol / or more, particularly preferably 0.4 mol / or more. The upper limit is preferably up to 2.5 mol /.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters.

Buffers such as JP-A-61-28708 (borate) and JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Additives other than the above components include development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethinol, methanol Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benzes such as 5-methylbenztriazole It may contain an antifoggant such as a triazole compound, and further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hard water softener,
It may contain an amino compound described in 106244 or the like.

In the present invention, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used in the developer.

Amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer of the present invention.

LFA Meson, "Photographic Processing Chemistry", Focal Press (1966
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933 and the like may be used.

In the present invention, the term "development time" and "fixing time" refer to the time from the time when the photosensitive material to be processed is immersed in the developing tank solution of the automatic machine to the time when the photosensitive material is immersed in the next fixing solution. It means the time from immersion to the next washing tank liquid (stabilizing liquid).

The term “washing time” refers to the time during which the sheet is immersed in the washing tank liquid.

Further, the "drying time" is usually 35 ° C to 100 ° C, preferably 4 ° C.
The drying zone to which the hot air of 0 ° C to 80 ° C is blown is installed in the automatic processing machine, but refers to the time in the drying zone.

The development temperature and time are about 25 ° C. to 50 ° C. for 15 seconds or less, preferably 30 ° C. to 40 ° C. for 6 seconds to 15 seconds.

The fixing solution is an aqueous solution containing a thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate. Thiosulfuric acid ions and ammonium ions are essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, and is generally about 0.1 to about 6 mol /.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, ammonium sulfate, potassium alum and the like.

Tartaric acid, citric acid or their conductors can be used alone or in combination of two or more in the fixing solution.
It is effective that these compounds contain 0.005 mol or more per fixing solution, particularly 0.01 mol / to 0.03 mol /.

Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like.

The fixing solution may optionally contain a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or nitric acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening property, The compounds described in JP-A-60-213562 can be included.

The fixing temperature and time are preferably from about 20 ° C to about 50 ° C for 6 seconds to 1 minute, more preferably from 30 ° C to 40 ° C for 6 seconds to 30 seconds, and still more preferably from 30 ° C to 40 ° C for 6 seconds to 15 seconds. It is.

When the fixer concentrate is replenished to the automatic processor by the method of the present invention together with water for diluting the photosensitive material as it is processed, it is most preferable that the fixer concentrate is composed of one agent. Is the same as in the case of the developer.

Fixing solution can be stably present as one agent at pH 4.5
And more preferably pH 4.65 or more. pH4.5
If it is less than 30, the thiosulfate is decomposed and finally sulfided, especially when the fixing solution is left for many years until it is actually used. Therefore, in the range of pH 4.5 or more, the generation of sulfurous acid gas is small and the working environment is improved. The upper limit of the pH is not so severe, but if the fixing is carried out at an excessively high pH, the membrane pH is increased even after washing with water, and the membrane swells and the drying load is increased. In the case of a fixing solution that hardens using an aluminum salt, the pH is limited to a pH of 5.5 or less, which prevents precipitation and precipitation of the aluminum salt.

In the present invention, either the developing solution or the fixing solution may be a so-called working solution which does not require the above-mentioned dilution water (that is, replenishes as an undiluted solution).

The supply amount of each concentrated solution to the treatment tank solution and the mixing ratio with the dilution water can be variously changed depending on the composition of the concentrated solution.
The total amount of each of these developing solution and fixing solution is preferably 50 ml to 1500 ml per 1 m ² of the photosensitive material.

In the present invention, the light-sensitive material is subjected to washing or stabilization after the current solution and fixing.

Any method known in the art can be applied to the washing or stabilizing treatment, and water containing various additives known in the art can be used as the washing water or the stabilizing solution. The use of water which has been subjected to antifungal means in the washing water or stabilizing solution, not only the possible water saving processing of the photosensitive material 1 m ² per 3 less replenishing rate, automatic processor installed in the piping is not required Further, the number of stock tanks can be reduced. That is, the preparation dilution water and the washing water or the stabilizing solution for the developing solution and the fixing solution can be supplied from one common stock tank, so that the automatic developing machine can be made more compact.

When water that has been subjected to antifungal means is used in combination with washing water or a stabilizing solution, the occurrence of scale can be effectively prevented.
0 to 3, preferably 0 to 1, water saving treatment can be performed per ² pieces.

Here, the case where the replenishment amount is 0 means that no replenishment is performed except for appropriately reducing the amount of the washing water in the washing tank due to spontaneous evaporation or the like. This refers to the case where the processing method is performed.

As a method for reducing the amount of replenishment, a multi-stage countercurrent direction (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material of the fixing solution is gradually processed in a clean direction, that is, the processing solution which is not contaminated with the fixing solution is successively contacted and processed. Washing is performed. According to this, unstable thiosulfate and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more remarkable stabilizing effect is obtained. The amount of washing water is very small compared to the conventional method.

When washing with a small amount of washing water, it is more preferable to provide a squeeze roller washing tank described in Japanese Patent Application No. 60-172968.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the water subjected to the fungicide means to the washing or stabilizing bath according to the treatment, is disclosed in JP-A-60-2351.
As described in No. 33, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. By doing so, it is more preferable because the stock water can be saved and the waste liquid can be reduced.

As the antifungal means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion-exchange resin described in JP-A-61-131632 are used. Method for making pure water, Japanese Patent Application No. 60-253807, 60-2958
No. 94, No. 61-63030, and No. 61-51396 can be used.

Furthermore, LEWest “Water Quality Criteria” Photo
Sci & Eng.Vol.9No.6 (1965) 、 MWBeach “Microbiolo
gical Growths in Motion-Picture Processing "SMPTE
Journal Vol.85, (1976) .RODeegan, “Photo Process
ing Wash Water Biocides "J.Imaging Tech.Vol 10, No.6
(1984) and JP-A-57-8542, JP-A-57-58143, and JP-A-57-58143.
-105145, 57-132146, 58-18631, 57-9
No. 7530, antibacterial agents described in Nos. 57-157244 and the like,
Anti-binders, surfactants and the like can be used in combination.

Furthermore, in the washing bath, RTKreiman's J. Image, Tech 10,
(6) Isothiazoline compounds described in 242 (1984), RESEARCH DISCLOSURE Vol. 205, Item 20526 (1981)
Compounds described in Japanese Patent Application No. 61-51396, vol. 228, Item 22845 (April 1983), and the like. Can be used in combination as a bacteriostatic agent (Microbiocide).

Further, specific examples of the anti-binder include phenol, 4-chlorophenol, pentachlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoate,
2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluorodichloromethylthio) -phthalimide, 2,4,4'-trichloro-2'-hydro Oxydiphenyl ether and the like.

The water stored in the water stock tank with the antifungal means is preferably used as both a diluting water for the processing solution stock solution such as the developer fixing solution and a washing water, in view of a small space requirement. However, the preparation dilution water and the washing water (or stabilizing solution) which have been subjected to the antifungal means can be separately stored in separate tanks, or only one of them may be taken directly from the tap water.

When stored separately in a separate tank, various additives can be added to the washing water (or stabilizing bath) in addition to the antifungal means of the present invention.

For example, aluminum and chelate stability logK value is 10
The above chelate compound may be contained. They are,
When the fixing solution contains an aluminum compound as a hardener, it is effective for preventing white precipitation in washing water.

Specific examples of the chelating agent include ethylenediaminetetraacetic acid (logK 16.1, the same applies hereinafter), cyclohexanediaminetetraacetic acid (17.6), and diaminopropanoltetraacetic acid (13.
8), diethylene triamine pentaacetic acid (18.4), triethylene tetramine hexaacetic acid (19.7) and the like, and sodium salts, potassium salts and ammonium salts thereof, and the amount of addition is preferably 0.01 to 10 g /, more preferably 0.1 to 5 g. /.

Further, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of a cationic type, an anionic type, a nonionic type and a zwitterionic type may be used. Specific examples of surfactants include, for example, compounds described in “Surfactant Handbook” issued by Kogyo Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (for example, pH 3 ~
8) Various buffering agents (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) And aldehydes such as formalin. In addition, various additives such as chelating agents, bactericides (thiazoles, isothiazoles, halogenated phenols, sulfanilamides, benzotriazoles, etc.), surfactants, optical brighteners, hardeners and the like may be used. Two or more of the same or different target compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster of the processing solution,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storability.

Washing or stabilizing bath temperature and time by the above method are 0
C. to 50.degree. C. for 6 seconds to 1 minute is preferable, but 15.degree. C. to 40.degree. C. for 6 seconds to 30 seconds is more preferable.
Seconds are preferred.

According to the method of the present invention, the photographic material which has been developed, fixed and washed is squeezed out of the washing water, that is, dried via a squeeze roller method. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions.
Usually, it may be about 5 seconds to 1 minute, but more preferably 40 ° C to 80 ° C.
C. for about 5 to 30 seconds.

In the present invention, the more excellent the effect that the drying time can be shortened as the swelling percentage in the photosensitive material is reduced.

According to the method of the present invention, the processing time of so-called Dry to Dry until development, fixing, washing and drying is performed within 100 seconds, preferably within 60 seconds, more preferably within 50 seconds.

Here, "dry to dry" refers to the time from the moment when the tip of the photographic material to be processed enters the film insertion part of the automatic processing machine to the time when it is processed and the same tip comes out of the automatic processing machine. .

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by this.

Example 1 A silver nitrate aqueous solution and 2 mol per mol of silver halide were placed in a container heated at 40 ° C. containing gelatin, sodium chloride and water.
× 10 ^-6 mol of potassium hexachloroiridate and 4
Silver bromochloride particles containing 35 mol% of silver bromide (double-distribution) by adding a mixed aqueous solution of potassium bromide and sodium chloride to which × 10 ^-7 mol of potassium hexabromorhodate is added by a double jet method. (12%, cubic, particle size 0.33μm)
Was adjusted while maintaining the pH at 3.0 pAg 7.7, and after returning to pH 5.9, desalting was carried out by a conventional method.

This emulsion was sensitized with gold and sulfur to give
1 was added in an amount of 240 mg per mole of silver halide, and 70 mg of 1-phenyl-5-mercaptotetrazole was added per mole of silver halide, and 4-hydroxy-6-methyl-1,3,3a, 7- After ripening was stopped by adding 1.2 g of tetrazaindene and gelatin, 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin, and a polymer of styrene-maleic acid were used per mol of silver halide. 2 g, 3 g of a high molecular weight polymer latex of ethyl acrylate, 1-hydroxy-3.5 dichlorotriazine sodium salt and formalin as a hardening agent, and then a silver amount of 4.3 on a subbed polyethylene terephthalate support. g / m ²
The amount of gelatin was adjusted to 2.5 g / m ² , and 40 g of the polymer compound of the present invention (Table 1), 10 g of potassium bromide, and 1-decyl-2- (3
-Isopentyl) succinate-2-sodium sulfonate (4 g) was added, and amorphous silica having an average particle size of 5 μm was added to 10 g of amorphous silica.
0 g was added and dispersed, and the emulsion layer and the protective layer were simultaneously coated so that the gelatin became 1.0 g / m ² .

On the other side of the coated surface, a gelatin solution containing dyes (a) and (b) was previously coated with gelatin.
3.3 g / m ² , dye (a) 130 mg / m ² , dye (b) 50 mg / m ²
It was applied so that it becomes.

The sample thus obtained was treated with the following developing solution and fixing solution using a conventional roller-type automatic developing machine under the following conditions, and the residual color was evaluated.

The surface resistivity of the emulsion layer side of each sample was evaluated under the conditions of 23 ° C. and 30% RH.

The residual color was evaluated in 10 steps, with 10 being the best and 1-4 being unusable and 5 or more being the usable level.
The results are shown in Table 1.

From Table 1, it can be seen that those of the present invention have little residual color.

Processing conditions (Process) (Temperature) (Time) Current image 38 ° C 12 seconds Fixed 36 ° C 12 seconds Rinse at room temperature 12 seconds Dry 50 ° C 10 seconds Developer formulation Pure water (ion exchange water) Approx. 800 ml Potassium sulfite 60 g Ethylenediaminetetraacetic acid disodium salt 2 g Potassium hydroxide 60 g 5-methylbenzotriazole 300 mg Diethylene glycol 50 g 1-phenyl-4,4-dimethyl-3-pyrazolidinone 300 mg 1-phenyl-5 mercaptotetrazole 60 mg Potassium bromide 3.5 g Hydroquinone 20g Potassium carbonate 15g Add pure water (ion exchange liquid water) to make 1,000ml. The developer pH was 10.8.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% w / v aqueous solution) 13.6ml (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% w / v aqueous solution) 4.7 g Aluminum sulfate (aqueous solution with an Al ₂ O ₃ equivalent content of 8.1% w / v) 26.5 g Water when using the fixing solution The above composition A and composition B were dissolved in 500 ml in this order and finished to 1 for use. The pH of this fixer is about
4.3.

[Effects of the Invention] According to the present invention, it is possible to provide a processing method with less occurrence of residual color or the like even when ultra-rapid processing is performed.

Claims (2)

(57) [Claims] 1. A silver halide photographic material having a support and a hydrophilic colloid layer including at least one silver halide emulsion layer coated on the support, wherein the hydrophilic colloid layer is contained in the hydrophilic colloid layer. A silver halide grain is spectrally sensitized by a compound represented by any one of the following formulas (Ia) and (Ib), and the at least one hydrophilic colloid layer is substituted with a sulfonic acid group; A silver halide photographic material characterized by containing a polymer compound having a ring. 2. The processing time of the silver halide photographic light-sensitive material according to claim 1 for developing, fixing, washing and / or a stabilizing solution.
A processing method for a silver halide photographic material, wherein the processing is performed within 45 seconds. [Wherein, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, and R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, respectively. R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom,
Substituted or unsubstituted alkyl, alkoxy, phenyl, benzyl, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle. R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ and X ₂₁ represent anions. When there is an acid group, m ₁₁ and m ₂₁ represent 0, and when there is no acid group, m ₁₁ and m ₂₁ represent 1. n ₁₁ , n ₁₂ , n ₂₁ and n
₂₂ represents 0 or 1. ]