JPH0329940A - Silver halide photographic sensitive material and method for processing this material - Google Patents

Abstract

PURPOSE:To decrease the generation of after-colors, etc., even when the above material is processed with ultra high speed processing by forming the material in such a manner that the silver halide particles contained in hydrophilic colloidal layers are spectrally sensitized by specific compds. and contain the high- polymer compd. having a heterocycle substd. with a sulfonic acid group. CONSTITUTION:The silver halide particles contained in the hydrophilic colloidal layers are spectrally sensitized by the compds. expressed by formula I and formula II and at least one of the hydrophilic colloidal layers contains the high-polymer compd. having the heterocycle substd. with the sulfonic acid group. In the formulas, Y11, Y12, Y21, and Y22 respectively denote the nonmetallic atom groups necessary for perfecting a 5- or 6-membered nitrogenous heterocycle; R11, R12, R21 and R22 respectively denote an alkyl group, aryl group or aralkyl group; R13 to R15, R23 to R26 respectively denote a hydrogen atom, alkyl group, alkoxy group, etc. The good after-colors are obtd. and the unequal after-colors are eliminated in this way even if the ultra high speed processing is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image formation or method for silver halide photographic materials, and more particularly to an image formation or method for printed light-sensitive materials suitable for rapid processing.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, as the immediacy and number of times information is rapidly increasing, it is becoming necessary to shorten delivery times and handle larger quantities of printing plate-making operations. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

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

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to eliminate residual color even when ultra-quick processing is performed, for example, in which processing time for development, fixing, washing, and/or stabilizing liquid is within 45 seconds. An object of the present invention is to provide a method for processing a silver halide photographic material without unevenness in residual color.

[Structure of the invention]

The second object of the present invention is to provide a silver halide photosensitive material having a support and a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer. The silver halide particles contained in the hydrophilic colloid layer have the following general formula [1a] and general formula [■
A silver halide photograph spectrally sensitized by the compound represented by b), and characterized in that the at least one hydrophilic colloid layer contains a polymer compound having a heterocycle substituted with a sulfonic acid group. A photographic material and a method for processing a silver halide photographic material, which is characterized in that the silver halide photographic material is processed within 45 seconds from development, fixing, washing and stabilizing solution. be done.

General formula [■a] (x++e)m General formula CI+))? In the formula, Yz. Y+■, Y2, and Y2■ are each 5
R1■, R1■, R2■ and R2■ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group. represents a group.

R13・R mouth・R15・R23・R2i・R
25 and R26 are each a hydrogen atom, substituted or unsubstituted a? represents an unsubstituted alkyl group (the number of carbon atoms in the alkyl moiety is 1 to 18, preferably 1 to 4), or an aryl group, and W and W2 are connected to each other to form a 5- or 6-membered nitrogen-containing hetero You can also shape the ring.

Further, R13 and R15 and R23 and R25 can be linked to each other to form a 5-membered ring or a 6-membered ring. X
．． and X21 represents an anion. nll+nl■,n
21 and n2■ do not represent O or l. ] The present invention will be explained in detail below.

The developing, fixing, washing and/or stabilizing solution of the present invention (X2+
. ) ln2, Processing time within 45 seconds means that the time from when the leading edge of the film enters the developer until it comes out of the fixer, washing solution, or/and stabilizing solution is within 45 seconds, and the processing time is within 45 seconds. This includes the transfer time from the solution to the fixer and the transfer time from the fixer to the washing solution.

First, general formula [■a] and general formula [Ib] will be explained.

General formula (Ia) (X+ 10)! l++ + General formula C I b:] Naf1-selenazole ring, penzoxazole ring, naph1-oxazole ring, quinoline ring, 3,3-dialkylindolenine ring, benzimitasol nucleus, pyridine ring, etc. I can do it.

These heterocycles include lower alkyl groups, alkoxy groups, hydroxyl groups, aryl groups, alkoxy groups,
It may be substituted with a halogen atom.

R ll+ R 121 R 21 and R2. each represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

RI31 Rl41 Rl61 R231 R241
R25 and R26 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, ? In the formula, Y ll+ Y 121 Y-21 and Y2■ each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a penzothiazole ring, a naphthothiazole ring, penzoselenazole ring,
or an unsubstituted alkyl group (alkyl moiety has 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms), an aryl group,
Wl and W2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

7 8? In addition, R13 and Rl6 and R23 and R26 can be linked to each other to form a 5- or 6-membered ring OY
■・Y12・Y 21,Y 22,R ,,・Rl2・
R13・RliR 15, R 2+. R 2■IR 2
One of 31R 241R 261R 21 is preferably an acid group (eg, carbonyl group, sulfonyl group, etc.) or a group substituted with an acid group. x1I and X2. represents an anion.

If there is an acid group, mll+m2+ represents O, and if there is no acid group, mll+m21 represents 1. ”ll+ nl2+
n2+ and n2■ do not represent 0 or l.

Next, specific examples of the sensitizing dye used in the present invention (hereinafter referred to as the sensitizing dye of the present invention) will be shown. ■ 14 ■ 15 ■ 16 CH2CH20H 10 IO IO IO Io IC + 1 IC) 1E Io CH2CH20H ■ 9 ■ 10 ■ L1 ■ 17 ■ L8

C2II5 ■ ■ ■ ■ 2l 22 23 24 C2H5 l5 C2H5 C2H. CH2CH20H He IO I0 The sensitizing dye of the present invention is preferably contained in the silver halide photographic emulsion in an amount of 1 mg to 2 g, more preferably 5 mg to 1 g per mole of silver halide.

The sensitizing dyes of the present invention can be directly dispersed into emulsions. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then 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. Furthermore, sensitizing dyes other than those of the present invention may be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye of the present invention can be easily obtained by referring to US Pat. No. 2,503,776, British Patent No. 742,112, French Patent No. 2,065,662, and Japanese Patent Publication No. 40-2346.

The polymer compound having a heterocycle substituted with a sulfonic acid group used in the present invention (hereinafter referred to as the polymer 16 of the present invention) preferably has a molecular weight in the range of 2,000,000 to 2,000,000. Preferred examples of the heterocycle in the polymer of the present invention include a pyridine ring, a pyrrolidine ring, a carbazole ring, a pyrrole ring, a thio-7-functional ring, a heptad-ring, and an indole ring. In addition, as a sulfonic acid group, carbon 1-1
6 alkylsulfonic acid groups or substituted alkylsulfonic acid groups.

The bonding group between the sulfonic acid group and the heterocyclic group may be any divalent bonding group composed of carbon, nitrogen, sulfur, oxygen, and phosphorus atoms.

Homopolymers, copolymers, and terpolymers are listed below as typical examples of the polymer compound of the present invention, but the invention is not limited to these.

SO3Na (6) (7) (8) (9) (14) (l5) (16) (17) So 3Na 19 C113 M 30) 75 (10) (11) (12) (13) (18) (20 ) (2l) 20 x:y:z:w=50:30:10:10M#600,000C113 x:y:z:w-40:30:20:10M! -500,000 M4-30, +5 (23) Forming a polymer using the above polymerization initiator in an alcohol such as methanol or ethanol, in a hydrophilic colloid solution matrix such as an aqueous gelatin solution, or in a high boiling point solvent such as tricresyl phosphate sodium salt, liquid paraffin, etc. I can do it.

The amount of these compounds added is lO-9~lo5mg/m2
up to 10'mg, particularly preferably 1O-2 to 10'mg
It is.

The polymer compound of the present invention can be obtained as a commercially available heptanomer capable of forming a polymer, and can be easily synthesized.

The silver halide photographic material of the present invention comprises a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support, and this silver halide emulsion is directly coated on the support. It may be coated or removed via a hydrophilic colloid layer that does not contain a silver halide emulsion, and a hydrophilic colloid layer may be further coated as a protective layer on the silver halide emulsion layer. good. Also, the silver halide emulsion layers have different sensitivities,
For example, it may be divided into high-speed and low-speed silver halide emulsion layers. In this case, the silver halide emulsion layer may be provided with an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. good. The layer containing the compound of general formula [■] 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. It is a layer.

In order to incorporate the polymer of the present invention into the hydrophilic colloid layer, the polymer of the present invention may be dissolved in appropriate water and/or an organic solvent and then added, or the solution dissolved in an organic solvent may be added to gelatin or a hydrophilic gelatin derivative. Examples include a method in which the compound is added after being dispersed in a sex colloid matrix, or a method in which the compound is added after being dispersed in latex.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Although any material used for
．． The thickness is preferably 5 μm or less.

In addition, the amount of gelatin on the emulsion layer side is 2.89/m2 or less,
Preferably it is 2.59/m2 or less.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

The silver halide grains may have a uniform silver halide composition or distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the interior of the grain and the surface layer. It may be a particle that is mainly formed on the surface, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having {100} planes as crystal surfaces.

Also, U.S. Patent Nos. 4,183.756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, and The Journal of Photographic Science (J.Photogr.
Sci). 21. Particles having shapes such as octahedrons, tetradecahedrons, and dihedrals can be prepared by the method described in literature such as 39 (1973) and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, particles with any particle size distribution may be used.
An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination.

Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

In the present invention, monodispersed emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, 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 weight of all silver halide grains. It is preferably at least 70%, particularly preferably at least 70%, even more preferably at least 80%.

Here, the average particle size 7 is the frequency n1 of particles having particle size ri.
The product old x ri3 of and r13 is the maximum grain size r
Define i.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on a print.

(The number of grains to be measured is indiscriminately 1000 or more.) Particularly preferred highly monodispersed emulsions of the present invention have a monodispersity defined by 20 or less, and even more preferably 20 or less.
is 15 or less.

27 28 Here, the average particle size and particle size standard deviation shall be determined from ri defined above. The monodispersed emulsion is disclosed in Japanese Patent Application Laid-Open No. 5448521.
No. 58-49938 and No. 60-1.22935
This information can be obtained by referring to the No. 1 Publication, etc.

The photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, or it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
elikman et al. or l{. Frieser
Edited by De Grun 1, Lagen del Fo I, Grafschen Hlotsese Mito Zilber Halogennieden (D
ie Grundlagen der Pbotogr
apliischen Prozesse mit S
ilberhalogeniden, Akademi
cche Verlagsgesellschafc,
(1968) can be used.

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

Further, there are no particular restrictions on the conditions such as pH and pAgX temperature during chemical sensitization, but the pll value is preferably 4 to 9, especially 5 to 8, and l) the Ag value is 5 to l1, especially 7 to 9. It is preferable to keep it at Also, the temperature is 40 to 90°C,
Particularly preferred is 45 to 75°C.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, and the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

In carrying out the present invention, for example, 4-hydroxy-6-methyl 1,3.3
a, 7-te 1 lazainden, 5-mercap 1 what = 7
Various stabilizers can also be used, including henylte-1.razole, 2-mercaf-1.penzothiazole, and the like.

Furthermore, if necessary, silver halide solvents such as thioethers, or crystal habit control agents such as mercap 1 group-containing compounds and sensitizing dyes may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron Metal ions can be added using salts or complex salts to be included inside the particles and/or on the surface of the particles.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the elongation of the silver halide grains is completed, or they may be left in the emulsion. In the case of removing the salts, it 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, a sensitizing dye may be further added and used in combination.

Dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar anine dyes, heminanine dyes, styryl dyes, and hemioxinol dyes.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary non-gauss type silver halide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10-
' to about 5 X 10-' moles of sensitizing dye are preferred, particularly from about 4 X 10-5 to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

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 the purpose of supersensitization.

The silver halide photographic 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 preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes: hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer 31 32 or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic material.

Further, the silver halide photographic abrasive material of the present invention contains U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Volume 176 I teml
7643 (December 1978) and Volume 187 It
em18716 (November 1979), and the additive types 1. Chemical sensitizer 2. Sensitivity enhancer4. Brightener 7. Stain inhibitor 8. Dye image stabilizer9. Hardener 10. Binder 11. Plasticizer/Lubricant 12. Coating aid/surfactant 13. Static inhibitor R D 17643 Page 23 Page 24 Page 25 Right column 25 Page 26 Page 26 Page 27 Page 26-27 Page 27 R D 18716 648 Page Right column Same as above 650 Page Left to right column 651 Page Left column Same as above 650 Right column In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers may be coated on one or both sides of a flexible support commonly used in photographic light-sensitive materials. can. Useful flexible supports include semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate-1, polycarbofluoride-1, etc. films, baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/
This paper is coated with or laminated with a butene copolymer (butene copolymer) or the like. The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally subjected to a subbing treatment to improve adhesion with emulsion layers and the like. The undercoating treatment is as described in JP-A-52-1049]. No. 3, No. 59-18949, No. 59-19940, No. 5
The treatments described in each publication of No. 9-11941 are preferred.

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

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

The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describe the developing, fixing, washing, and drying steps that take less than seconds.

The developing agent used in the black and white developer used in the present invention has a dihydroxybenzene chain and 1-
Most preferred is a combination of phenyl-3-vilasolidones. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chloronohydroquinone, promhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-cyclohydroquinone,
．． Among them, hydroquinone is particularly preferred.

l-phenyl-3-vilasolidone or 35 36 used in the present invention is a developing agent of I-7 enyl-4,4
Dimethyl-3-pyrazoli-1·n, ■-phenyl-4-methyl-4-hydroxymethyl-3-birasolidone, ■-
7-enyl-44-dihydroquinemethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, 1) monoaminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl). There are glycine, 2-methyl-p-aminophenol, p-pendylaminophenol, among others, N-methyl-p-
Aminophenols are preferred.

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

Sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium/lium bisulfite.

The sulfite is preferably 0.2 mol/Q or more, particularly 0.4 mol/Q or more. Further, it is preferable that the upper limit is 2.5 mol/Q.

It is preferable that the developer used in the present invention has a pl+ of 9 to 13. More preferably, the pH range is from 10 to 12.

The alkaline agent used for setting p1 is sodium hydroxide.
- Contains pl{regulators such as potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, sasocallose, acetoxime, 5-sulfozalcylic acid), phosphates, carbonates, etc. may also be used.

Additives that may be used in addition to the above include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, l-lyethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethynol, methanol: 1-phenyl-5-mercaptotetrazole, 2-menolecapbenzimitazole-5
-Mercapto compounds such as sulfonic acid sodium salts, 5
-Indazole compounds such as nitroindazole, 5-
It may contain an antifoggant such as a penntriazole compound such as methylbenttriazole, and if necessary, a coloring agent, a surfactant, an antifoaming agent, a water softener, and the like described in JP-A-56-106244. It may also contain amino compounds and the like.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

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

Besides this, L. F. A. “Photographic Processing Chemistry” by Meson, published by Focal Press (1
966), pages 226-229, U.S. Patent No. 2,193.
, No. 015, No. 2,592,364, Japanese Unexamined Patent Publication No. 48-6
Those described in No. 4933 may also be used.

In the present invention, "development time" and "fixing time" respectively mean
The time from when the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution, and the time from when it is immersed in the fixing tank solution until it is immersed in the next washing tank solution (stabilizing solution). say the time

In addition, "washing time j" refers to the time during which the product is immersed in the washing tank liquid.

Furthermore, "drying time" refers to the drying time in which the automatic processing machine is equipped with a drying zone where hot air is blown at a temperature usually between 35°O and 100°C, preferably between 40°C and 80°C. It refers to the time spent.

The developing temperature and time are about 25 DEG C. to 50 DEG C. for less than 15 seconds, preferably 30 DEG C. to 40 DEG C. for 6 seconds to 15 seconds.

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

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which essentially contain thiosulfate ions and ammonium ions, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/0. It is.

The fixer may also contain water-soluble aluminum 39 40 salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

The fixing solution may include tartaric acid, citric acid, or conductors thereof alone or in combination of two or more thereof.

Those containing 0.005 mol or more of these compounds per fixer IQ are effective, especially 0.005 mol or more per fixer IQ. Ol mol/Q to 0.03 mol/a is particularly effective.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, and potassium tartrate!・The fixing solution contains citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, etc. If desired, preservatives (e.g. sulfites, bisulfites), pH buffering agents (e.g. , acetic acid, nitric acid), pH adjuster (e.g. sulfuric acid)
, chelating agent with hard water softening ability and patent application No. 60-2135
The compound described in No. 62 may be included.

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
The time is preferably 6 seconds to 30 seconds at 30°C to 40°C, more preferably 6 seconds to 15 seconds at 30°C to 40°C.

When the fixer concentrate is refilled in the automatic processor in the method of the present invention with water to dilute the abrasive material as it is processed, the fixer concentrate is most preferably comprised of l-agents. The preferable conditions are the same as those for the developer.

The fixer solution can stably exist as a l agent at pH 4.
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used.

Therefore, in a pH range of 4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of po is not so strict, but if it is fixed at too high a pH, the pH of the membrane will be high even after washing with water, the membrane will swell, and the drying load will increase, so the upper limit is around pH 7. Fixing solutions that use aluminum salts to harden films have a pH limit of 5.5 to prevent precipitation of aluminum salts.

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

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8. The total amount of each of the developer and fixer is preferably from 50 mff to 1500 mj per m2 of the light-sensitive material.

In the present invention, the photosensitive material is developed, fixed, and then subjected to water washing or stabilization treatment.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water for washing water or stabilizing liquid, not only is it possible to conserve water by reducing the amount of replenishment to less than 3Q per m2 of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. Furthermore, the number of stock tanks can be reduced.

That is, the solution dilution water, washing water, or stabilizing solution for the developing solution and the fixing solution can be supplied from a common stock tank, making it possible to make the automatic developing machine more compact.

When water treated with anti-mildew measures is used in combination with washing water or stabilizing liquid, the formation of limescale can be effectively prevented.
It is possible to perform water saving treatment of 0 to 3 Q per 2, preferably 0 to H.

Here, when the replenishment amount is O, there is no replenishment at all other than the amount of wash water in the wash tank that has decreased due to natural evaporation, etc., in other words, the so-called "reservoir water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (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 in the fixer will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of washing water is also much smaller than that of the conventional 43 44.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with water treated with antimicrobial means, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in Japanese Patent Application No. 5133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. By doing this, it is possible to conserve the stock water described in Section 2, and moreover, the amount of waste liquid is reduced, which is more preferable.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, No. 61-6
The method using the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L. E. WesL ”WaLer Qual
ity CriteriaPhoLo Sci &
Eng. Vol. 9No. 6 (1965)
, M. W. Beach “Microbiolog
ical Growtbs in Motion
-PicnJre Processing'' SMP
TE Journal Vol. 1.85, (1976
). R. O. Deegan, “Photo P
rocessing Wasb WaterBio
cides” J.lmaging Tech.Vol1
10, No. 6 (1984) and JP-A-57-854
2, No. 57-58143, No. 58-105145, No. 57-132146, No. 58-18631, No. 57-97530, No. 57157244, etc. A surfactant or the like can also be used in combination.

Furthermore, in the washing bath, R. T. Kreiman, J. l
mage, Tech10, (6) 242 (1
984), an inthiazoline compound described in RES
EARCH DISCLOSURE Volume 205, l L
Isothiazoline compounds described in em20526 (May 1981 issue), Volume 228, Item 2
2845 (April issue, 1983) and the compounds described in Japanese Patent Application No. 61-51396 are used as antibacterial agents (Microbiocide).
) can also be used together.

Furthermore, specific examples of anti-pepper agents include phenol, 4-chlorophenol, pediachlorophenol, cresol, 0-phenylphenol, chlorophene, dichlorophene, formaldehyde, cultaraldehyde, chloroacetamide, p- Hydroquine benzoate, 2-(4-thiazoline)pensoimitazole, penzisothiazolin-3one, dodecyl-penzyl-dimethylammonium chloride, N-(fluorodimethylthio)phthalimide, 2,4.4'-1 -lichloro-2'-hydroxydiphenyl ether.

The water treated with antifungal measures and stored in the water stock tank is diluted with water for diluting the undiluted solution of the processing solution such as the developer/fixer, and the amount thereof added is preferably 0.01 to 1Og/4, more preferably 0.1
~5g/ff.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in the "Surfactant Handbook" published by Kogaku Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting membrane pH (e.g. pu3
~8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin. In addition, various additives such as chelating agents, fungicides (thiazole series, inthiazole series, halogenated phenols, sulfanilamide, penzotriazole, etc.), surfactants, optical brighteners, and hardening agents are used. Alternatively, two or more of the same or different target compounds may be used in combination.

In addition, ammonium chloride,
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 storage stability.

The water washing or stabilization bath temperature and time using the above method is Q.
6 seconds to 1 minute at 0~50°C is preferred, but 6 seconds to 30 seconds at 15°C~47 48 40°C is more preferred, and even 15
6 seconds to 15 seconds at °C to 40 °C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, but more preferably about 4 minutes.
It is about 5 seconds to 30 seconds at 0°C to 80°C.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive material, the shorter the drying time thereof.

According to the method of the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is within 100 seconds, preferably within 60 seconds, and more preferably within 5 seconds.
It is to be processed within 0 seconds.

Here, "dry to dry" is the period from the moment the leading edge of the photosensitive material to be processed enters the film insertion section of the processor to the moment the leading edge of the photosensitive material comes out of the processor after being processed. say the time until

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 In a container heated to 40°C containing ceratin, sodium chloride, and water, an aqueous silver nitrate solution, 2 x 10-6 mol of potassium hexachloroiridate salt per 1 mol of silver halide, and 4 x 10- A mixed aqueous solution of potassium bromide and sodium chloride to which 1 mol of potassium hexabutylmoridate was added was added by a double jet method to obtain 35 mol of silver bromide.
Silver chlorobromide particles containing mol% (width of distribution 12%, cubic crystal,
Particle size: 0.33 μm) was adjusted while maintaining the pH at 3.0 pAg at 7.7, and after returning to pH 5.9, it was desalted by a conventional method.

This emulsion was gold-sensitized and sulfur-sensitized and used as a sensitizing dye in Table-1.
240 mg per mole of silver halide was added, and further 70 mg of 1-phenyl-5-mercaptotetrasol, 4-hydroxy-6-methyl-1.3.3a. 1.2 g of 7-tetrazaindene, gelatin was added to stop the ripening, and 4 g./% hydroquinone per mole of silver halide. Add 3 g of potassium bromide, 5 g of noponin, 2 g of styrene-maleic acid polymer, and 3 g of ethyl acrylate polymer latex, and use 1 as a hardening agent.
- H1 Wakin = 35 N After addition of chlorotriazinium salt and formalin, silver amount 4.3 g/m2 was deposited on a subbed polyethylene terephthalate support.
The amount of gelatin was adjusted to 2-5 g/m2, and as a protective film, 40 g of the polymer compound of the present invention (Table 1) was added to an aqueous solution of 500 g of seratin, 1 IOg of potassium bromide, 1 decyl-2-(3-isopentyl) 4g of sodium 1-2-sulfonic acid was added, 100g of amorphous silica with an average particle size of 5pm was added and dispersed, and 1. og
The emulsion layer and the protective layer were coated at the same time in such a manner that the thickness of the emulsion layer and the protective layer were equal to /m2.

In addition, dyes (a) and (b) are applied to the opposite side of the above-coated surface.
) with a gelatin amount of 3.
3g/m2, dye (a) or 130mg/m2, dye (
b) was applied so that it was 50 mg/m2.

Dye (a.) Dye (b) The sample obtained in this way was processed under the following conditions using a normal roller-type automatic processor using the developer and fixer shown below, and the residual color was evaluated. did.

In addition, the surface resistivity on the emulsion layer side of each sample was measured at 23°C and 30% l.
Evaluation was made under the following conditions.

Note that the residual color is evaluated in 10 levels, with 10 being the best, 1 to 4 being unusable, and 5 or higher being usable. The results are shown in Table 1.

From Table 1, it can be seen that the product of the present invention has good residual color51 52 Karu.

Processing conditions (process) (temperature) Development 38°C fixation
Wash with water at 36°C
Dry at room temperature 50 °C Developer formulation Pure water (ion-exchanged water) Nonolium sulfite ethylenediaminetetraacetic acid di-potassium hydroxide 5-methylbenzo-l-lyazole diethylene glycol l-phenyl-4,4-dimethyl-3 Virazolidinone 1-phenyl-5-mercaf 1.tel.laso approx. 8 0
0 m 0 60 g um salt 2 g 60 g 3 0 0 m g 50 g 3 0 0 m g Noshi 6 0 m g Hydroquinone 20 g Potassium carbonate 15 g Pure water (ion exchange liquid water) was added. ,000m (finished to +).The developer pH was 10.8.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0m (1 Sodium sulfite 1 Lium 17g Sodium acetate 1
Helium trihydrate 6.5g boric acid
6g sodium citrate dihydrate 2g acetic acid (90% w/v aqueous solution)
13.6 mN+ (assemble B) Pure water (ion exchange water) 1 7 mQ sulfuric acid (50% w/v aqueous solution) 4.7 g aluminum sulfate (AQ203 equivalent content 8.1% w/v (7) aqueous solution)
26.5g Liumium bromide 3.5g When using a fixer, dissolve in 500n++2 of water in the order of the above groups A1 and B, 10. It was finished and used. The pH of this fixer was about 4.3.

Procedural amendment 1. Case Description Patent Application No. 165746 2. Name of the invention Silver halide photographic material and processing method thereof 3. Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo [Effects of the invention] The present invention provides a processing method that produces less residual color even when ultra-quick processing is performed. I was able to provide it.

Claims (2)

[Claims] (1) In a silver halide photographic material having a support and a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer, halogenated in the hydrophilic colloid layer. Silver particles have the following general formula [I
a] and a compound represented by the general formula [I b], and the at least one hydrophilic colloid layer contains a polymer compound having a heterocycle substituted with a sulfonic acid group. A silver halide photographic light-sensitive material. (2) A method for processing a silver halide photographic material according to claim 1, which comprises processing the silver halide photographic material according to claim 1 within a processing time of 45 seconds from development, fixing, washing and/or stabilizing solution. . General formula [I a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y_1_1, Y_1_2, Y_2_1 and Y
_2_2 each represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, R_1_1, R_1
_2, R_2_1 and R_2_2 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group. R_1_3, R_1_4, R_1_5, R_2_3, R
_2_4, R_2_5 and R_2_6 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Represents phenyl group, benzyl group, ▲numerical formula, chemical formula, table, etc.▼. Here, W_1 and W_2 are each a substituted or unsubstituted alkyl group (the number of carbon atoms in the alkyl part is 1 to
18, preferably 1 to 4), represents an aryl group, W_
1 and W_2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Also, R_1_3 and R_1_5 and R_2_3 and R_
2_5 can be linked to each other to form a 5-membered ring or a 6-membered ring. X_1_1 and X_2_1 represent anions. n_1_1, n_1_2, n_2_1 and n
_2_2 represents 0 or 1. ]