JP2597134B2 - Development processing method of silver halide photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for developing a silver halide light-sensitive material, and more particularly to a method for developing a silver halide photosensitive material with improved residual color.

(Prior Art) With the advancement and development of the electronics field, all fields are required to be prompt, and the field of silver halide photographic processing is no exception.

In particular, for example, in the development processing of a sheet-shaped photosensitive material such as a graphic arts photosensitive material, an X-ray photosensitive material, a photosensitive material for a scanner, a photosensitive material for CRT image recording,
The need for rapid processing is increasing.

In addition, the more rapid processing is performed, the smaller the tank capacity required for developing a unit amount of photosensitive material per unit time, that is, there is an advantage that an automatic developing machine can be reduced. Is significant.

However, with the speeding up of the development processing, the problem that the sensitizing dye contained in the silver halide light-sensitive material does not elute during processing and remains colored in the light-sensitive material (so-called residual color) increases.

Accordingly, an object of the present invention is to firstly provide a method for rapidly developing a silver halide light-sensitive material, and secondly to solve the problem of residual color due to a sensitizing dye in rapid processing. An object of the present invention is to provide a developing method.

(Constitution of the Invention) An object of the present invention is to provide a compound represented by the following general formula [I] or a salt thereof after exposing, developing and fixing a silver halide photosensitive material spectrally sensitized with a sensitizing dye. The present invention has been attained by a method for developing a silver halide light-sensitive material, characterized by processing with at least one washing water or a stabilizing solution.

General formula [I] Wherein A is a saturated or unsaturated pyrrole ring, imidazole ring, triazole ring, thiadiazole ring, tetrazole ring, oxazole ring, 1,3-dithiolane ring, 1,3,5
-To form a thiadiazine ring, a thiazole ring, a selenazole ring, a benzthiazole ring, a benzimidazole ring, a benzselenazole ring, a benzoxazole ring, a pyridine ring, a triazine ring, a quinoxaline ring, a tetraazaindene ring, and a pyrazolotriazole ring. Indicates the necessary atomic group. However, a structure in which a thioxo group can be enolized by tautomerism is excluded.

A may have a substituent, and two or more substituents may together form a saturated or unsaturated 3- to 8-membered ring.

 Specific examples of the substituent of A include a hydroxyl group,
Coxy group, aryloxy group, carboxyl group, amino
Group, ammonium group (where amino group and ammonium group are
, A sulfo group, a phosphonic acid group,
Sulfonyl group, ureido group, acyl group, alkylthio
Group, arylthio group, carbamoyl group, sulfamoyl
Group (where carbamoyl and sulfamoyl are substituents
), Acylamino group, sulfonamido
Groups, oxo groups, halogen groups, cyano groups, nitro groups,
Alkyl, alkenyl, alkynyl, and aryl
Group. These substituents are plural for A
Individual or two or more types may be substituted. Also possible
If present, these substituents are further substituted with the above functional groups.
It may be replaced. The functional groups contained in the formula
A carboxyl group, a sulfo group, and a phosphonic acid group
Is an alkali metal (eg, sodium, potassium, etc.)
), Or a monovalent positive atom (eg, NH_Four Etc.)
It may be in the form of a salt.
Various acids and salts such as acid, nitric acid, phosphoric acid, oxalic acid and acetic acid
It may be formed.

In the general formula [I], a preferable substituent of A is a hydroxyl group, an alkoxy group, an amino group, an ammonio group, an alkyl group, an alkylthio group, a carbamoyl group, a sulfamoyl group or a group in which these are combined (for example, an amino group Or, an alkyl group substituted by an ammonium group, an alkylthio group substituted by an amino group or an ammonium group). More preferably, an alkoxy group,
An amino group, an ammonio group, an alkyl group, an alkylthio group, an alkyl group substituted by an amino group or an ammonio group, or an alkylthio group substituted by an amino group or an ammonio group.

The number of ring members of A is preferably 5 or 6 members regardless of whether it is saturated or unsaturated.

Further, the compound of the general formula [I] has a total carbon number of 30
The following are preferable, and those having 20 or less are particularly preferable.

Specific examples of the compound of the general formula [I] in the present invention are shown below, but the present invention is not limited thereto.

The compound represented by the general formula [I] used in the present invention can be synthesized based on a method described in German Published Patent Application (OLS) 2043944 or the like.

The compound of the present invention may be added to a developer for the purpose of suppressing fog of a silver halide light-sensitive material, as described in JP-A-50-43923, or disclosed in JP-A-57-64.
No. 236, described in JP-A-53-28426 and JP-A-61-112.
As described in JP-A No. 146, it is known to add a bleaching solution or a bleach-fixing solution or a prebath thereof for accelerating the bleaching of the color photographic light-sensitive material in the bleaching or bleach-fixing step. However, the method of the present invention to be added to washing water or a stabilizing solution is not known, and the effect of reducing residual color by a sensitizing dye has been found for the first time.

The combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is the most preferable in that the developing agent used in the developing solution used in the development processing of the present invention easily obtains good performance. 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.

The p-aminophenol-based developing agents 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, p-benzylaminophenol and the like, among which N-methyl-p
-Aminophenol is preferred.

The 3-pyrazolidone-based developing agents used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-P-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and so on.

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

As the sulfite preservative used in the development treatment of the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The amount of 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 development processing of 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 Japanese Patent Application No. 61-28708 (borate), Japanese Patent Application Laid-Open No. 60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Further, a hardener may be used in the developer. As the hardener, a dialdehyde-based hardener or a bisulfite adduct thereof is preferably used. Specific examples thereof include glutaraldehyde and bisulfite adduct thereof.

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, ethanol, and 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.
sure, Vol. 176, No. 17643, Section XXI (December, 1978), and, if necessary, a color tone agent, a surfactant, a defoaming agent, a water softener, It may contain an amino compound described in JP-A-56-106244.

In the development process of the present invention, a silver stain inhibitor is added to the developer,
For example, compounds described in JP-A-56-24347 can be used.

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

In addition, LFA Mason's "Photographic Processing Chemistry", published by the Focal Press (19
66), pp. 226-229, U.S. Patent Nos. 2,193,015 and 2,591
Nos. 2,364 and JP-A-48-64933 may be used.

The fixing solution is an aqueous solution containing a thiosulfate as a fixing agent, and has a pH of 3.8 or more, preferably 4.2 to 7.0. More preferably, the pH is 4.5 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, 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, aluminum sulfate, potassium alum and the like.

Tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more in the fixing solution. These compounds are used in an amount of 0.00
Those containing 5 mol or more are effective, especially 0.01 mol / ~ 0.03
Mol / is particularly effective.

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water, or a patent application. The compounds described in JP-A-60-218562 can be included.

In the development processing of the present invention, it is more preferable to reduce the swelling percentage of the light-sensitive material (preferably 150% to 50%) and to weaken the processing hardened film, since rapid processing can be performed. That is, it is more preferable that there is no hardening during development, and it is more preferable that there is no hardening during fixing. However, the pH of the fixing solution may be set to 4.6 or more to weaken the hardening reaction. This makes it possible to form a replenisher consisting of one solution for each of the developing solution and the fixing solution, and there is also an advantage that the preparation of the replenisher requires only dilution with water.

In the method for processing a silver halide photographic light-sensitive material of the present invention, after the developing and fixing steps, the light-sensitive material is washed with water containing at least one compound represented by the general formula [I] of the present invention or stabilized. Treat with liquid. Here, the stabilizing solution is the same as the water washing, and is different only in the name.

The preferred addition amount of the compound of the general formula [I] of the present invention is 5 × 10 ^-5 mol to 10 ^-1 mol, especially 10 ^-4 mol to 5 × 10 ^-2 mol, more preferably 5 × 10 ^-5 mol to 10 ^-1 mol per washing water or stabilizing solution. It is 10 ^-3 mol to 10 ^-2 mol.

The replenishment amount of washing water or stabilizing solution is ² per 1 m2 of photosensitive material.
The following (including 0, that is, washing with water) is preferable.

By doing so, not only the water saving process can be performed, but also the piping for installing the automatic processing machine can be eliminated.

As a method for reducing the amount of replenishment, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in a clean direction, that is, a processing solution that is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washing is performed.

In order to make the above-mentioned development processing of the present invention a water-saving treatment or a non-pipe treatment, it is preferable to apply a fungicide to the washing water or the stabilizing solution.

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, 60-295894
Nos. 61-63030 and 61-51396 can be used.

Furthermore, LEWest, “Water Quality Criteria” Phot
o.Sci, & Eng.Vol.9 No.6 (1965), MWBeach, “Micro
biological Growths in Motion-Picture Processi
ng "SMPTE Journal Vol.85, (1976), RODeegan," P
hoto Processing Wash Water Biocides "J.Imaging
Tech 10, No. 6 (1984) and JP-A-57-8542, 57-5
No. 8143, No. 58-105145, No. 57-132146, No. 58-1863
No. 1, No. 57-97530, No. 57-157244, etc. can be used in combination.

Further, the washing bath or stabilizing bath of the present invention includes RTKreima.
n, Isothiazoline compounds described in J. Image. Tech 10, (6) p. 242 (1984), Research Disclosure No. 20
Vol. 5, No. 20526 (May 1981), isothiazoline compounds, Vol. 228, No. 22845 (1983, Apr.
Monthly Issue), Japanese Patent Application No. 61
No. 51396, and the like.
ide).

In addition, "The chemistry of antibacterial and fungicide" by Hiroshi Horiguchi, Sankyo Publishing (Akira
57), "Handbook of antibacterial and antifungal technology" may contain compounds as described in the Japan Society of Antifungal and Antifungal Technology / Hakuhodo (Showa 61).

In the method of the present invention, when washing with a small amount of washing water or stabilizing with a stabilizing solution, it is more preferable to provide a squeeze roller washing tank described in Japanese Patent Application No. 163217/1986. It is also preferable to adopt a configuration of a washing step as disclosed in Japanese Patent Application No. 61-290619.

Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in As described in JP-A-60-235133, the present invention can also be used for a processing solution having a fixing ability, which is a preceding processing step.

The silver halide light-sensitive material of the present invention, when processed by an automatic processor including at least the steps of developing, fixing, washing or stabilizing and drying, the process from development to drying is 90 times.
Time within a second, that is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip is dried through a fixing and washing (or stabilization) process until the tip comes out of the drying zone. (Dry to Dry time) is preferably within 90 seconds, particularly preferably within 70 seconds.
More preferably, the Dry to Dry time is within 60 seconds.

In the present invention, the `` development process time '' or `` development time '' is the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the next fixing liquid, "Fixing time" refers to the time from immersion in the fixing tank solution to immersion in the water washing tank solution (stabilizing solution). "Washing time" refers to the time of immersion in the washing tank solution.

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

In order to achieve rapid processing within the above Dry to Dry 70 seconds, the development time is within 20 seconds, preferably within 15 seconds,
The development temperature is preferably from 25C to 50C, more preferably from 30C to 40C.

According to the present invention, the fixing temperature and time are preferably from about 20 ° C. to about 50 ° C. for 6 seconds to 20 seconds, more preferably from 30 ° C. to 40 ° C. for 6 seconds to 15 seconds.

Rinse or stabilize bath temperature and time from 0 to 50 ° C for 6 seconds
It is preferably 20 seconds, more preferably 6 to 15 seconds at 15 ° C to 40 ° C.

Within this range, the sensitizing dye can be eluted to such an extent that no residual color is produced.

According to the method of the present invention, the developed, fixed and rinsed or stabilized photographic material is squeezed out of the rinse water, i.e. dried through a squeeze roller. Drying is about 40 ° C to about 100
C., and the drying time may be appropriately changed depending on the surrounding conditions, but it is usually about 5 seconds to 30 seconds, and particularly preferably 40 ° C. to 80 ° C. for about 5 seconds to 20 seconds.

When developing with a light-sensitive material / processing system of the present invention for 70 seconds or less by Dry to Dry, in order to prevent development unevenness peculiar to rapid processing, as described in Japanese Patent Application No. 61-297672. Applying a rubber roller to the roller at the exit of the development tank, or increasing the discharge flow rate for stirring the developer in the developer tank to 10 m / min or more as described in Japanese Patent Application No. 61-297673. And furthermore, Japanese Patent Application
As described in the specification of JP-A-61-315537, it is more preferable to perform stronger stirring at least during development processing than during standby. Furthermore, for rapid processing as in the present invention, the configuration of the roller of the fixing liquid tank is more preferably an opposing roller in order to increase the fixing speed. By using the opposed rollers, the number of rollers can be reduced, and the processing tank can be reduced. That is, it is possible to make the self-developing machine more compact.

In the method for developing a photographic material of the present invention, the photographic material is not particularly limited, and a general black-and-white photographic material is mainly used. In particular, photographic materials for laser printers for medical images and scanner sensitizers for printing, direct X-ray photographic materials for medical use, X-ray photographic materials for medical indirect use, sensitizers for CRT image recording, hard contrast materials for printing, etc. Can be used.

The production of a photosensitive material suitable for rapid development according to the present invention can be realized, for example, by one or a combination of two or more of the following methods.

A silver halide having a small or no iodine content is used. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. having a silver iodide content of 0 to 5 mol% are used.

A water-soluble iridium salt is contained in a silver halide emulsion.

The amount of coated silver in the silver halide emulsion layer is reduced. For example, it is 1 to 3.5 g / m ² , preferably 1 to 3 g / m ^{2 on} one side. More preferably, it is 1 to 2.2 g / m ² .

Reduce the average grain size of silver halide in the emulsion. For example, it is 1.0 μm or less, preferably 0.7 μm or less.

As the silver halide grains in the emulsion, tabular grains, for example, those having an aspect ratio of 4 or more, preferably 5 or more are used.

The swelling percentage of the silver halide photosensitive material is set to 200% or less.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular grains having regular crystals such as tetradecahedrons may also be used, and those having irregular crystal forms such as spheres, those having crystal defects such as twin planes, tabular grains or A composite form thereof may be used.

The tabular grain aspect ratio is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain.
In the present invention, the preferred form of the tabular grains is 4 to less than 20, preferably 5 to less than 10, aspect ratio. Further, the thickness of the particles is preferably 0.3 μm or less, particularly preferably 0.2 μm or less.

Tabular grains are preferably present in an amount of preferably 80% by weight, more preferably 90% by weight or more of all the grains.

The grain size of the silver halide may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure, No. 176
43 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion
preparation and types) ”and No. 18716 (197
Nov. 9), p. 648.

The photographic emulsion used in the present invention is described in "Graduation of Chemistry and Physics", published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 1
967), “Photographic Emulsion Chemistry” by Daffin, published by Focal Press (GFDuffin. Photographic Emulsion Chemist)
ry (Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VLZelikman)
et al, Making and Coating Photographic Emuls
ion, Focal Press, 1964) and the like.

In forming the silver halide grains used in the present invention, for example, ammonia, rodankari, rodanammon, as a silver halide solvent in order to control the growth of the grains.
Thioether compounds (for example, US Pat. No. 3,271,157,
No. 3,574,628, No. 3,704,130, No. 4,297,439
Nos. 4,276,374) and thione compounds (for example, JP-A-53-144,319, JP-A-53-82,408, and JP-A-55-77,73).
No. 7, etc.) and amine compounds (for example, JP-A-54-100,717).

In the present invention, a water-soluble rhodium salt or a water-soluble iridium salt can be used.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. PA in the liquid phase where silver halide is formed as a form of the double jet method.
A method of keeping g constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion used in the method of the present invention is preferably chemically sensitized.

In case of chemical sensitization, normal sulfur sensitization, reduction sensitization,
Noble metal sensitization and combinations thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine;
Potassium chloroaurate, auras, thiosulfate and Potassium chloroparadate
Noble metal sensitizers such as Palladate: reduction sensitizers such as tin chloride, phenylhydrazine and reductone.

The silver halide emulsion used in the present invention is optionally spectrally sensitized by a known spectral sensitizing dye. Examples of spectral sensitizing dyes used include, for example, Hemmer, "Heterocyclic Compounds-The Cyanine Soybean".
And Related Compounds ", Jillon Wheely and Sons (1964) (FMHamer," He
terocyclic Compounds-The Cyanine Dyes and Related
"Compounds", John Wiley & Sons (1964), and Starmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry," Jillon Wheely and Sons (1977) (DMSturmer, "Heterocyclic"). Compounds-Specia
l Topics in Heterocyclic Chemistry ", John Wiley &
Sons (1977). For example, cyanine, merocyanine, rhodacyanine, styryl, hemicyanine, oxonol, benzylidene, and holopolar described in, for example, can be used, and cyanine and merocyanine are particularly preferable.

Sensitizing dyes that can be preferably used in the present invention include JP-A-60-133442, JP-A-61-75339, JP-A-62-6251, and JP-A-60-62591.
And cyanine dyes and merocyanine dyes represented by the general formulas described in JP-A-212827, JP-A-50-122292, JP-A-59-1801553 and the like. Specifically, pages (8) to (11) of JP-A-60-133442 and (5) of JP-A-61-75339 are described.
To (7), pages (24) to (25), pages (10) to (15) of JP-A-62-6251, and (5) to (5) of JP-A-59-212827.
Page (7), pages (7) to (9) of JP-A-50-1222928,
A sensitizing dye which spectrally sensitizes silver halide to a blue region, a green region, a red region or an infrared region of the spectrum described in pages (7) to (18) of JP-A-59-180553 is used. Can be mentioned.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization. In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensate (for example, see U.S. Pat. No. 3,743,510) Described)), cadmium salt,
An azaindene compound may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

The above sensitizing dye is used in an amount of 5 × 10 ⁻⁷ mol to 5 × 10 ⁻² mol, preferably 1 × 10 ⁻⁶ mol to 1 × 10 ⁻³ mol per mol of silver halide.
Mol, particularly preferably 2 × 10 ^-6 mol to 5 × 10 ^-4 mol, in the silver halide photographic emulsion.

The sensitizing dye can be directly dispersed in the emulsion layer. 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. Also, ultrasonic waves can be used for dissolution. Further, as a method for adding the sensitizing dye, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is dispersed. As described in JP-B-46-24185, etc., by dispersing in a water-soluble solvent without dissolving a water-insoluble dye, and adding this dispersion to the emulsion; A method of mechanically pulverizing and dispersing a water-insoluble dye in an aqueous solvent as described in -45217, and adding this dispersion to an emulsion; a surfactant as described in U.S. Pat. No. 3,822,135; A method of dissolving a dye in an emulsion and adding the solution to an emulsion; a method of dissolving using a compound for redshift as described in JP-A-51-74624, and adding the solution to the emulsion; The dyes substantially as described in No. 50-80826 contain water A method of dissolving in an acid, and adding the solution to the emulsion. Others
U.S. Pat.Nos. 2,912,343 and 3,342,6
Methods described in No. 05, No. 2,996,287 and No. 3,429,835 can also be used. The above-mentioned sensitizing dyes may suitably be dispersed uniformly in the silver halide emulsion before being coated on the support, but may of course be dispersed in any step of the preparation of the silver halide emulsion. .

Other sensitizing dyes can be used in combination with the above sensitizing dyes. For example, U.S. Patent Nos. 3,703,377, 2,688,545, 3,397,060, 3,615,635,
No. 3,628,964, UK Patent No. 1,242,588, No. 1,293,
No. 862, No. 43-4936, No. 44-14030, No. 43-1077
No. 3, U.S. Pat.No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Pat.Nos. 2,615,613, 3,615,632, 3,617,295
And sensitizing dyes described in JP-A No. 3,635,721 and the like can be used.

In order to rapidly process the silver halide light-sensitive material, the swelling percentage of the silver halide light-sensitive material is preferably 200% or less.

On the other hand, if the swelling percentage is too low, the speed of development, fixing, washing with water and the like will decrease.

The preferred swelling percentage is 200% or less and 30% or more, particularly preferably 150% or less and 50% or more.

To control the swelling percentage to 200% or less, those skilled in the art can easily control the swelling percentage by increasing the amount of a hardening agent used in a photosensitive material, for example.

The percentage of swelling was determined by (a) incubating the photographic material at 38 ° C. and 50% relative humidity for 3 days, (b) measuring the thickness of the hydrophilic colloid layer, and (c) distilling the photographic material at 21 ° C. It can be determined by immersing in water for 3 minutes and (d) measuring the percentage change in layer thickness compared to the thickness of the hydrophilic colloid layer measured in step (b).

Examples of the hardening agent that can be used in the present invention include aldehyde compounds, compounds having an active halogen described in U.S. Patent No. 3,288,775, and reactive ethylenically unsaturated groups described in U.S. Patent No. 3,635,718. And organic compounds such as epoxy compounds described in US Pat. No. 3,091,537 and halogenocarboxaldehydes such as mucochloric acid. Among them, vinyl sulfone hardeners are preferred. Further, a polymer hardener can also be preferably used.

As the polymer hardener, a polymer having an active vinyl group or a group which is a precursor thereof is preferable. Among them, an active vinyl group or a polymer having a long spacer as described in JP-A-56-142524 is preferable. Particularly preferred are polymers in which the precursor groups are attached to the polymer backbone. The amount of these hardeners added to achieve the above-mentioned swelling percentage varies depending on the type of hardener used and the kind of gelatin used.

In the rapid processing of the present invention, it is preferable to incorporate an organic substance which flows out in the development processing step into the emulsion layer and / or the other hydrophilic colloid layer. When the substance to be discharged is gelatin, a gelatin species which is not involved in the cross-linking reaction of gelatin by a hardener is preferable. For example, acetylated gelatin and phthalated gelatin correspond to these, and those having a small molecular weight are preferable. On the other hand, as a polymer substance other than gelatin, polyacrylamide as described in U.S. Pat.No. 3,271,158, or polyvinyl alcohol, a hydrophilic polymer such as polyvinylpyrrolidone can be effectively used, and dextran or Satsukarose, Sugars such as pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. In addition, Research Disclos
Antifoggants and stabilizers described in ure, Vol. 176, No. 17643, Section VI (December issue, 1978) can be used.

Development processing method of the present invention is U.S. Pat.No.4,224,401, 4,168,977, 4,166,742, 4,311,781,
Nos. 4,272,606, 4,221,857, and 4,243,739 can be applied to image formation processing of a silver halide photosensitive material capable of obtaining high photographic characteristics with high sensitivity by using a hydrazine derivative described in the same. .

As hydrazine derivatives, RESEARCH DISCLOSURE N
o. 23516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,269,929
No. 4,276,364, No. 4,278,748, No. 4,385,10
No. 8, No. 4,459,347, No. 4,560,638, No. 4,478,9
No. 28, British Patent No. 2,011,391B and JP-A-60-1779734 can be used. The hydrazine derivative is used in an amount of 1 × 10 ⁻⁶ mol to 5 × per mol of silver halide.
It is preferably contained in an amount of 10 ⁻² mol, and particularly preferably in the range of 1 × 10 ⁻⁵ mol to 2 × 10 ⁻² mol.

Further, it is preferable that the developer used in this case contains an amino compound described in U.S. Pat. No. 4,269,929 as a high contrast accelerator.

Next, specific examples of the present invention will be described, but the present invention is not limited to these examples.

Example 1 Preparation of emulsion 30 g of gelatin and 6 g of potassium bromide were added to water 1 and an aqueous silver nitrate solution (as silver nitrate) was stirred in a container kept at 60 ° C.
An aqueous potassium bromide solution containing 5 g) and 0.15 g of potassium iodide was added over 1 minute by the double-jet method. Further, an aqueous potassium bromide solution containing 4.2 g of potassium iodide and an aqueous solution of silver nitrate (145 g as silver nitrate) was added by a double jet method. At this time, the flow rate was accelerated so that the flow rate at the end of the addition was five times that at the start of the addition. After the addition is complete,
After removing soluble salts at ℃, the temperature was raised to 40 ℃, and 75 g of gelatin was added to adjust the pH to 6.7. The resulting emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. In this emulsion,
Chemical sensitization was performed in combination with gold and sulfur sensitization.

Preparation of photographic material 101 As a surface protective layer, in addition to gelatin, polyacrylamide having an average molecular weight of 8000, sodium polystyrene sulfonate,
Polymethyl methacrylate fine particles (average particle size 3.0
μm), an aqueous solution of gelatin containing polyethylene oxide, a hardener and the like.

Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt as a sensitizing dye in the above emulsion at a ratio of 500 mg / 1 mol Ag, Potassium iodide 200mg / 1mol
Ag was added at the rate. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5
A photographic material by adding triazine and nitrone, trimethylolpropane as a dry antifoggant, a coating aid, and a hardening agent to form a coating solution, and coating and drying the both sides of the polyethylene terephthalate support simultaneously with the surface protective layer, respectively; It was created. The coated silver amount of this photographic material is 2 g / m ² per side. The swelling ratio according to the above definition was 120%.

This photographic material was exposed to X-rays and developed with the following developing solution, fixing solution and washing solution formulation.

<Developer concentrate> Potassium hydroxide 60 g Sodium sulfite 100 g Potassium sulfite 125 g Diethylenetriaminepentaacetic acid 6 g Boric acid 25 g Hydroquinone 87.5 g Diethylene glycol 28 g 4-Hydroxymethyl-4-methyl-1-phenyl-3
-Pyrazolidone 6.25 g 5-methylbenzotriazole 0.15 g Make up to 1 with water (adjust to pH 11.00).

Replenisher solution size 5 <Fixing solution concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid disodium dihydrate 0.10 g Sodium hydroxide 24 g Water 1 (Adjust to pH 5.10 with acetic acid.) Replenisher kit size 5 <Water stock tank solution> Ethylenediaminetetraacetic acid disodium salt / dihydrate (antifungal agent) 0.5 g / Adjusted to the compound of the present invention at pH 5.2 See Table 1 Automatic developing machine (see FIG. 1) Dry 55 seconds processing with To Dry.

Developing tank (1) 7.5 35 ° C x 11.5 seconds (opposite roller) Fixing tank (2) 7.5 35 ° C x 12.5 seconds (opposite roller) Rinse tank (3) 6 20 ° C x 7.5 seconds (opposite roller) Squeeze roller cleaning tank ( 7) 200ml water stock tank (4) 25 Drying The heater was used to maintain the temperature of both the developing and fixing tanks, but the cooling water was not used.

When the developing process was started, each tank was filled with the following processing solution.

Developing tank (1): The pH was adjusted to 10.50 by adding 400 ml of the above-mentioned concentrated solution of developing solution, 600 ml of water and 10 ml of an aqueous solution containing 2 g of potassium bromide and 1.8 g of acetic acid.

Fixing tank (2): 250 ml of fixing solution concentrate and 750 ml of water Washing tank (3) and washing tank (7): the same composition as the stock tank solution As shown in the schematic diagram of the automatic developing machine in FIG. Each time one sheet of photosensitive material (10 inch x 12 inch) is processed, 20 ml of developer concentrate and 30 ml of stock tank water in the developing tank 10 ml of fixer concentrate in the fixing tank and a part of the overflow solution in the washing tank 30 ml The squeeze roller washing tank was refilled with 60 ml of stock tank water (in the direction opposite to the film direction) to the washing tank, and the running process was continued for 50 pieces per day (40% development rate of one film) per day. During this time, if the developing solution, the fixing solution and the water disappeared, a new replenishing solution was similarly added.

When the photosensitive material is subjected to the development processing, the amount of the circulating stirring liquid of the developer is set to 20 / min.
Set to minutes.

At the end of a day's development work, 80 ml of water from the above-mentioned water storage tank is automatically and intermittently sprayed onto the crossover rollers between the development and fixing and between the fixing and water washing through 10 small holes. (Japanese Patent Application No. 61-1313)
No. 38).

Dry-to-dry processing time was 60 seconds as described above. Table 1 shows the residual color after processing (the value obtained by measuring the transmission optical density of the non-image area with green light).

As shown in Table 1, when treated with a washing solution containing the compound of the present invention, the treatment is very rapid, and with a small amount of replenisher,
It can be seen that the residual color after the processing is small.

Example 2 As in Example 1, photosensitive materials 201, 202, and 203 using the following various sensitizing dyes A, B, and C as sensitizing dyes, respectively.
And processed in the same manner on an automatic developing machine.

Example 3 A 0.3 micron cubic silver iodobromide emulsion containing 2.5 mol% iodide was anhydro-5,5-dichloro-9-ethyl-
230 mg of 3,3'-bis (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt (sensitizing dye)
1 mol of silver, 1.3 g of hydrazine derivative (the following compound) / 1 mol of silver, and 30 mol of polyethylene glycol (molecular weight: about 1000)
0 mg / 1 mol of silver was added, and a dispersion of 5-methylbenztriazole, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and polyethyl acrylate, 2-hydroxy-1,3,5 -Triazine sodium salt was added. Further, as a hardening agent, 1,3-divinylsulfonyl-2-propanol was added in an adjusted amount so that the swelling percentage was 120%.

The coating solution thus prepared was coated on a polyethylene terephthalate film support together with a protective layer at a silver coating amount of 3.
5g / m ² , gelatin coating amount (with emulsion layer and protective layer) 3.0
g / m ² to give a film.

These films were exposed through a sensitometric exposure wedge using a 150-line magenta contact screen, developed with a developer having the following composition at 40 ° C. for 15 seconds, and then fixed with a fixer GR-F1 manufactured by Fuji Photo Film Co., Ltd. Fixing, washing and drying. The automatic developer used here is Dry to Dry
It is set to 65 seconds.

(Developer composition) tetrasodium ethylenediaminetetraacetate 1.0 g sodium hydroxide 9.0 g 5-sulfosalicylic acid 44.0 g potassium sulfite 100.0 g 5-methylbenztriazole 0.5 g potassium bromide 6.0 g N-butyl-diethanolamine 15.0 g N-methyl- p- aminophenol 1 / 2H ₂ SO ₄ 0.4g hydroquinone 54.0 g p- compound of adding toluene sulfonic acid sodium 30.0g water present invention in 1 pH 11.7 aqueous wash I- a (3) 1.5 g / added to pH5 .2, and processing was performed while replenishing 250 ml per sheet (20 inch × 24 inch). The residual color after the processing was measured in the same manner as in Example 1. As a result, the residual color density was 0.044 less than that of the processed light-sensitive material without using the compound of the present invention.

Example 4 An aqueous gelatin solution maintained at 50 ° C. was added in an amount of 4 × 10
^In the presence of ^-7 mol of iridium (III) chloride potassium and ammonia, an aqueous nitrate solution, an aqueous potassium iodide solution and an aqueous potassium bromide solution were simultaneously added over 60 minutes, and the average particle size was 0.25 μm by maintaining pAg at 7.8 during that period. A cubic monodispersed emulsion having an average silver iodide content of 1 mol% was prepared. In these silver iodobromide emulsions, the following compounds as sensitizing dyes
5 × 10 ^-5 mol per mol And 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, a dispersion of polyethyl acrylate, polyethylene glycol, 1,3-vinylsulfonyl-2-propanol, -Phenyl-5-
Mercaptotetrazole, 1,4-bis [3- (4-acetylamino-pyridinio) propionyloxy] -tetramethylenedibromide and the same hydrazine derivative as in Example 3 (4.8 × 10 ⁻³ mol per mol of silver) were added. The pH of the film surface was adjusted to 5.5 with ascorbic acid, and the film was coated on a polyethylene terephthalate film so that the silver amount was 3.4 g / m ² (the film surface pH was measured as described in
25745). At the same time, a gelatin layer was coated on the emulsion layer at a gelatin coating amount of 1.0 g / m ² . The sample thus obtained was exposed and developed, and the photographic characteristics were measured.

 The formulation of the developer is as follows.

Developer formula Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 nitrate 0.8 g Sodium hydroxide 13.0 g Potassium tertiary phosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid tetrasodium salt / dihydrate 1.0 g Bromide Potassium 4.0 g 5-Methylbenzotriazole 0.6 g 3-Diethylamino-1,2-propanediol 15.0 g Water was added to 1 (pH = 11.65) Fixer formulation is as follows.

Ammonium thiosulfate 150 g Sodium sulfite 30 g Acetic acid 30 g Add water 1 image 40 ° C. 15 seconds Fix 37 ° C. 16 seconds Rinse 12 seconds Dry to Dry 67 seconds Add 1.5 g / l of the compound I- (3) of the present invention to the water wash. In addition, the sample after processing had good photographic performance (Dmax, sensitivity, gamma, black spot) and 0.033 less residual color in Red density.

Example 4 Photographic materials 401 to 402 using the following various sensitizing dyes as sensitizing dyes were prepared in the same manner as in Example 1, and processed similarly on an automatic developing machine.

In each case, the residual color was reduced when treated with a washing solution containing the compound of the present invention.

[Brief description of the drawings]

FIG. 1 shows one embodiment of an automatic processor system for performing the method of the present invention. 1: Developing tank 2: Fixing tank 3: Rinse tank 4: Water stock tank 5: Developer concentrated solution stock tank 6: Fixer concentrated solution stock tank 7: Squeeze roller cleaning tank P: Pump

Continuation of the front page (56) References JP-A-61-148448 (JP, A) JP-A-61-151538 (JP, A) JP-A-61-151649 (JP, A) JP-A-61-151650 (JP, A) JP-A-61-151651 (JP, A) JP-A-61-170742 (JP, A) JP-A-61-175638 (JP, A) JP-A-59-193447 (JP, A)

Claims (1)

(57) [Claims] A silver halide light-sensitive material spectrally sensitized with a sensitizing dye is exposed, developed and fixed, and then washed with water containing at least one compound represented by the following general formula [I] or a salt thereof. A method for developing a silver halide light-sensitive material, characterized by processing with a stabilizing solution. General formula [I] In the formula, A is a saturated or unsaturated pyrrole ring, imidazole ring, triazole ring, thiadiazole ring, tetrazole ring, oxazole ring, 1,3-dithiolane ring, 1,3,5-
Necessary to form thiadiazine ring, thiazole ring, selenazole ring, benzthiazole ring, benzimidazole ring, benzselenazole ring, benzoxazole ring, pyridine ring, triazine ring, quinoxaline ring, tetraazaindene ring, pyrazolotriazole ring Atomic group. However, a structure in which a thioxo group can be enolized by tautomerism is excluded.