JPH07119974B2 - Development processing method of silver halide light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a development processing method for a silver halide photosensitive material, and more particularly to a development processing method with improved residual color and fixability.

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

In particular, in the development processing of sheet-shaped photosensitive materials such as photosensitive materials for graphic arts, photosensitive materials for X rays, photosensitive materials for SCANNER, and photosensitive materials for CRT image recording, the need for rapid processing is increasing more and more. .

In addition, the faster the development process, the smaller the tank capacity required to develop a unit amount of the photosensitive material per unit time, that is, the advantage that the automatic developing machine can be made smaller. Is significant.

However, as the development processing is accelerated, the problem that the sensitizing dye contained in the silver halide photosensitive material does not elute during the processing and remains colored in the photosensitive material (so-called residual color) becomes large.

(Object of the Invention) Accordingly, the object of the present invention is to 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 the rapid processing. It is to provide a development processing method.

(Structure of the Invention) An object of the present invention is to expose and develop a silver halide light-sensitive material, and then use a fixing solution containing at least one compound represented by the following general formula [I] or a salt thereof from development to drying. It was achieved by processing the total processing time in 90 seconds or less.

General formula [I] In the formula, A represents an atomic group necessary for forming a saturated or unsaturated 3 to 8 membered ring which always contains any one of an oxygen atom, a nitrogen atom, a sulfur atom and a selenium atom, and a substituent group As at least one alkyl group substituted with an amino group or an ammonio group or an alkylthio group substituted with an amino group or an ammonio group. However, a structure in which a thioxo group can be enolized by tautomerism is excluded.

It is desirable that = S in the general formula [I] is bonded to the carbon atom of A.

A nitrogen-containing ring is preferable as an example of the 3- to 8-membered ring formed by A,
Saturated or unsaturated pyrrole ring, imidazole ring, triazole ring, thiadiazole ring, tetrazole ring, thiazole ring, selenazole ring, benzthiazole ring, benzimidazole ring, benzselenazole ring, benzoxazole ring, pyridine ring, pyrimidine ring, triazine ring Examples thereof include a ring, a quinoxaline ring, a tetraazaindene ring, a pyrazolotriazole ring and the like.

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

As the compound of the general formula [I], those having a total carbon number of 30 or less are preferable, and those having a total carbon number of 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. However, 1- (8), 1- (9), and 1- (12) are reference examples.

The above-mentioned compounds of the present invention are added to a developing solution for the purpose of suppressing fog of a silver halide light-sensitive material, as described in JP-A-50-43923, or JP-A-53-28426.
No. 61-112146, it is known to add it to a bleaching solution or a bleach-fixing solution or their pre-bath to accelerate bleaching in a bleaching or bleach-fixing step of a color photographic light-sensitive material. There is. However, the method of the present invention for adding it to the fixing solution is not known, and the effect of reducing the residual color due to the sensitizing dye was found for the first time.

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

The amount of the compound represented by the general formula [I] of the present invention added to the fixing solution is 5 × 10 ⁻⁵ mol / l to 10 ⁻¹ mol / l, preferably 10 ⁻⁴ mol / l to 5 × 10 5. ^-2 mol / l, more preferably 10
^-3 mol / l to 10 ^-2 mol / l.

The fixer is an aqueous solution containing thiosulfate as a fixing agent,
It has a pH of 3.8 or higher, preferably 4.2-7.0. The pH is more preferably 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 used can be appropriately changed and is generally about 0.1 to about 6 mol / l.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum.

Tartaric acid, citric acid, gluconic acid or their derivatives may be used alone or in combination of two or more in the fixing solution. These compounds are 0.005 per fixer
Those containing more than 1 mol are effective, especially 0.01 mol / l to 0.03 mol
/ l is especially useful.

Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a water softening ability and Japanese Patent Application No. The compounds described in 60-218562 may be included.

The development processing method of the present invention basically comprises steps of developing, fixing, washing with water and drying an exposed silver halide light-sensitive material.

The combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferable in that a good performance is easily obtained for the developing agent used in the developing solution used in the developing treatment of the present invention. Of course, a p-aminophenol-based developing agent may be contained in addition to the above.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5
-Dimethylhydroquinone, etc., but hydroquinone is particularly preferable.

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, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

The 3-pyrazolidone-based developing agent used in the present invention is 1
-Phenyl-3-pyrazolidone, 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 usually preferably used in an amount of 0.01 mol / l to 1.2 mol / l.

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

The pH of the developer used in the developing treatment 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 to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
It contains a pH adjusting agent such as sodium triphosphate or potassium triphosphate.

A buffer agent such as Japanese Patent Application No. 61-28708 (borate), JP-A No. 60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate may be used.

A hardener may be used in the developer. As the hardener, a dialdehyde hardener or a bisulfite adduct thereof is preferably used, and specific examples thereof include glutaraldehyde, or a bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. A mercapto-based compound, an indazole-based compound such as 5-nitroindazole, an antifoggant such as a benztriazole-based compound such as 5-methylbenztriazole may be included, and Research Disclosure
Development accelerators described in Volume 176, No. 17643, Item XXI (December issue, 1978) and, if necessary, toning agents, surfactants, defoaming agents, aminopolycarboxylic acids, aminopoly Chelating agents such as phosphonic acid and phosphonocarboxylic acid, JP-A-56
The amino compound described in No. 106244 may be included.

In the developing treatment of the present invention, a silver stain inhibitor such as the compounds 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.

In addition, LPA Mason's "Photographic Processing Chemistry", published by 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.

For the rapid processing of the present invention, it is preferable that the swelling percentage of the light-sensitive material is made small (preferably 150% to 50%) as described later to weaken the processing hardening film. 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 hardening reaction may be weakened by setting the pH of the fixing solution to 4.6 or more. By doing so, a replenisher consisting of one liquid for each of the developing solution and the fixing solution can be constituted, and there is an advantage that the replenishing solution can be prepared by simply diluting with water.

In the method for developing and processing a silver halide photographic light-sensitive material of the present invention, after the developing and fixing steps, a replenishing amount of 3 l or less per 1 m ^{2 of the} light-sensitive material (including 0, that is, washing with water) or stable washing water It can also be treated with a liquid chemical.

That is, not only water saving processing is possible, but also piping for installing the automatic processing machine can be eliminated.

As a method for reducing the replenishment amount, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the light-sensitive material after fixing is gradually processed in a cleaner direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water.

In the above water-saving treatment or pipeless treatment, it is preferable to apply antifungal means 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 60-263940, and an ion exchange resin described in 61-131632 are used. How to make pure water, Japanese Patent Application No. 60-253807, No. 60-295894,
The methods using the antibacterial agents described in JP-A-61-63030 and JP-A-61-51396 can be used.

Furthermore, LFWest, “Water Quality Criteria” Photo.Sc
i, & Eng.Vol.9 No.6 (1965), MWBeach, “Microbiolo
gical Growths in Motion-picture Processing "SMPTE J
ournal Vol.85, (1976) RODeegan, “Photo Processin
g Wash Water Biocides "J.Imaging Tech10, No.6 (198
4) and JP-A-57-8542, JP-A-57-58143, and JP-A-58-105145.
No. 57, No. 57-132146, No. 58-18631, No. 57-97530, No. 5
Antibacterial agents, antifungal agents, surfactants and the like described in 7-157244 can also be used in combination.

Furthermore, for the washing bath or stabilizing bath, RT Kreiman, J.Ima
ge.Tech10, (6) p.242 (1984), isothiazoline compounds, Research Disclosure Vol. 205, No.205.
26 (May 1981), isothiazoline compounds, Vol. 228, No. 22845 (April, 1983), idothiazoline compounds, Japanese Patent Application No. 61-51396. The described compounds and the like can also be used in combination as a bacteriostatic agent (Microbiocide).

Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Sho 5
7), "Handbook of antibacterial and antifungal technology" A compound as described in Hakuhodo (Showa 61) of Japan Society for Antibacterial and Antifungal Agents may be included.

When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank described in Japanese Patent Application No. 61-163217. Further, it is also preferable to adopt a structure of a water washing step as in Japanese Patent Application No. 61-290619.

Further, some or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the process by the method of the present invention As described in JP-A No. 60-235133, it can also be used for a processing solution having a fixing ability which is a processing step before that.

When the silver halide light-sensitive material of the present invention is processed by an automatic processor including at least the steps of development, fixing, washing (or stabilizing) and drying described above, the steps from development to drying are performed.
Complete within 90 seconds, that is, from the time when the tip of the light-sensitive material starts to be dipped in the developing solution, through the fixing, washing (or stabilizing) step, and drying until the tip comes out of the drying zone. The time (so-called Dry to Dry time) is preferably 90 seconds or less, and particularly preferably 70 seconds or less. More preferably, the Dry to Dry time is within 60 seconds.

In the present invention, the "development process time" or "development time" means the time from when the leading edge of the photosensitive material to be processed as described above is immersed in the developing tank solution of the developing machine until it is immersed in the next fixing solution, The "fixing time" is the time from the immersion in the fixing tank liquid to the next immersion in the washing tank liquid (stabilizing liquid). The "washing time" is the time of immersion in the washing tank liquid.

The "drying time" is usually 35 ° C to 100 ° C, preferably 40 ° C.
A drying zone to which hot air of ℃ ~ 80 ℃ is blown is installed in the automatic processing machine, and it means the time to enter the drying zone.

In order to achieve the above rapid processing within 70 seconds, it is possible to develop within 20 seconds, preferably within 15 seconds, but the developing temperature is preferably 25 ° C to 50 ° C.
30 ° C to 40 ° C is more preferable.

According to the present invention, the fixing temperature and time are about 20 ° C. to about 50 ° C.
Seconds to 20 seconds are preferable, and 30 to 40 ° C. is more preferably 6 to 15 seconds. Within this range, sufficient fixing can be performed and the sensitizing dye can be eluted to the extent that residual color is not generated.

Washing or stabilizing bath temperature and time are preferably 0 to 50 ° C. and 6 seconds to 20 seconds, and more preferably 15 ° C. to 40 ° C. and 6 seconds to 15 seconds.

According to the method of the present invention, the developed, fixed and washed (or stabilized) photographic material is squeezed out of the washing water, that is, dried through a squeeze roller. Drying is about 40 ℃ to about 10
It is carried out at 0 ° C., and the drying time can be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 30 seconds, and particularly preferably 40 ° C. to 80 ° C. for about 5 seconds to 20 seconds.

When dry-to-dry development processing of 70 seconds or less is performed in the light-sensitive material / processing system of the present invention, as described in Japanese Patent Application No. 61-297672 in order to prevent development unevenness peculiar to rapid processing. Applying a roller made of rubber material to the roller at the outlet of the developing tank, and as described in Japanese Patent Application No. 61-297673, the discharge flow rate for stirring the developing solution in the developing tank is 10 m / min or more. What to do and Japanese Patent Application Sho 61-315
As described in Japanese Patent No. 537, it is preferable to perform stronger stirring than during standby at least during the development processing. Furthermore, for rapid processing as in the present invention, it is more preferable that the roller of the fixing solution tank is a facing roller in order to increase the fixing speed. By configuring with opposed rollers, the number of rollers can be reduced,
The processing tank can be made smaller. That is, the automatic processing machine can be made more compact.

In the developing method of the light-sensitive material of the present invention, the photographic light-sensitive material is not particularly limited, and a general black-and-white light-sensitive material is mainly used, and also a color light-sensitive material can be used.
In particular, photographic materials for laser printers of medical images, scaner sensitive materials for printing, and direct X-ray sensitive materials for medical use,
It can be used for medical indirect photography X-ray sensitive material, CRT image recording sensitive material, and the like.

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

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

The silver halide emulsion contains a water-soluble iridium salt.

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

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

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

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

The silver halide grains in the photographic emulsion may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes 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 and the average value of the grain thickness of each tabular grain. In the present invention, the preferred tabular grain form is an aspect ratio of 4 or more and less than 20, more preferably 5 or less.
It is more than less than 10. Furthermore, the particle thickness is preferably 0.3 μm or less, and particularly preferably 0.2 μm or less.

It is preferable that the tabular grains are present in an amount of preferably 80% by weight, more preferably 90% by weight or more based on all the grains.

The grain size of 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. 17643.
(December 1978), pp. 22-23, "I. Emulsion p
reparation and types) ”and ibid., No. 18716 (1979)
November), page 648.

The photographic emulsion used in the present invention is described in "Graphic Chemistry and Physics" by Graphide, published by Paul Montel (P.Glafkides, Chem.
ie et Physique Photographique Paul Montel, 1967),
Photographic Emulsion Chemistry (GFDuffin.Photographic Emulsion Chemistry (Foca
Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikman et al., published by Forcal Press (VLZelikman et al, Mak
ing and Coating Photographic Emlsion, Focal Press, 1
964) and the like.

When forming the silver halide grains used in the present invention, as a silver halide solvent for controlling the growth of the grains, for example, ammonia, rodancali, rhodammone, thioether compounds (e.g., U.S. Pat.Nos. 3,271,157, 3,574,628, and 3574,628, No. 3,704,130, No. 4,297,439,
No. 4,276,374, etc.), thione compounds (JP-A-53-144,
No. 319, No. 53-82,408, No. 55-77,737, etc.), amine compounds (for example, JP-A-54-100,717, etc.) and the like.

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

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
To keep constant, that is, so-called controlled
The double jet method can be used, which gives a silver halide emulsion having a regular crystal form and a nearly uniform grain size.

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

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used.

More specific chemical sensitizers include allyl thiocarbamide, thiourea, thiosulfate, sulfur sensitizers such as thioether and cystine; P
Noble metal sensitizers such as alladate): reduction sensitizers such as tin chloride, phenylhydrazine and reductone.

The silver halide emulsion used in the present invention is optionally spectrally sensitized with a known spectral sensitizing dye. Examples of the spectral sensitizing dye to be used include, for example, "Heterocyclic Compounds-The Cyanine Soybean and Relativated Compounds" by Hamer, Jiyon Wheelie and Size (1964) FMHamer, "Heterocy.
clic Compounds-The Cyanine Dyes and Related Compo
unds ", John Wiley & Sons (1964). and Starmer,
"Heterocycle Compounds-Special Topics in Heterocycle Chemistry", Jiyoung Wheelie & Sons (1977)
(DMSturmer, “Heterocyclic Compounds−Special To
pics in Heterocyclic Chemistry ", John Wiley & Sons
(1977). Cyanine, merocyanine, rhodacyanine, styryl, heminanine, oxonol, benzylidene, holopolar, and the like described in, for example, can be used, but cyanine and merocyanine are particularly preferable.

Examples of sensitizing dyes that can be preferably used in the present invention include those disclosed in
60-133442, 61-75339, 62-6251, 59-21282
No. 7, No. 50-122928, No. 59-1801553, etc., and cyanine dyes and merocyanine dyes represented by the general formula. Specifically, JP-A-60-133442 (8)
To (11), pages (5) to (7) of JP-A-61-75339,
Pages (24)-(25), JP-A No. 62-6251 (10)-(1)
5), pages (5) to (7) of JP-A-59-212827, pages (7) to (9) of JP-A-50-122928, and JP-A-59-180553.
Examples thereof include sensitizing dyes for spectrally sensitizing silver halide in the blue region, green region, red region or infrared region of the spectrum described on pages (7) to (18).

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. 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), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. Listed)), cadmium salt,
An azaindene compound or the like 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 to} 5 × 10 ⁻² mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, and particularly preferably 2 × 10 ⁻⁶ mol per mol of silver halide. It is contained in the silver halide photographic emulsion at a ratio of 5 to ^10-4 mol.

The above sensitizing dye can be directly dispersed in the emulsion layer. Further, these may be first dissolved in a suitable solvent such as 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. Ultrasonic waves can also be used for dissolution. Further, as a method for adding the sensitizing dye, as described in US Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid to obtain a dispersion of this dispersion. A method of adding to an emulsion, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving, and adding this dispersion to an emulsion, as described in JP-B-46-24185.
As described in JP-B-61-45217, a method of mechanically pulverizing and dispersing a water-insoluble dye in an aqueous solvent, and adding this dispersion to an emulsion: as described in U.S. Pat.No. 3,822,135. A method in which a dye is dissolved in a surfactant and the solution is added to an emulsion; a method in which a compound for redshifting is used, as described in JP-A-51-74624, and the solution is added to the emulsion; A method in which a dye as described in JP-A-50-80826 is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, U.S. Pat.Nos. 2,912,343, 3,342,605, and
The methods described in 2,996,287 and 3,429,835 can also be used. The above sensitizing dyes may be uniformly dispersed in the silver halide emulsion before coating on a suitable support,
Of course, it can be dispersed in any step of preparing a silver halide emulsion.

The above sensitizing dye can be used in combination with other sensitizing dyes. For example, U.S. Pat.
2,688,545, 3,397,060, 3,615,635, 3,628,964, British Patents 1,242,588, 1,293,86
No. 2, Japanese Patent Publication No. 43-4936, No. 44-14030, No. 43-10773,
U.S. Patent 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Patent No. 2,
No. 615,613, No. 3,615,632, No. 3,617,295, No. 3
The sensitizing dyes described in 3,635,721 and the like can be used.

In order to rapidly process the silver halide light-sensitive material of the present invention according to the present invention, the swelling percentage of the silver halide light-sensitive material is set to 20%.
It is preferably 0% or less.

On the other hand, if the swelling percentage is too low, the speed of development, fixing, washing with water, etc. will decrease, so it is not preferable to lower it more than necessary.

The preferred swelling percentage is 200% or less and 30% or more, especially 1
50% or less, 50% or more is preferable.

Those skilled in the art can easily control the swelling percentage to 200% or less by, for example, increasing the amount of the hardener used in the light-sensitive material.

The swelling percentage is (a) photographic material at 38 ° C and 50% relative humidity of 3
Incubation is carried out for a day, (b) the thickness of the hydrophilic colloid layer is measured, and (c) the photographic material is diluted with distilled water at 21 ° C.
It can be determined by soaking for minutes and (d) measuring the percentage change in layer thickness compared to the hydrophilic colloid layer thickness measured in step (b).

Examples of the hardener that can be used in the present invention include aldehyde compounds, compounds having an active halogen described in U.S. Pat.No. 3,288,775, and reactive ethylenically unsaturated groups described in U.S. Pat. Are known, organic compounds such as epoxy compounds described in US Pat. No. 3,091,537, halogenocarboxaldehydes such as mucochloric acid, and the like are known. Of these, vinyl sulfone type hardeners are preferable. Further, a polymer hardener can also be preferably used.

As the polymer hardener, a polymer having an active vinyl group or a group serving as a precursor thereof is preferable.
Especially preferred are polymers in which the active vinyl group or its precursor group is attached to the polymer backbone by a long spacer, as described in 56-142524. The amount of these hardeners added to achieve the above swelling percentage depends on the type of hardener used and the type of gelatin.

In the rapid processing of the present invention, it is preferred that the emulsion layer and / or the other hydrophilic colloid layer contain an organic substance which flows out in the development processing step. When the substance that flows out is gelatin, a gelatin species that is not involved in the crosslinking reaction of gelatin with a hardening agent is preferable, and examples thereof include acetylated gelatin and phthalated gelatin, and those having a small molecular weight are preferable. On the other hand, as a high molecular substance other than gelatin, polyacrylamide as described in U.S. Pat.No. 3,271,158, or also polyvinyl alcohol, hydrophilic polymers such as polyvinylpyrrolidone can be effectively used, dextran and Satsuka rose, Sugars such as pullulan are also effective.
Among them, polyacrylamide and dextran are preferable,
Polyacrylamide is a particularly preferred substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. Besides this, Research Disclosure
The antifoggants and stabilizers described in Volume 176, No. 17643, Item VI (December issue, 1978) can be used.

Development processing method of the present invention, U.S. Pat.Nos. 4,224,401, 4,168,977, 4,166,742, 4,311,781,
No. 4,272,606, No. 4,221,857, No. 4,243,739 and the like can be applied to the image forming process of a silver halide light-sensitive material capable of obtaining photographic characteristics with superhigh contrast and high sensitivity using the hydrazine derivative. .

As a hydrazine derivative, RESEARCH DISCLOSURE Item
23516 (November 1983, P.346) and documents cited therein, U.S. Patent Nos. 4,080,207 and 4,269,929,
No. 4,276,364, No. 4,278,748, No. 4,385,108
No. 4,459,347, 4,560,638, 4,478,92
No. 8, British Patent No. 2,011,391B and JP-A-60-179734 can be used. The hydrazine derivative is 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, the developer used in this case preferably contains the amino compound described in US Pat. No. 4,269,929 as a contrast enhancing agent.

Next, specific examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 Preparation of Emulsion 30 g of gelatin and 6 g of potassium bromide were added to 1 part of water, and a silver nitrate aqueous solution (5 g of silver nitrate was added to a container kept at 60 ° C. with stirring).
g) and 0.15 g of potassium iodide and an aqueous solution of potassium bromide were added by the double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide were added by the double jet method. At this time, the flow rate was accelerated so that the flow rate at the end of the addition was 5 times that at the start of the addition. After the addition is complete, the sedimentation method
After removing the soluble salts at 40 ° C, the temperature was raised to 40 ° C 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 by combining 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, and polymethylmethacrylate fine particles (average particle size 3.0 μm
m), polyethylene oxide, and a gelatin aqueous solution containing a hardener and the like were used.

Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) was added to the above emulsion as a sensitizing dye.
Oxacarbocyanine hydroxide sodium salt was added at a ratio of 500 mg / 1 mol Ag, and potassium iodide was added at a ratio of 200 mg / 1 mol Ag. Furthermore, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene and 2,6bis (hydroxyamino) -4-diethylamino-1,3,5-
Triazine and nitrone, trimethylolpropane as a dry antifoggant, a coating aid, and a film hardener are added to form a coating solution, and both sides of the polyethylene terephthalate support are coated and dried simultaneously with the surface protective layer to form a photographic material. Created. The coated silver amount of this photographic material is per side
It is 2 g / m ² . The swelling rate according to the above definition was 120%.

This light-sensitive material was exposed to X-rays and developed with the developer fixing solution and washing solution formulations shown below.

<Developer concentrate> Potassium hydroxide 60g Sodium sulfite 100g Potassium sulfite 125g Diethylenetriamine pentaacetic acid 6g Boric acid 25g Hydroquinone 87.5g Diethylene glycol 28g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 6.25g 5-methylbenzo Triazole 0.15g Adjust to 1 with water (adjust to pH 11.00).

Replenisher solution Kit size 5l <Fixer solution concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid / disodium dihydrate sodium hydroxide 24g Compound of the present invention See Table 1 Set to 1 with water (adjust to pH 5.10 with acetic acid) To).

Replenishing solution Kit size 5l <Water stock tank solution> Ethylenediaminetetraacetic acid disodium salt / dihydrate (mold inhibitor) 0.5g / l Automatic processor (see Fig. 1) Dry to Dry processing for 60 seconds.

Development tank (1) 7.5l 35 ℃ x 11.5 seconds (opposing roller) Fixing tank (2) 7.5l 35 ℃ x 12.5 seconds (opposing roller) Water washing tank (3) 6l 20 ℃ x 7.5 seconds (opposing roller) Squeeze roller cleaning Tank (7) 200ml Water stock tank (4) 25l Drying However, the heater was used to maintain the temperature of both the developing and fixing tanks, but the cooling water was not used.

When the development processing was started, each tank was filled with the following processing solutions.

Developing tank (1): 400 ml of the developer concentrate, 600 ml of water, and 10 ml of an aqueous solution containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.50.

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. For each processing of 1 sheet of four-sided photosensitive material (10 inches x 12 inches), 30 ml of developer concentrate and 20 ml of stock tank water are placed in the developer tank, and 10 ml of fixer concentrate concentrate and overflow liquid of the wash tank are placed in the fixing tank. A part of 30 ml squeeze roller washing tank is replenished with 60 ml of stock tank water (in the direction opposite to the film direction) to the washing tank, and 50 sheets of quarter cut size (developing rate of one film 40%) are run per day. Processing continued. During this period, a new replenisher was added in the same manner if the developer, fixer and water were all consumed.

When the light-sensitive material was developed, the circulating stirring liquid amount of the developing solution was set to 20 l / min, and when it was not developed, it was set to 6 l / min.

When one day of development work is completed, 80 ml of water from the above washing water stock tank is intermittently and automatically sprayed from the 10 small holes to the rollers of the crossover between development and fixing and between fixing and washing. Yes (Japanese Patent Application No. 61-131338
Method described in No.).

The dry-to-dry processing time was set to 60 seconds as described above.

Table 1 shows the residual colors after the treatment (values obtained by measuring the transmission optical density of the non-image area with green light).

As shown in Table 1, all the fixing solutions containing the compound of the present invention have little residual color after processing.

Example 2 Photographic materials 201 to 203 using the following various sensitizing dyes as sensitizing dyes were prepared in the same manner as in Example 1 and similarly developed in an automatic developing machine.

In all cases, residual color was reduced when treated with a fixing solution containing the compound of the present invention.

Example 3 A 0.3μ cubic silver iodobromide emulsion containing 2.5 mol% iodide was added to anhydro-5,5-dichloro-9-ethyl-3,
230 mg / silver 1 mol of 3'-bis (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt (sensitizing dye), 1.3 g / silver 1 of hydrazine derivative (the following compound)
Mol, polyethylene glycol (molecular weight about 1000) 300m
g / silver 1 mol, 5-methylbenztriazole,
A dispersion of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene polyethylene acrylate, 2-hydroxy-1,3,5-triazine sodium salt was added. Furthermore,
As a hardener, 1,3-divinylsulfonyl-2-propanol was added in an amount adjusted so that the swelling percentage was 120%.

The coating solution thus prepared was coated on a polyethylene terephthalate film support with a protective layer so that the silver coating amount was 3.5 g.
/ m ² , gelatin coating amount (with emulsion layer and protective layer) 3.0 g /
A film was obtained by coating so as to be m ² .

These films were exposed using a 150-line magenta contact screen through an exposure wedge for sensitometry, then developed with a developer having the following composition at 40 ° C for 15 seconds, and then using Fuji Photo Film Co., Ltd. fixer GR-F1. It was fixed, washed with water and dried.

The automatic processor used here was set to 65 seconds in Dry to Dry.

(Developer composition) Tetrasodium ethylenediaminetetraacetate 1.0g Sodium hydroxide 9.0g 5 ・ Sulfosalicylic acid 44.0g Potassium sulfite 100.0g 5 ・ Methylbenztriazole 0.5g Potassium bromide 6.0g N-methyl p-aminophenol 1 / 2H ₂ SO ₄ 0.4 g Hydroquinone 54.0 g Sodium p-toluenesulfonate 30.0 g Water was added to 1 pH 11.7 The same aqueous solution as used in Example 1 was used for washing water, and 250 ml was replenished for each large size (20 inch × 24 inch) sheet. Did.

Similarly, the above-mentioned fixing solution GR-F1 was treated with Compound I- (1) of the present invention.
The treatment was performed by adding 1.0 g / l. The residual color after treatment was measured in the same manner as in Example 1, and it was found that the residual color density was 0.043 lower than that of the photosensitive material treated without using the compound of the present invention.

Example 4 4 × 10 ⁻⁷ per mol of Ag in an aqueous gelatin solution kept at 50 ° C.
An aqueous solution of nitrate, an aqueous solution of potassium iodide and an aqueous solution of potassium bromide were added simultaneously for 60 minutes in the presence of a molar amount of potassium iridium (III) hexachloride and ammonia, and the pAg was kept at 7.8 during that period to obtain an average particle size of 0.25μ and an average iodine content. Silver halide content 1 mol%
A cubic monodisperse emulsion of was prepared. To these silver iodobromide emulsions, the following compounds as sensitizing dyes were added in an amount of 5.6 × 10 ^-5 mol per 1 mol of Ag, and further added as a stabilizer.
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, Polyethylene acrylate dispersion, polyethylene glycol, 1,3-vinylsulfonyl-2-propanol,
1-phenyl-5-mercaptotetrazole, 1,4-bis [3- (4-acetylamino-pyridinio) propionyloxy] -tetramethylene dipromide and the same hydrazine derivative as in Example 3 (4.8 × 10 ⁻ per mole of silver). ⁽³ mol) was added and the pH of the film surface was adjusted to 5.5 with ascorbic acid, and coating was performed on the polyethylene terephthalate film so that the silver amount was 3.4 g / m ² (the film surface p
H was measured by the method described in JP-A-62-25745. ).
At the same time, a gelatin layer on the emulsion layer is 1.0 g
It was applied so as to be / m ² . The sample thus produced was exposed and developed, and the photographic characteristics were measured.

The developer formulation is as follows.

Developer formulation Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 13.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid tetrasodium salt / dihydrate 1.0 g Odor Potassium iodide 4.0 g 5-Methylbenzotriazole 0.6 g 3-Diethylamino-1,2-propanediol 15.0 g Water was added 1 (pH = 11.65) The fixer formulation is as follows.

Ammonium thiosulfate 150.0 g Sodium sulfite 30.0 g Acetic acid 30.0 g Compound I- (6) of the present invention 1 g Water was added and 1 NaOH was added to pH = 5.00 Development 40 ° C. 15 seconds Fixing 47 ° C. 16 seconds Washing 12 seconds Dry to Dry 67 seconds Above After processing, the sample is photographic performance (Dmax, sensitivity, gamma,
Black spots were good and there were few residual colors (0.0% at Red density)
30).

Example 5 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 similarly developed in an automatic developing machine.

In all cases, residual color was reduced when treated with a fixing solution containing the compound of the present invention.

[Brief description of drawings]

FIG. 1 shows one embodiment of an automatic processor system for carrying out the method of the present invention. 1: Development tank, 2: Fixing tank 3: Rinsing tank, 4: Water stock tank 5: Developer concentrate stock tank 6: Fixer concentrate stock tank 7: Squeeze roller cleaning tank P: Pump

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-61-183645 (JP, A) JP-A-58-122535 (JP, A) JP-A-61-112146 (JP, A) JP-A-60- 147735 (JP, A)

Claims (1)

[Claims] 1. A silver halide light-sensitive material spectrally sensitized with a sensitizing dye is exposed and developed, and then treated with a fixing solution containing at least one compound represented by the following general formula [I] or a salt thereof. A method of developing a silver halide light-sensitive material, wherein the total processing time from development to drying is 90 seconds or less. General formula [I] In the formula, A represents an atomic group necessary for forming a saturated or unsaturated 3- to 8-membered heterocycle, and as a substituent, an alkyl group substituted with an amino group or an ammonio group, or an amino group or an ammonio group is used. It has at least one substituted alkylthio group. However, a structure in which a thioxo group can be enolized by tautomerism is excluded.