JPH07119941B2 - Processing method of silver halide light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide light-sensitive material, and particularly when a silver halide light-sensitive material containing a specific sensitizing dye is rapidly processed. The present invention relates to a method for processing a silver halide light-sensitive material which is improved so that the residual color due to the sensitizing dye is reduced.

(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 for developing a unit amount of the light-sensitive material per unit time, that is, the advantage that the automatic developing machine can be made smaller. The significance of processing is great.

(Problems to be Solved by the Invention) However, with the speeding up of the processing, the sensitizing dye contained in the silver halide light-sensitive material is not completely eluted during the processing, and coloring remains in the light-sensitive material, so-called The problem of residual color becomes large.

By the way, JP-A-63-267739 describes that a carbocyanine-based sensitizing dye is added to a silver halide light-sensitive material having a reduced gelatin coating amount in order to enhance rapid processing property, thereby increasing sensitivity. However, as described above, such a carbocyanine sensitizing dye also has a problem of leaving a residual color.

Therefore, it is an object of the present invention to provide a method for processing a silver halide light-sensitive material capable of rapidly processing the silver halide light-sensitive material without leaving any residual color.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide light-sensitive material having at least one silver halide emulsion layer spectrally sensitized with a sensitizing dye represented by the following general formula [I]. In the processing method of exposing, developing, fixing, and washing (or stabilizing), at least the compound represented by the following general formulas [III] to [V] is added to the fixing solution and / or the washing solution (or stabilizing solution). It was achieved by a method for processing a silver halide light-sensitive material characterized by containing one type and having a total processing time (Dry to Dry) of 90 seconds or less.

General formula [I] (In the formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, an alkenyl group or an aryl group, and at least _one of R ₁ and R ₃ is a sulfoalkyl group or a carboxyalkyl group.
Z ₁ and Z ₂ are non-metallic atomic groups required to form a carbocycle, X ₁
Represents an anion, and n represents 1 or 2. However, n is 1 when forming an intramolecular salt. ) General formula [III] XR ″ ₁ —S _n R ″ ₂ —S—R ″ ₃ —Y In the formula, R ″ ₁ , R ″ ₂ and R ″ ₃ alkylene groups are represented. These alkylene groups may have an ether bond. R ″ ₁ and R ″ ₃ or R ″ ₂ and R ″ ₃ may form a ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an amino group, an ammonio group, a hydroxyl group, a carboxyl group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group, and
And Y may form a ring. n represents an integer of 0-10.

General formula (IV) 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 obtains an enol by tautomerism is excluded.

General formula [V] In the formula, A'is a pyrrole ring, a tetrazole ring, a thiazole ring, a thiazoline ring, a benzthiazole ring, a benzimidazole ring, a benzselenazole ring, a benzoxazole ring, a pyridine ring, a pyrimidine ring, a tetrahydropyrimidine ring, a triazine ring, a quinoxaline ring. Represents a tetraazaindene ring or a pyrazolotriazole ring, and has at least one alkyl group substituted with an amino group or an ammonio group as a substituent.

M'represents a hydrogen atom or a counter cation.

The present invention will be described in detail below.

In the general formula [I], the alkyl groups represented by R ₁ , R ₂ and R ₃ include those having a substituent. For example, lower alkyl groups such as methyl, ethyl, propyl, and butyl, and those in which substituents such as hydroxy group, acetoxy group, sulfo group, and carboxy group are substituted (specifically, 2-hydroxyethyl, 4-hydroxybutyl). , 2-acetoxyethyl, 3
-Acetoxybutyl, 2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, etc. ) Include acetoxy groups of R ₁ , R ₂ and R ₃ that have a substituent, and specifically include allyl, vinylmethyl, butenyl, octenyl and the like.

The aryl groups of R ₁ , R ₂ and R ₃ include those having a substituent,
Specific examples include phenyl and carboxyphenyl.

At least one of R ₁ , R ₂ and R ₃ is a sulfoalkyl group or a carboxyalkyl group.

A benzene ring is preferable as the carbon ring formed by the non-metal atom group of Z ₁ and Z ₂ , and a substituent may be substituted on this benzene ring. Examples of this substituent include an alkyl group (methyl, ethyl, hydroxyethyl, trichloromethyl, etc.), an alkoxy group (methoxy, ethoxy, etc.), an aryl group (phenyl, etc.), an alkoxycarbonyl group (methoxycarbonyl, propoxycarbonyl, butoxy). Carbonyl, etc.), halogen atom (fluorine, chlorine, bromine, etc.), carbamoyl group (-CONH ₂ , N-ethylcarbamoyl, N, N-diethylcarbamoyl, morpholinocarbonyl, etc.), sulfamoyl group (N-ethylsulfamoyl, Examples thereof include morpholinosulfonyl, a sulfonyl group (such as methylsulfonyl), a carboxy group, a sulfo group, a hydroxy group, and a cyano group.

Examples of the anion of X ₁ include a halogen ion and p ^- toluenesulfonate ion.

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

(Compound example) 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, an aminostilbenzene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721) and an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510). Described in), 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. And a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to the 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 US 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 may be added at any step of preparing the silver halide emulsion.

The compounds represented by the general formulas [III] to [V] will be described below.

General formula [III] XR ″ ₁ —S _n R ″ ₂ —S—R ″ ₃ —Y In the formula, R ″ ₁ , R ″ ₂ and R ″ ₃ represent an alkylene group. These alkylene groups may have an ether bond. R ″ ₁ and R ″ ₃ or R ″ ₂ and R ″ ₃ may form a ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an amino group, an ammonio group, a hydroxyl group, a carboxyl group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group,
X and Y may form a ring. n represents an integer of 0-10.

The alkylene group represented by R ″ ₁ , R ″ ₂ and R ″ ₃ has 1 to 10 carbon atoms, and preferably 1 to 6 carbon atoms, for example, —CH ₂ CH ₂ .
₂₋ , − (CH _{2 3} , CH _{2 4} CH _{2 2} OCH _{2 2} , There is. Substituents represented by X and Y include an alkyl group having 1 to 10 carbon atoms in addition to a hydrogen atom (wherein the alkyl group has a substituent, such as a methyl group or an ethyl group), an amino group (here, an amino group). Include those having a substituent, for example, dimethylamino group, diethylamino group, -N (CH ₂ CH ₂
CN) ₂ , NH ₂ , a morpholino group, an ammonio group (here, an ammonio group includes those having a substituent, such as a trimethylammonio group), an aminocarbonyl group (here, an aminocarbonyl group includes a substituent, such as dimethyl) Aminocarbonyl group) and aminosulfonyl group (wherein the aminosulfonyl group includes those having a substituent, for example, dimethylaminosulfonyl group) are preferable. Of these, a hydrogen atom, an amino group and an ammonio group are preferable.

n is preferably an integer of 1 to 4.

The compound represented by the general formula [III] may be in the form of a salt of an inorganic or organic acid. Preferred examples of inorganic or organic acids are hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid,
Examples thereof include hydroiodic acid, perchloric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid.

Specific examples of the compound represented by the general formula [III] are shown below, but the present invention is not limited to these compounds.

The compound represented by the general formula [III] can be synthesized by a very general method, for example, French Patent 1,108,
788, U.S. Pat.Nos. 2,503,776, 2,912,329, and 3,0
21,215, British Patent 950,089, The Journal of the Organic Chemistry, Volume 26, 1991-199.
5 pages (1961), edited by The Chemical Society of Japan, "New Experimental Chemistry Lecture No. 14"
Volume Synthesis and reaction of organic compounds (III), pp. 1713 to 1726, Maruzen (1978), etc.

General formula (IV) In the formula, A represents an atomic group necessary to form a saturated or unsaturated 3- to 8-membered ring that always contains any one of an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom. However, a structure in which a thioxo group can be enolized by tautomerism is excluded.

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

A has, as a substituent, 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.

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.

The compound of the general formula [IV] preferably has a total carbon number of 30 or less, and more preferably 20 or less.

Specific examples of the compound represented by the general formula [IV] in the present invention are shown below, but the present invention is not limited thereto. However, compounds IV- (8), IV- (9) and IV- (12) are reference examples.

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

General formula [V] In the formula, A'is a pyrrole ring, a tetrazole ring, a thiazole ring, a thiazoline ring, a benzthiazole ring, a benzimidazole ring, a benzselenazole ring, a benzoxazole ring, a pyridine ring, a pyrimidine ring, a tetrahydropyrimidine ring, a triazine ring, a quinoxaline ring. Represents a tetraazaindene ring or a pyrazolotriazole ring, and has at least one alkyl group substituted with an amino group or an ammonio group as a substituent.

M'represents a hydrogen atom or a counter cation.

It is desirable that -SM 'of the general formula [V] is bonded to the carbon atom of A'.

The compound of the general formula [V] preferably has a total carbon number of 30 or less, and more preferably 20 or less.

M'is an alkali metal (eg sodium, potassium etc.) or an organic base (eg triethylamine,
Pyridine, DBU (1,8-diazabicyclo [5.4.0] -7-
(Undecene) etc.) and a counter cation such as a conjugated acid, and may represent a hydrogen atom.

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

The compound represented by the general formula [V] is known, and most of them are commercially available. Further, it can be easily synthesized according to the description in "New Experimental Chemistry Course", Volume 14, III, pp. 1699-1713 (Maruzen Co., Ltd.) and JP-A-60-61749.

The amount of the compounds represented by the general formulas (III) to (V) added to the fixing solution and / or the washing solution (or stabilizing solution) is 5 × 10 ⁻⁵ mol / l to 10 ⁻¹ mol // l. , Preferably 10 ^-4 mol / l
To 5 × 10 ^-2 mol / l, in particular 10 ^-3 mol / l~10 ^-2 mol / l.

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 buffering 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 and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. Antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole may be included.
176, No. 17643, Item XXI (December, 1978), development accelerators, and if necessary, toning agents, surfactants, defoaming agents, water softeners, JP-A-56 The amino compound described in No. 106244 may be included.

In the developing treatment of the present invention, a silver stain preventing agent 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, LFA Mason's "Photographic Processing Chemistry", published by Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 62, JP-A-48-64933, etc. may be used.

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, sulfurous acid, bisulfite), pH buffering agents (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.

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. This makes it possible to form a replenisher consisting of one developer and one fixer, and the replenisher can be prepared simply by diluting with water. In the development processing method of a silver halide photographic light-sensitive material, after the developing and fixing steps, the light-sensitive material is treated with a replenishing amount of 3 l or less per 1 _m ^{2 of the} light-sensitive material (including O, that is, washing with water) or a stabilizing solution. You can also do it.

That is, according to the method of the present invention, not only the water-saving treatment can be achieved, but also the 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, LEWest, “Water Quality Criteria” Photo.Sc
i, & Eng. Vol.9 No.6 (1965), MWBeach, “Microbiol
ogical Growths in Motion-Picture Processing "SMPTE
Journal Vol.85, (1976), RODeegan, “Photo Proces
sing Wash Water Biocides "J.Imaging Tech 10, No.6 (1
984) and JP-A-57-8542, JP-A-57-58143, and JP-A-58-10514.
No. 5, 57-132146, 58-18631, 57-97530,
The antibacterial agents, antifungal agents, surfactants and the like described in No. 57-157244 can also be used in combination.

Furthermore, for the washing bath or stabilizing bath, RT Kreiman, J.Ima
ge.Tech 10, (6) p.242 (1984), isothiazoline compounds, Research Disclosure Vol. 205, No.205.
26 (May 1981 issue), isothiazoline compounds, Vol. 228, No. 22845 (April 1983 issue), isothiazoline compounds, Japanese Patent Application No. 61-51396 Compounds and the like can also be used together 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” The chemicals 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 4 ° C.
A drying zone to which hot air of 0 ° C to 80 ° C is blown is installed in the automatic developing machine, and it means the time to enter the drying zone.

It is possible to achieve rapid processing within 70 seconds in the above Dry to Dry because the development time is possible within 15 seconds, but the development temperature is preferably 25 ℃ ~ 50 ℃, 30 ℃ ~ 40 ℃
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. for 6 seconds to 20 seconds, and more preferably 15 ° C. to 40 ° C. for 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 solution tank is 10 m / min or more. In addition to that, Japanese Patent Application No. 61-3
As described in the specification of 15537, it is more preferable to stir more strongly than during standby at least during the development processing.
Furthermore, for rapid processing such as in the present invention, in particular, the structure of the roller of the fixing solution tank is used to accelerate the fixing speed and to accelerate the elution of the dye in the case of a sensitizing dye-containing photosensitive material. More preferably, it is a facing roller. By constructing the counter callers, the number of rollers can be reduced and the processing tank can be reduced in size. 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 present invention is particularly suitable for processing a black and white light-sensitive material for observing a silver image.

The following methods are available for producing the light-sensitive material suitable for rapid development according to the present invention.

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 tank. 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.

Two or more silver halide emulsion layers can be provided in the light-sensitive material of the present invention.
Range of 1g / m ² ~3.5g / m ² on one surface is desired. Still more preferably from 1g / m ² ~3g / m ² on one surface.

In the case of a black-and-white light-sensitive material, the average grain size of silver halide is preferably 1.0 μm or less, as described above.
0.7 μm or less is preferable.

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 an irregular crystal shape 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 that 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 "Graphide's Chemistry and Physics", published by Paul Montel (P.Glafkides, Chim.
ie et Physique Photographique Paul Montel, 1967),
Photographic Emulsion Chemistry (GFDuffin.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 Emulsion, Focal Press,
1964) 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 (for example, JP-A-5
3-144,319, 53-82,408, 55-77,737, etc.), amine compounds (for example, JP-A-54-100,717, etc.)
Etc. can be used.

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.

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.
Polymers in which the active vinyl group, or the group which is the precursor thereof, is bound to the polymer main chain by a long spacer, as described in 56-142524, are particularly preferable. 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 No. 2
3516 (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 enhancement accelerator.

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, polystyrene sulfonate sozo, 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.

Sensitizing dyes listed in Table 1 were added to the above emulsion at 500 mg / 1 mol Ag.
(However, the sensitizing dye C was 400 mg / 1 mol Ag), and potassium iodide was added at the ratio of 200 mg / 1 mol Ag. Furthermore, 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine and nitrone as stabilizers, dry fogging prevention A photographic material was prepared by adding trimethylol, propane, a coating aid, and a film hardener as agents to prepare a coating solution, and coating and drying the coating solution on both sides of the polyethylene terephthalate support simultaneously with the surface protective layers. The coated silver amount of this photographic material is 2 g / m ² per side. The swelling rate according to the above definition was 120%.

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

<Developer concentrate> Potassium hydroxide 60g Sodium sulfite 100g Potassium sulfite 125g Diethylenetriaminepentaacetic 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 size 5l <Fixer solution concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid / dinatrium / dihydrate 0.10g Sodium hydroxide 24g Compound of the present invention See Table 1 (1) with water (pH 5. Adjust to 10.) Replenisher Kit size 5l <Water stock tank solution> Ethylenediaminetetraacetic acid disodium salt / dihydrate (antimold agent) 0.5g / l Automatic processor (See Fig. 1) Dry to Dry 60 Second processing.

Development tank (1) 7.5l 35 ° C x 11.5 seconds (opposing roller) Fixing tank (2) 7.5l 35 ° C x 12.5 seconds (opposing roller) Water washing tank (3) 6l 20 ° C x 7.5 seconds (opposing roller) Squeeze roller washing 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), 20 ml of developer concentrate and 30 ml of stock tank water in the developing tank, 10 ml of fixer concentrate and 30 ml of overflow liquid in the washing tank From the squeeze roller washing tank to the washing tank (in the direction opposite to the film direction), 60 ml of stock tank water was replenished, and the running process of 50 sheets of four-section size (developing rate of one film 40%) was continued per day. . During this period, a new replenisher was added in the same manner if the developer, fixer and water were all consumed.

When the photosensitive material was developed, the circulating stirring liquid amount of the developing solution was set to 20 l / min, and to 6 l / min in the standby state where no development was performed.

When one day's development work is completed, 80 ml of each water in the above washing water stock tank is intermittently and automatically sprayed from the 10 small holes to the crossover roller between the fixed development and fixing-washing process. (JP-A-61-131338
Method described in No.).

The dry-to-dry processing time was set to 60 seconds as described above. Second
In the table, the residual color after processing (the transmission optical density of the non-image area was measured with green light, and [the residual color when the compound of the present invention was not used in the fixer]] to [the compound of the present invention was used in the fixer] The residual color when present was shown].

It can be seen that a more excellent residual color improving effect can be achieved by the combination of the sensitizing dye of the present invention and the residual color improving agent.

Similar effects were obtained even when the sensitizing dye was changed to I- (2), I- (4), and I- (22).

Example 2 In the same manner as in Example 1, except that the compounds added to the fixing solution were changed as shown in Table 3, the following results were obtained.

It can be seen that a more excellent residual color improving effect can be achieved by the combination of the sensitizing dye of the present invention and the residual color improving agent.

Example 3 In the same manner as in Example 1, except that the compounds added to the fixing solution were changed as shown in Table 4, the following results were obtained.

It can be seen that a more excellent residual color improving effect can be achieved by the combination of the sensitizing dye of the present invention and the residual color improving agent.

Example 4 As in Example 1, except that the compound of the invention was added to the water stock tank instead of the fixer and the following results were obtained.

It can be seen that the effect of the combination of the sensitizing dye of the present invention and the residual color improving agent can be obtained by adding the residual color improving agent to the washing solution.

[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

Front Page Continuation (56) References JP-A-63-8644 (JP, A) JP-A-61-20945 (JP, A) JP-A-60-95540 (JP, A) JP-A-53-94927 (JP , A) JP-A-61-112146 (JP, A) JP-B 5-55051 (JP, B2)

Claims (1)

[Claims] 1. A silver halide light-sensitive material having at least one silver halide emulsion layer spectrally sensitized with a sensitizing dye represented by the following general formula [I] is exposed, developed, fixed, washed with water (or In the processing method of stabilizing), the fixing solution and / or the washing solution (or the stabilizing solution) are represented by the following general formula [II
A method for processing a silver halide light-sensitive material, which comprises at least one of the compounds represented by I] to [V] and has a total processing time of 90 seconds or less. General formula [I] (In the formula, R ₁ , R ₂ and R ₃ each represent an alkyl group, an alkenyl group or an aryl group, and at least _one of R ₁ and R ₃ is a sulfoalkyl group or a carboxyalkyl group.
Z ₁ and Z ₂ are non-metallic atomic groups required to form a carbocycle, X ₁
Represents an anion, and n represents 1 or 2. However, n is 1 when forming an intramolecular salt. ) "In ₃ -Y formula, R" formula (III) _{XR "1 -S n R" 2} -S-R represents a _1, R _"2 and R" ₃ alkylene group. These alkylene groups may have an ether bond. R ″ ₁ and R ″ ₃ or R ″ ₂ and R ″ ₃ may form a ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group, an amino group, an ammonio group,
Represents a hydroxyl group, a carboxyl group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group, and X and Y
And may form a ring. n represents an integer of 0-10. General formula (IV) 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 obtains an enol by tautomerism is excluded. General formula [V] In the formula, A'is a pyrrole ring, a tetrazole ring, a thiazole ring, a thiazoline ring, a benzthiazole ring, a benzimidazole ring, a benzselenazole ring, a benzoxazole ring, a pyridine ring, a pyrimidine ring, a tetrahydropyrimidine ring, a triazine ring, a quinoxaline ring. Represents a tetraazaindene ring or a pyrazolotriazole ring, and has at least one alkyl group substituted with an amino group or an ammonio group as a substituent. M'represents a hydrogen atom or a counter cation.