JPH04155331A - Processing method for silver halogenide photosensitive material - Google Patents

Abstract

PURPOSE:To constantly obtain a fixed and stable developing level even when the amount of processing varies substantially by processing a photosensitive material by an alkaline solution before or after it is processed by developing solution. CONSTITUTION:The photosensitive material is immersed in an alkaline solution before or after it is developed-processed. The immersion is preferably done before the processing. A pH of the alkaline solution ranges from 9.0 to 14. The processing temperature is preferable in the range of 10 to 60 deg.C, and the processing time is 3 to 30 seconds. For developing solution, halogen-quinone, chlorohydroquinone, etc. are listed, but the addition is 1 to 35g per liter of the developing solution. A developing solution pH of 7 - 9 is preferably employed, especially a pH of 7 to 8 is favorable. When the development is performed outside the developing solution, the photosensitive material is heated by an infrared heater, and the surface temperature of the photosensitive material of 20 to 80 deg.C is preferably employed, and the carrying speed (time) is favorable in the range of 0.1 to 8.0m/min.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for developing exposed silver halide photographic materials, and more specifically, a silver halide photographic material that can stably obtain a constant level of development without uneven development processing. The present invention relates to a development processing method. [Background of the Invention] It goes without saying that stabilization of the development level is essential when processing photosensitive materials. For example, mistakes in souvenir photos or medical photos cannot be tolerated. In particular, in the case of the latter, the stability of the development process becomes a serious problem, considering the urgency of the diagnosis. Conventionally, silver halide photographic light-sensitive materials have generally been processed in automatic processors. For example, after imagewise exposure, the light-sensitive material is transported by a roller transport mechanism and placed in a developer stored in a developing tank for a predetermined period of time. Images are obtained by immersion. Problems with this type of development processing method include that the active ingredients in the developer stored in the developer tank deteriorate due to fatigue during the running process, and that the developing agent becomes inactivated due to oxidation over time. Can be mentioned. Many proposals have been made as techniques for preventing the deterioration of these developing solutions.
-62004, 55-115039, 56-1
Each publication such as No. 2645 describes a technique for replenishing a developer replenisher continuously or intermittently depending on the processing amount to recover the fatigue deterioration of the developer. However, in all of these techniques, different phenomena occur between the developer components of the first and subsequent developer components, and strictly speaking, each time the photographic processing is performed with different characteristics, the result is that the finished product is different. It had the disadvantage of inconsistent performance. Therefore, it is desirable to use a new developer for each treatment, but conventional developing methods consume a large amount of developer, resulting in cost problems. Under these circumstances, the present applicant has proposed in Japanese Patent Application No. 1-27820 a method of developing a silver halide photographic light-sensitive material by supplying a developer to the exposed surface of the light-sensitive material without immersing the material in a developer. Proposed. That is, a method of applying a developer or a slit development method with an extremely small capacity is used. This processing method has the advantage that it is free from the phenomenon caused by a tired developer, and can be processed with a fresh developer at all times, and moreover, with a small amount of developer. However, when silver halide photographic light-sensitive materials are developed outside of a solution, it is extremely difficult to maintain a constant activity level of the developer, including temperature control, and this has the serious drawback of not causing fluctuations in the level of phenomena. It had [Object of the Invention] In order to solve the above-mentioned problems, the object of the present invention is to provide a method for stably maintaining a constant level of development even when the processing amount varies greatly in a viscous developer supply development method. An object of the present invention is to provide a method for developing the resulting silver halide photographic material. [Structure of the Invention] The above object of the present invention is to process a silver halide photographic light-sensitive material with an alkaline solution before or after processing with a processing solution containing a developing agent, in a processing method of processing a silver halide photographic light-sensitive material with a viscous developer, and The pH of the processing solution containing the developing agent is 7 to 9.
This is achieved by a method for processing a silver halide photographic material, which is characterized by the following. Furthermore, the above-mentioned processing solution containing a developing agent must always be fresh. The present invention will be explained in detail below. In the present invention, the film is immersed in an alkaline solution before or after the development process, but preferably before the process. The pH of the alkaline solution varies depending on processing conditions such as processing liquid components, development speed, temperature, etc., but is preferably pH 9.0 to 14, particularly preferably pH 12 to I4. As the alkaline solution in this case, salts of alkali metals, alkaline earths, etc. are used, and they may be used alone or in combination, but those having 9H buffering properties are preferred. The treatment temperature is preferably 10 to 60°C, particularly preferably 25 to 4°C.
It is 0°C. The treatment time is 3 to 30 seconds, particularly preferably 5 to 15 seconds. There is no particular limitation on the type of alkaline bath, and a conventional tank type may be used. The viscosity of the viscous developer according to the present invention is 5 to 20 at 20°C.
It is necessary to have CP, and an alkali-soluble hydrophilic polymer is used as the thickener. Specific examples include sodium salts of polyacrylamide, hydroquinepropyl cellulose, polyethylene oxide, carboxymethyl cellulose, and hydroquine ethyl cellulose. Furthermore, an alkali-soluble polymer compound made of sugar such as polysaccharide gum may be used. The viscosity of the viscous developer according to the present invention varies depending on the coating device, conveyance device, etc., but preferably 5 to 2 at 20°C.
It may be in the range of 0 cP, more preferably 5 to 10 cP. In the present invention, the amount of the viscous developer applied to the photosensitive material is preferably 70 to 300 g/m2, more preferably 100 g/m2.
~200g/n'. The amount of the thickener used is determined based on the above conditions or the type of compound, but for example, in the case of carboxyl methyl cellulose, it may be in the range of 0.5 to 2.5 g per developer IQ. The thickener may be added from the beginning when preparing the developer, or may be mixed with the developer just before development. The thickener may be used alone or in combination, and a viscous developer having desired flow characteristics can be obtained. Next, the process of heating the exposed silver halide photographic material in the present invention will be described. Generally, unlike heating a solution in a tank, external development involves physically extremely difficult elements. For example, when warm air is blown onto a photosensitive material, drying takes priority, impairing developability and furthermore causing fog to occur on the photosensitive material. Further, heating with an infrared heater or the like causes the silver halide photographic material to be exposed to light and lose its photographic properties. After various studies by the present inventor, it was found that heating using a far-infrared heater is the best method to meet the object of the present invention. As the far-infrared heater, one with a low expansion coefficient and good thermal efficiency is selected due to issues such as water resistance, and for example, a far-infrared heater manufactured by Asahi Glass Co., Ltd. is preferably used. In the present invention, a specific method of viscous development processing without immersion of a photosensitive material after exposure will be described below. In the development processing method of the present invention, on the ft optical surface of a silver halide photographic light-sensitive material having a hydrophilic colloid layer on a support,
A developing solution containing hydroquinones is supplied, and the silver halide photographic light-sensitive material is developed without being immersed in the developer. This silver halide photographic light-sensitive material is typically a high-speed film such as X-ray, and has at least a hydrophilic colloid layer on both sides of a support, which is made of a transparent material. The supply of the viscous developer to both sides of the silver halide photographic light-sensitive material is preferably carried out by transporting the silver halide photographic light-sensitive material, and this transport may be carried out horizontally or vertically; It is preferable to supply the viscous developer to the silver halide photographic light-sensitive material because the installation area of the apparatus can be reduced. By supplying the developer in a predetermined amount without immersing it in the developer, it is possible to supply a predetermined amount of developer necessary for the development process, which prevents fatigue of the developer over time and saves the developer. It also becomes. The supply of the developer is achieved by applying a viscous developer to the exposed surface of the silver halide photographic light-sensitive material,
Specifically, examples include a roller transfer method, a dab coating method, and a curtain coating method. If the viscosity is low, it may be applied by spraying under pressure. In this case, the amount of developer used is arbitrary; preferably 30 to 300 cc per 1 m2 of one side of the photosensitive material.
It is. The developer may be supplied not only once but several times. Examples of the hydroquinones used in the developer of the present invention include hydroquinone, chloro/monohydroquinone, methylhydroquinone, etc. Hydroquinone is preferably used. The amount of added calories (1 g to 35 g per developer solution lI2, preferably 115 g to 25 g
It is. Further, the developing solution of this invention includes Japanese Patent Application Laid-Open No. 63-10158
A 3-pyrazolidone developing agent, a dialdehyde hardening agent, an anti-capri agent selected from intazoles, benzimidazoles, penztriazoles, and mercaptothiazoles, other chelating agents, buffers, and alkalis as shown in the No. Agents, solubilizers, pH adjusters, development accelerators, surfactants, etc. may also be added as necessary. The pH of the developer used in the present invention is preferably 117 to 9, particularly preferably 7 to 8. In this invention, a viscous developer containing hydroquinones is supplied to the exposed surface of a silver halide photographic material having hydrophilic colloid layers on both sides of the support. Do not immerse it in water. In this way, the photosensitive material is not immersed in the stored developer, but the developer is supplied; therefore, it is possible to process the photosensitive material with a developer that does not cause development fatigue due to processing or oxidation fatigue due to contact with air. . Hereinafter, the present invention will be explained in detail based on the accompanying drawings. FIG. 1 is a block diagram showing an example of a processing apparatus using a viscous developer used in the present invention. However, the present invention is not limited to this device. In FIG. 1, the photosensitive material is immersed in an alkaline bath (not shown), and then a pair of transport rollers (1
) The exposed photosensitive material 4 inserted through the rollers (D) is fed in the direction of the arrow, and the viscous developer flowing out from the viscous developer (D) through the two transfer rollers (3) is evenly distributed over the surface of the photosensitive material. : Apply. Next, the applied viscous developer and photosensitive material are heated by a far-infrared heater (H) having a heater cover (HC), and development proceeds. The fully developed photosensitive material is sent to a fixing and water washing process (not shown) by the next pair of transport rollers (2), and is then dried to complete the processing. In the above, any number of far infrared heaters (H) may be installed as needed, and one on the front and back sides of the photosensitive material.
It may be installed as appropriate in the range from a pair to an IO pair. When heating with the far infrared heater in the present invention,
The time and temperature can be chosen freely, but usually
The surface temperature of the photosensitive material coated with the viscous developer is 20°C or more.
It may be in the range of 80°C, more preferably 30°C to 70°
Should I set it so that it becomes C? The conveyance speed (time) may be in the range of 0.1 m to 8.0 L11/min, more preferably 0.5 M to 3.0+11/min. The alkaline bath is installed before or after this developing device. In the present invention, the fixing solution is not particularly limited, and any known fixing solution can be used. Further, the form of the fixing bath is not particularly limited, and a conventional tank-type fixing bath can be used. The silver halide photographic light-sensitive material to be applied to the development processing method according to the present invention may be any silver halide such as silver iodobromide, silver iodochloride, and silver iodochlorobromide, but it is particularly sensitive. Silver iodobromide is preferable in that it yields the following. Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may be of a crystalline type such as a tetrahedron, which is all grown in the same direction, a polyhedral crystalline type such as a sphere, a crystalline type consisting of twins having planar defects, or a mixed or composite type thereof. The grain size of these silver halide grains may range from fine grains of 0.1 μm or less to large grains of up to 20 μm. The emulsion used in the present invention can be produced by a known method. For example, Research Disclosure (RD) No.
47643 (December 1978), pages 22-23, 1
・Emulsion Preparation method
ion and types) and the same (RD) No. 1
8716 (1979, 11A), p. 648. The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "The theory" by T., Fl. James.
of thephotographic processes
s” 4th edition, published by Mac+m1llan (1977)
Methods described on pages 38-104, G.F., Dauffin
Author: “Photographic Emulsion Chemistry” Photographic e+
mulsionChemistry”, Focal
Press (1966), Glafkide, P.
“Physics and Chemistry of Photography” by S. Chia+ie etphy
Paul
Published by ManteJ (1967), V, L, Zel
ikman et al. [Manufacture and Coating of Photographic Emulsions J”Mak
ing and coating photograp
hice+mulsion” Focal press
It is prepared by the method described in Shakan (1964). That is, solution conditions such as neutral method, acidic method, ammonia method, etc.
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, fan/well method, and combination methods thereof. A preferred embodiment is a monodispersed emulsion in which silver iodide is localized inside the grains. The monodisperse emulsion referred to here means that when the average grain diameter is measured by a conventional method, for example,
At least 95% of the grains, by number or weight, are silver halide grains having a mean grain size within ±40%, preferably within ±30%. The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. The crystal structure of silver halide may have different silver halide compositions inside and outside. In a preferred embodiment, the emulsion has a core/7 layer having a clear two-layer structure consisting of a high-iodity core portion and a low-iodine/L layer.
The silver iodide content of the high-density part is 20 to 40 mol %, particularly preferably 20 to 30 mol %. The manufacturing method of such a monodispersed emulsion is known, for example, J. Ph
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
55-142329, 58-49938, British Patent No. 1,413.748, US Patent No. 3,574゜6
It is described in publications such as No. 28 and No. 3,655.394. As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using seed crystals and supplying silver ions and halide ions using the seed crystals as growth nuclei is particularly preferred. Note that methods for obtaining core/shell emulsions include, for example, British Patent No. 1,027,146 and U.S. Patent Nos. 3 and 50.
5. No. 068, No. 4,444,877, Japanese Unexamined Patent Publication No. 1986-1
It is described in detail in publications such as No. 4331. The silver halide emulsion may be tabular grains having an aspect ratio of 5 or more. The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness, as described in British Patent No. 2. l12.157, U.S. Patent No. 4.4
No. 39.520, No. 4,433.048, No. 4,
It can be prepared by the method described in publications such as No. 414.310 and No. 4,434,226. The emulsion mentioned above may be a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. good. In these emulsions, cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be used in the stage of physical ripening or grain preparation. The emulsion may be washed with water to remove soluble salts, such as a noodle washing method, a flocculation/yellow sedimentation method, or an ultrafiltration method. Preferred water washing methods include, for example, the method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 35-16086, or the method described in Japanese Patent Publication No. 16086
Agglomerated polymer agent example G 3 described in No. 3-158644,
A particularly preferred desalting method includes a method using G 8 or the like. Various photographic additives can be used in the emulsion according to the present invention in the steps before and after physical ripening or chemical ripening. Examples of known additives include compounds described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979). The types of compounds shown in these two Research Disclosures and their descriptions are listed in the table below.
Page Classification Page Classification Chemical sensitizer 23 I[1648-Upper right sensitizing dye 23 IV 648
Right-649 Left Development Accelerator 29 II+
648-Right upper blade anti-blur agent 24 V
l 649-Lower right stabilizer /
/ 11 color stain prevention agent 25
■ 650 left-right image stabilizer 25
■ Ultraviolet absorber 25-26 ■ 649 right-650 left filter dye /I
//Brightener 24 V Hardener 26 X 651
Left coating aid 26-27 n 65
0 right surfactant 26-27 n 6
50 right plasticizer 27 U
y Slip agent /l Static inhibitor 27 nl
tt cloak agent 28 1VI
650 right binder 26 I!
651 Left Examples of supports that can be used in the photosensitive material according to the present invention include the above-mentioned RD-17643.
Examples include those described in the left column of page 28 and page 647 of RD-187]6. Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve adhesion of the coating layer. The emulsion according to the present invention can then be coated on one or both sides of the support thus treated. The present invention is applicable to all silver halide photographic materials, but is particularly suitable for high-sensitivity black-and-white photographic materials. When applying the present invention to medical X-ray radiography,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. This is adhered to both sides of a photosensitive material coated with the emulsion of the present invention on both sides. It is desirable to expose the screen to light.The penetrating radiation referred to here is a high-energy electromagnetic wave, and means Refers to an intensifying screen having a fluorescent component, or a fluorescent intensifying screen having a rare earth compound activated with terbium as a main component. The present invention is not limited to this example. Example 1 Preparation of a coating sample While controlling the temperature at 60°C, pAg = 8, and pH = 2.0, the average particle size was 0.3 μm using the double jet method. A monodisperse cubic emulsion of silver iodobromide containing 2 mol% of silver iodide (A
) was obtained. This emulsion has an occurrence rate of twins of less than 1% in terms of number, as seen from electron micrographs. Using this emulsion (A) as a seed crystal, it was grown as follows. That is, this seed crystal (A) was dissolved in solutions 8 and 5Q containing preserved gelatin and, if necessary, ammonia, kept at 40°C, and the pH was further adjusted with acetic acid. Using this solution as a mother liquid, a 3.2N aqueous ammoniacal silver ion solution was added by the tablugent method. That is, I) Ag was controlled to 7.3, pH was controlled to 9.7, and a layer with a silver iodide content of 30 mol % was formed. Next, particle size 9
5%, changing pH from 9 to 8.2 and pAg to 9.
．． It was kept at 0 and allowed to grow. Thereafter, a potassium bromide solution was added using a nozzle over a period of 8 minutes to reduce I)Ag to 11.0, and the mixing was completed 3 minutes after the addition of potassium bromide was completed. This emulsion has an average grain size of 0.7 μm and a silver iodide content of the entire grains of about 2.0 mol %. Next, a desalting step was performed to remove excess soluble salts from this reaction solution. That is, the reaction solution was kept at 40°C, and the following compound (1) was added at 5 g/8 g x 1 mol, Mg5O+ 8
g/AgX l mole was added, stirred for 5 minutes and then allowed to stand. Thereafter, the supernatant liquid was discharged to make a liquid volume of 200 cc per mole of AgX. Next, 40°C pure water], 8ff/1 mol of AgX was added, and the mixture was stirred for 5 minutes. Next, 50.20 g of Mg/1 mole of AgX was added, stirred and left to stand in the same manner as above, and the supernatant liquid was removed to perform desalting. The solution was then stirred and post-gelatin was added to redisperse the AgX. Compound (1) The resulting emulsion was kept at 55°C, the following sensitizing dyes (1) and (2) were added, and then ammonium thiocyanate, chloroauric acid, and hypo were added to perform gold/sulfur sensitization. . After completion of sensitization, 4-hydroxy-6-methyl-1,3,3a,
7-Chitrazaindene was added. Sensitizing dye (1) Sensitizing dye (2) 20 g 1 mol AgX These emulsions each contain AgX 1 as an additive.
400 mg per mole of L-butyl-catechol, polyvinylpyrrolidone (molecular weight 10.000) 1. Og, styrene/maleic anhydride copolymer 2.5g, trimethylolpropane 1Og, diethylene glycol 5g 1 nitrophenyl-triphenylphosphonium chloride F
50 mg, l, 4 g of ammonium 3-dihydroquinobenzene-4-sulfonate 15 mg of sodium 2-mercaptobenzimidazole-5-sulfonate 1. 10+ng of t-dimethylol-1-bromo-1-nitromethane was added to prepare an emulsion coating solution. Additionally, the following compound was added as a protective layer additive. (The amount added is shown as the amount per 1 g of gelatin.) CI (2COO
(C)! ), CH. C) ICOO(CH2)2CH(CH,). SO3Na 7mg Matting agent 7 consisting of polymethyl methacrylate with an average particle size of 5 μm tr + g, colloidal strength 70 mg with an average particle size of 0.013 μm, (CHO)z 81Ig, 1 (
CHO6+++g was added to prepare a coating solution for a protective layer. Each of the obtained coating solutions was mixed with Grindyl methacrylate 5
0w

[%, methyl acrylate 1Qvt%, and butyl methacrylate 4Qvt% copolymer consisting of three types of heptamers were subbed with an aqueous copolymer dispersion obtained by diluting the copolymer to a concentration of 1Qwt%. It was coated on a polyethylene terephthalate blue base with a thickness of 180 μm. That is, an emulsion layer and a protective layer were simultaneously coated on both sides of the base in order from the support, dried to obtain a sample, and then heated at 23°
After the hardening film was stabilized by leaving it in an atmosphere of C155%R1 (C155%R1) for 3 days, the following development experiment was performed. A 3% gelatin solution was used, and the amount of gelatin applied including the emulsion layer protective layer was 6.5 g/+n' on both sides. (Preparation of processing solution) Alkaline solution, developer solution and A fixing solution was prepared. Alkaline liquid The following three types of alkaline liquids, A, B, and C, were prepared.Formulation A KOHlOQ/Q aqueous solutionFormulation B K2COs 0.5mo12/12, KOH
Aqueous solution formulation of O,5aoQ/12 C N a OH0,6moff/LCHsCOOHO,1
moQ/Q aqueous developer Potassium sulfite 55g Hydroquinone 25g 1-phenyl-3
-Pyrazolidone 1.2g boric acid
]0. Og sodium hydroxide
105g triethylene glycol
17.5g 5-nitrobennoimitanol
0. lOg glutaraldehyde bisulfite 1
5.0g glacial acetic acid 16.0
gPotassium bromide 4.0gTriethylenetetramine6acetic acid 2.5g90011IQ with water
After that, carboquine methyl cellulose was added to give the viscosity shown in Table 1, and the whole was finished to IQ. (If not added, finish with water to 1p.) Fixing solution Ammonium thiosulfate 130.0g Anhydrous sodium sulfite 7.3g Boric acid
7.0g acetic acid (9Qvt%)
5.5g Sodium acetate trihydrate 258g Aluminum sulfate 18hydrate
146g sulfuric acid (50vt%)
Finishing with 6.77g water
Q Development Experiment Using the developing apparatus shown in Figure 1, development was carried out by changing the amount of developer and the developing pH as shown in Table 1. Note that the alkaline solution was used before development. Alkali temperature 33
℃ for 20 seconds. The processing temperature of the developer was 33°CCl2O seconds, and the temperature of the photosensitive material when passing through the heater was 33-36°C. The developer was supplied from each roller, and the amount of supplied solution is the total amount. After passing through the developer, use a fixing tank with the above fixing solution at 33°C.
The fixing process was carried out while stirring for 20 seconds. Next, the film was washed with water and dried, and development unevenness was evaluated. Evaluation of development unevenness: ◎ No occurrence. ○ Occurs a little, but there is no problem. △ Although it occurs, it is usable. × Occurred and there is a problem. The results are shown in Table 1. As is clear from Table 1, in the case of the present invention, at least the amount of developer is good, and uneven development is good. Furthermore, similar results were obtained through experiments when alkali treatment was performed after development. [Effects of the Invention] According to the present invention, it was possible to provide a method for developing a silver halide photographic light-sensitive material, in which a constant level of development can be stably obtained even when the amount of development processing varies greatly.

[Brief explanation of drawings]

FIG. 1 is a block diagram showing one example of the viscous developing device of the present invention. l, 2: Conveyance roller 3: Transfer roller 4 = Photosensitive material D: Developer storage tank

Claims (2)

[Claims] (1) In a processing method in which a silver halide photographic light-sensitive material is processed with a viscous developer, it is treated with an alkaline solution before or after processing with a processing solution containing a developing agent, and the processing solution containing the developing agent is treated with an alkaline solution. A method for processing a silver halide photographic material, characterized in that the pH is 7 to 9. (2) The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing solution containing a developing agent is always a new solution when processing the silver halide photographic light-sensitive material.