JPH04277738A - Development processing method for silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To decrease the silver stains arising in the development processing of a silver halide photosensitive material without exerting an adverse influence to other photographic performances. CONSTITUTION:The compd. expressed by formula (I) is added to a developer for the silver halide photosensitive material, by which the silver stains are decreased without exerting the adverse influence on the other photographic performances. In the formula, Z denotes the atom group necessary for forming a ring; X denotes a substituent; n denotes O or 1 to 5 integer.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for developing silver halide photosensitive materials, and more specifically, the present invention relates to a method for developing silver halide photosensitive materials, and more specifically, silver stains (also referred to as silver sludge) that adhere to developing tanks, developing racks, and rollers during processing of photographic photosensitive materials. ), and it relates to a method that facilitates the daily maintenance of instruments and equipment.

0002

[Prior Art] Generally, when a silver halide photographic light-sensitive material (hereinafter sometimes abbreviated as "sensitive material" or "light-sensitive material") is developed, the walls of the developing tank, vat, and developing tank of an automatic processor gradually develop depending on the amount of processing. It has been known for a long time that silver adheres and accumulates on developing tanks and developing rollers. This is also called silver stain or silver sludge, and it adheres to the photosensitive material being processed and stains the image, requiring regular cleaning and maintenance of the machine.

Incidentally, in recent years, there has been an increasing demand for rapid processing in the development processing of silver halide photographic materials. In order to perform rapid processing, it is necessary to increase the activity of the developer, but this is largely due to the properties of the silver halide photographic light-sensitive material. When using an automatic processor (hereinafter referred to as an automatic processor), there are usually steps such as development, fixing, washing, and drying, and the drying step is particularly important. In order to finish drying quickly, it is most effective to reduce the amount of silver in the photosensitive material.

Since tabular silver halide grains have a high covering power, it is possible to reduce the amount of silver without impairing performance such as photographic properties and image quality. This is advantageous not only in the drying process but also in rapid processing of development, fixing, and water washing processes. Therefore, it is most suitable to use tabular silver halide grains for rapid processing. Regarding the properties of these tabular silver halide grains, please refer to Rese
archDisclosure Volume 225 Item 22
534 p20-p58 (January 1983 issue), JP-A-5
No. 8-127921, No. 58-113926, and US Pat. No. 4,425,425. However, since the surface area of these tabular silver halide grains is much larger than that of conventional potato-like grains, the amount of silver halide dissolved during development is also large, and therefore the degree of silver staining is also smaller than that of conventional potato-like grains. They have the disadvantage that they are larger than particles and cannot take advantage of the advantages of rapid processing.

On the other hand, there are photosensitive materials that do not originally require such high sensitivity, such as printing photosensitive materials, and photosensitive materials for laser printers, which can be systemically supported by electronics to achieve such high sensitivity. In unnecessary sensitive materials, the grain size becomes smaller, and the silver halide composition becomes a grain structure that is more easily soluble from silver iodide to silver bromide and silver chloride, resulting in a composition that is more likely to cause silver staining. On the other hand, by doing so, it is possible to respond to rapid development processing even though it is a single-sided photosensitive material.

In addition, the amount of coated silver in industrial X-ray sensitive materials is nearly three times greater than that in medical X-ray sensitive materials, and the silver halide grains are also smaller, making the problem of silver staining even more serious. It's serious. Furthermore, in the processing of negative photosensitive materials for general photography, the graininess of images is emphasized, so the sulfite concentration in the developer is increased, and the development time is rather extended as much as possible to minimize the contribution of so-called dissolution physical development. Since it is so large, silver contamination is a very big problem.

As mentioned above, in each of the various sensitive material processing systems, there are major reasons why the problem of silver staining cannot be avoided, and it has become a major problem that cannot be solved. Moreover, environmental problems have recently come into the spotlight, and waste liquid from developing processing solutions is no exception. Reducing the amount of replenisher and waste fluid is extremely important in terms of environmental conservation, and it is desirable to reduce this amount as much as possible. However, if the amount of replenisher is reduced, the concentration of silver eluted into the developer increases inversely.
Silver stains are further increased. Furthermore, even if waste liquid is reduced, maintenance of the processor is complicated and may even cause a decline in the performance of the finished photograph. Due to this problem, it is currently not possible to easily reduce the amount of replenisher.

Each time cleaning is performed to remove this silver stain, the developer is drained from the developing tank, and the tank is filled with a very strong oxidizing agent solution such as cerium sulfate. must be left stirring for at least 30 minutes. Furthermore, if traces of this oxidizing agent remain in the developing tank after this, the developing solution will be oxidized and deteriorated, so it must be thoroughly washed with water. This cleaning work is one of the biggest daily maintenance burdens, especially for automatic processors, and improvements are desperately needed from the standpoint of work safety and the pollution burden of cleaning agents. It is.

On the other hand, as a method for reducing this silver stain, as disclosed in Japanese Patent Application Laid-Open No. 56-24347, methods are proposed to reduce the amount of silver ions eluted into the developer and/or to suppress the reduction of silver ions to silver. A method of adding a mercapto compound as a silver stain preventive agent is known. In this case, the mercapto compound used is one having a sulfo group as a water-soluble group. However, this method has the disadvantage that the effect of suppressing the development itself is unavoidable, which is accompanied by a decrease in sensitivity. Moreover, the sensitivity to this compound varies depending on the characteristics of the photosensitive material, so it cannot be expected to be effective even if used uniformly. Further, in a photosensitive material/development processing system that is intended to be used with as high a sensitivity as possible, a decrease in sensitivity is a serious drawback. In addition, changes in gradation are also a problem that must be avoided. Further, Japanese Patent Publication No. 56-46585 discloses the use of a disulfide having a carboxy group as a silver stain preventive agent. However, in this case, when the amount added is large enough to obtain a sufficient silver stain prevention effect, a decrease in sensitivity and a change in gradation occur.

0010

SUMMARY OF THE INVENTION An object of the present invention is, first, to reduce silver stains that occur in a developing tank and/or a developing rack and roller when developing a silver halide photographic material. Second, it facilitates the maintenance of automatic processing machines and developing equipment; third, it reduces silver stains without affecting photographic properties; and fourth, it does not impair the stability of the developer. The fifth purpose is to reduce silver stains.The fifth purpose is to reduce silver stains even if the amount of replenisher is reduced.

[0011]

[Means for Solving the Problems] It is an object of the present invention to provide a method for developing a silver halide photosensitive material in which a silver halide photosensitive material is exposed and then developed, in which the developer used in the development process is as follows: This was achieved by adding at least one compound represented by general formula (I). General formula (I)

0012

[Case 2]

In the formula, Z represents an atomic group necessary to form a ring. X represents a substituent. n represents 0 or an integer of 1 to 5.

Next, the compound represented by the general formula (I) will be explained in detail. In the formula, Z represents an atomic group necessary to form a ring. Z preferably represents an atomic group necessary to form a 5- to 10-membered ring, and specifically includes a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, and the like. Preferably it is a carbon atom. Z may be fused with an aromatic ring. X represents a substituent. Preferred examples include hydroxy group, carboxy group, sulfonic acid group, amino group, and halogen atom. n represents 0 or an integer of 1 to 5. n is 2
In the above cases, X may be the same or different.

Specific examples of the compound represented by the general formula (I) will be described below, but the present invention is not limited thereto.

[0016]

[Chemical formula 3]

[0017]

[C4]

The compounds of the present invention are Tetrahydron Letters.
9, 655-656 (1973), Journal of
Organic Chemistry (J. Org. Che
m. ) Volume 34, 157 (1963), Synthesis (Syn
Thesis) 607-608 (1963), Journal of the American Chemical Society (J.
Am. Chem. Soc. ) Volume 77 6632 (1
955), Journal of Organic Chemistry (J. Org. Chem.) Volume 33, 1257 (
It can be synthesized by the method described in (1968) et al.

The preferred concentration of the compound of the present invention in the developer solution (working solution) is 0.01 mmol to 50 mmol, particularly 0.05 mmol to 10 mmol, more preferably 0.1 mmol to 5 mmol per liter of the working solution. It is.

The preferred concentration of the compound of the present invention in the developing solution (working solution) is 0.01 mmol to 50 mmol, more preferably 0.01 mmol to 50 mmol per liter of the developing solution (working solution).
．． 05 mmol to 10 mmol, particularly preferably 0.1
mmol to 5 mmol.

The developing agent used in the developer of the present invention is mainly composed of hydroquinones, but a combination of hydroquinones and 1-phenyl-3-pyrazolidones, or a combination of hydroquinones and pyrazolidones is preferred, since it is easy to obtain good performance. - Good combination with aminophenols. Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,
, 3-dibromohydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonate and the like, with hydroquinone being particularly preferred.

The p-aminophenol developing agent used in the present invention includes N-methyl-p-aminophenol,
p-aminophenol, N-(β-hydroxyethyl)
-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, p
-benzylaminophenol, among others, N-
Methyl-p-aminophenol is preferred.

The 3-pyrazolidone developing agents used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 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, etc.

[0024] Hydroquinone type developing agent usually has a concentration of 0.01
It is used in an amount of mol/l to 1.5 mol/l, preferably 0.05 mol/l to 1.2 mol/l. In addition to this, p-aminophenol-based developing agents or 3-pyrazolidone-based developing agents are usually used in amounts ranging from 0.0005 mol/l to 0.
．． 2 mol/l, preferably 0.001 mol/l to 0
．． It is used in an amount of 0.01 mol/l.

Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
These include ammonium sulfite, sodium bisulfite, potassium metabisulfite, etc. Sulfite is 0.1 mol/l
Particularly preferably 0.3 mol/l or more. Further, the upper limit is preferably up to 2.5 mol/l in the developer concentrate.

The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 18. More preferably, the pH range is from 10 to 12. Alkaline agents used for setting pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. JP-A-62-186259 (Borate), JP-A-62-186259 (Borate)
Buffers such as No. 0-93433 (eg, sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. Here is the chelate stability constant:
L. G. Sillen A. E. Martell
Author, H “Stability Constant
s of Metal-ion Complexes”,
The Chemical Society,London
Don (1964). S. Chaberek・A. E
．． “Organic Seques” by John Martell.
tering Agents”, Wiley (1959)
. etc. means a commonly known constant. In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe3+).

In the present invention, specific examples of compounds of the chelating agent having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetraminehexaacetic acid,
Diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diamino-2- Propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N,N,
N',N'tetrakismethylenephosphonic acid, nitrilo-
N,N,N-trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,
Examples include 2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. .

Further, a dialdehyde hardener or its bisulfite adduct is used in the developer, and specific examples include glutaraldehyde and its bisulfite adduct. Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol, and methanol. Organic solvents such as: 1-phenyl-
Antifoggants such as mercapto compounds such as 5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole. Research Disclosure No. 176
Volume, No. 17643, Section XXI (December Issue, 1
Development accelerators described in 1978) and, if necessary, color toning agents, surfactants, antifoaming agents, water softeners, and JP-A-56
It may also contain the amino compound described in No.-106244.

The developing solution of the present invention contains amino compounds such as alkanolamines described in European Patent Publication No. 136582, British Patent No. 958678, US Pat. It can be used for elevating and other purposes. Besides this, L. F. A. Mason, “Photographic
"Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent No. 2,1
No. 93,015, No. 2,592,364, Japanese Unexamined Patent Publication No. 1973
-64933 etc. may be used.

[0031] The fixing solution is an aqueous solution containing thiosulfate;
It has a pH of 3.8 or higher, preferably 4.2 to 7.0. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/l. The fixer may also contain aqueous aluminum salts that act as hardeners, including, for example, aluminum chloride,
Examples include aluminum sulfate and potassium alum. In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. It is effective to contain these compounds at 0.005 mol or more per liter of fixer, especially from 0.01 mol/l to 0.0 mol/l.
3 mol/l is particularly effective. The fixer may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), and pH adjusters (e.g. sulfuric acid).
, chelating agents with hard water softening ability and JP-A-62-7855
The compound described in No. 1 can be included.

In the present invention, the term "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution. "Fixing time" is the time from immersion in the fixing tank liquid until immersion in the next washing tank liquid (stabilizing liquid). "Washing time" refers to the time during which the film is immersed in the washing tank liquid. In addition, "drying time" is usually 35℃ to 100℃ for automatic processors.
A drying zone is installed in which hot air, preferably 40°C to 80°C, is blown, and the term refers to the time spent in the drying zone. In the development process of the present invention, the development time is 5 seconds to 1 minute, preferably 10 seconds to 30 seconds, and the development temperature is 2
5°C to 50°C is preferable, and 25°C to 40°C is more preferable. Fixing temperature and time are approximately 20℃ to approximately 50℃ for 5 seconds to 1
minutes is preferred, and 10 seconds to 30 seconds at 25°C to 40°C is more preferred. Water washing or stabilization bath temperature and time are 0 to 50℃
The temperature is preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds at 15°C to 40°C. According to the method of the present invention, development,
The fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is carried out at a temperature of about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, particularly preferably about 5 seconds to 1 minute at 40°C to 80°C. It is 30 seconds.

The preferred photosensitive material to which the developer of the present invention is applied is not particularly limited, and general black and white photosensitive materials are mainly applicable, as well as, for example, the first color reversal photosensitive material.
It can also be used as a developer. In particular, photosensitive materials for laser printers and scanner photosensitive materials for printing that record medical images, direct X-ray photosensitive materials for medical use, indirect X-ray photosensitive materials, CRT photosensitive materials, photosensitive materials for X-ray cinema photography, and black and white negative films for photography. , black and white photographic paper, microfilm, etc.

A silver halide photographic material to which the processing method of the present invention can be applied comprises a support and at least one silver halide emulsion coated thereon. Furthermore, the silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary. A silver halide emulsion is one in which silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide are dispersed in a hydrophilic colloid. Silver halide emulsions are typically prepared by methods well known in the art (
For example, a water-soluble silver salt (for example, silver nitrate) and a water-soluble halide salt are mixed in the presence of water and a hydrophilic colloid by a single jet method, a double jet method, a controlled jet method, etc., and then physically ripened and gold sensitized. and/or produced through chemical ripening such as sulfur sensitization. The emulsion thus obtained has cubic, octahedral, spherical, and Res
arch Disclosure 22534 (Ja
High aspect ratio tabular silver halide grains described in Nuary (1983) can be used. It can also be used in combination with internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2068.

Silver halide emulsions are prepared with spectral sensitizers (for example, cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (for example, 4-
hydroxy-6-methyl-1,3,3a,7-tetrazaindene), sensitizers (e.g., U.S. Pat. No. 3,619,
No. 198), antifoggants (e.g. benzotriazole, 5-nitrobenzimidazole, polyethylene oxide, hardeners, coating aids (e.g. saponin, sodium lauryl alphate, dodecylphenol polyethylene oxide) ether, hexadecyltrimethylammonium bromide), etc.The silver halide emulsion thus produced can be coated on a support such as cellulose acetate film or polyethylene terephthalate film by dipping method, air knife method, bead method, etc. It is applied and dried using extrusion doctor method, double-sided coating method, etc.

In particular, it is preferable to use tabular silver halide grains in the X-ray treatment. In the case of the above-mentioned tabular grains, the preferred grain form is an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Further, the thickness of the particles is preferably 0.3μ or less, particularly preferably 0.2μ or less. Here, the aspect ratio of a tabular grain 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 individual tabular grain to the average value of the grain thickness of each tabular grain. It is preferred that the tabular grains are present in an amount of preferably 80% by weight or more, more preferably 90% by weight or more of the total grains. Tabular silver halide emulsions are prepared by adding spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-6-methyl-1,3 ,3
a,7-tetrazaindene), sensitizers (e.g., the compounds described in U.S. Pat. No. 3,619,198), antifoggants (e.g., benzotriazole, 5-nitrobenzimidazole, polyethylene oxide, Hardeners, coating aids (e.g., saponin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide), etc. can be added to the tabular silver halide emulsion produced in this way. is coated and dried on a support such as a cellulose acetate film or a polyethylene terephthalate film by a dipping method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method, etc. Next, the method of the present invention will be described in Examples. However, the present invention is not limited thereto.

[0037]

[Example] Next, the present invention will be explained in detail. Example-1 (1) Preparation of tabular grains Preparation of emulsion In 1 liter of water, 5 g of potassium bromide, 0.05 g of potassium iodide,
30 g of gelatin and 2.5 cc of a 5% aqueous solution of thioether HO(CH2)2S(CH2)2S(CH2)2OH were added and kept at 73°C, and with stirring, an aqueous solution of 8.33 g of silver nitrate and 5 ml of potassium bromide were added.
．． 94 g of potassium iodide and an aqueous solution containing 0.726 g of potassium iodide were added in 45 seconds using a double jet method. Subsequently, 2.5 g of potassium bromide was added, and then an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition. After this, 20cc of 25% ammonia solution, 50% NH
4 After adding 10 cc of NO3 and physically ripening for 20 minutes, 240 cc of 1N sulfuric acid was added to neutralize. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added in 40 minutes by a controlled double jet method while maintaining the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate after the addition was completed was nine times the flow rate at the start of the addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, followed by 25 cc of 1% potassium iodide aqueous solution.
c was added over 30 seconds. After that, the temperature was lowered to 35°C and soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C, 30g of gelatin and 2g of phenol were added, and the caustic soda was adjusted to pH 6.40 and pAg 8.1 with potassium bromide.
Adjusted to 0.

After raising the temperature to 56° C., 600 mg of sensitizing dye and 150 mg of stabilizer were added.

[0039]

[C5]

Ten minutes after the addition, 2.4 mg of sodium thiosulfate pentahydrate, 140 mg of potassium thiocyanate, and 2.1 mg of chloroauric acid were added to each emulsion, and after 80 minutes, the emulsions were rapidly cooled and solidified to form an emulsion. . In the obtained emulsion, 98% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 1.4 μm, standard deviation 22%, and thickness. The average was 0.187 μm and the aspect ratio was 7.5.

Preparation of Emulsion Coating Solution The following chemicals were added to the emulsion per mole of silver halide to prepare a coating solution.・Gelatin Silver/binder ratio (gelatin + polymer) is 0.7.
Adjust the amount added to ensure that ・Aqueous polyester 20% (wt% to gelatin)
・Polymer latex (poly(ethyl acrylate/methacrylic acid) = 97/3)

25.0g・Hardening agent 1,2-bis(sulfonylacetamido)ethane 8 mmol/Surface protection

layer emulsion layer ge
l.

Per 100g/Phenoxyethanol

2g

0042
]

[C6]

・2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine

80mg・Sodium polyacrylate (average molecular weight 41,000)
4.0 g of potassium polystyrene sulfonate (average molecular weight: 600,000) 1.0 g The above coating solution was coated on a 175 μm thick transparent PET support simultaneously with the surface protective layer coating solution.

[0044] The total amount of coated silver on both sides was 3.2 g/m2. The surface protective layer was prepared so that each component had the following coating amount. Contents of surface protective layer

Application amount/gelatin

1.15g/m2・Polyacrylamide (average molecular weight 45,000)
0.25 Sodium polyacrylate (average molecular weight 400,000)
0.02・pt-octylphenoxydiglyceryl butyl fluoronate sodium salt
0.02・Poly(methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm)
0.
020・Poly(degree of polymerization 10) oxyethylene cetyl ether 0.035・Poly(
Polymerization degree 10) Oxyethylene-poly(polymerization degree 3)
Oxyglyceryl-p-octylphenoxy ether 0.01・C8 F17SO
3K
0.0
03

[0045]

[C7]

・Proxel

0.001・Polymethyl methacrylate (
Average particle size 3.5μm) 0
．． 025

(2) Preparation of developer The formulations of developer concentrate part A, part B, part C and starter are shown below. Part A

Potassium hydroxide for 10 liters

291g potassium sulfite

442g sodium bicarbonate

75g boric acid


10g hydroquinone

300g diethylene glycol
1
20g 5-methylbenzotriazole

0.2g potassium bromide

Add 15g water
2.
5 liter part B

Triethylene glycol for 10 liters
200g
glacial acetic acid

40g 5-nitroindazole
2.5g 1-
Phenyl-3-pyrazolidone
15g
add water

250ml part C

Glutaraldehyde (50wt%) for 10 liters
1
00g sodium metabisulfite

126g add water

250ml starter glacial acetic acid

150g potassium bromide

30
Add 0g water

To prepare 1.5 liters of liquid, add approximately 6 liters of water.
Part A 2.5l, Part B 400ml, Part C
250 ml of the solution was sequentially added and dissolved while stirring, and finally the volume was made up to 10 liters with water, and the pH was adjusted to 10.40. This used solution is used as a developer replenisher. The starter was added at a ratio of 20 ml to 1 liter of this replenisher. This liquid is the developer and is used at the start of running. A developer as shown in Table 1 was prepared using the above developer replenisher. The pH was then adjusted to 10.40.

[0048]

[Table 1]

Next, using various developing solutions, the following development treatments were carried out using a roller conveyance type automatic processing machine FPM-9000 (manufactured by Fuji Photo Film Co., Ltd.). Treatment process Temperature Time
Replenishment amount development 35℃
14 seconds 30ml/10 x 12 inches (
4-cut size) Fixation 32℃ 11 seconds 40ml/10 x 12 inches (4-cut size) Washing with water 20℃ 10 seconds (*)
Dry 3 liters/1 minute at 55℃
10 seconds, total 45 seconds (*total time of washing and squeezing) Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

To check the photographic properties of this light-sensitive material, stepwise exposure was applied using an optical wedge using a sensitometer. In addition, the automatic developing machine is operated 6 days a week, and on the working days, 4 half-exposed 4-cut sizes (10 inches x 1
2 inch) were processed. The running experiment as described above was continued for a total of 3 weeks. The total number of sheets processed was 900 sheets. Table 2 shows the photographic properties and silver stain results from the running experiment. The sensitivity was determined as a relative value of the reciprocal of the exposure amount required to obtain a degree of blackening of fog value +1.0. Fog values were measured as the net density increase corrected for the base density. The average gradation G was expressed as the slope of a straight line connecting the density point of fog+0.25 and the density point of fog+2.0. D
m represents the maximum concentration.

[0051]

[Table 2]

From the results in Table 2, the following can be said. When processed with developer NO-1 (comparative example), silver stains occur,
The performance is not high enough to withstand rapid processing using an automatic processing machine. On the other hand, developing solutions NO-2 to NO-4 using the compounds of the present invention had very little silver staining and were able to achieve the object of the present invention. Moreover, unexpectedly, the sensitivity increased by 10 to 15%, and the sensitivity remained stable even with running.

Example 2 (1) Preparation of silver halide emulsion After putting an appropriate amount of ammonia into a container heated to 55°C containing gelatin, potassium bromide and water, the pAg value in the reaction container was determined. A silver nitrate aqueous solution and a potassium bromide aqueous solution to which hexachloroiridate (III) salt was added so that the molar ratio of iridium to silver was 10-7 mol were added by a double jet method while maintaining the average particle size at 7.60. Two types of monodisperse silver bromide emulsion grains with sizes of 0.70μ and 0.40μ were prepared with varying amounts of ammonia. These emulsion grains had 98% of the total number of grains within ±40% of the average grain size. Also, 1.times.10@-3 mole of potassium iodide was added per mole of silver at a later stage of grain formation. After desalting these emulsions, the pH was adjusted to 6.2, p
After adjusting the Ag to 8.6, gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain desired photographic properties. The (100) plane/(111) plane ratio of these emulsions was measured by the Kubelkamunk method and was found to be 93/7.

(2) Preparation of emulsion coating solution Weighed 0.5 kg of each of the above two types of emulsions into a container containing 4
After heating to 0°C to dissolve the emulsion, 30 cc of a methanol solution of an infrared sensitizing dye (9 x 10-4 mol/l) and an aqueous solution of the following supersensitizer (4.4 x 10-3 mol/l)
130cc, methanol solution of photosensitive material storage improver (2.
8 x 10-2 mol/l) 35cc, 4-hydroxy-
6-methyl-1,3,3a,7-tetrazaindene aqueous solution, coating aid dodecylbenzenesulfonate aqueous solution,
An aqueous solution of a thickener polypotassium-p-vinylbenzenesulfonate compound was added to prepare an emulsion coating solution.

[0055]

[Chemical formula 8]

(Supersensitizer) 4,4'-bis[2,6-
Di(2-naphthoxy)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt

0
(3) Preparation of coating solution for surface protective layer of sensitive material layer 40
To a 10 wt % aqueous gelatin solution heated to ℃, a thickener polystyrene sulfonate aqueous solution and a matting agent polymethyl methacrylate fine particles (average particle size 3.0 μm) were added.
), a hardening agent N,N'-ethylenebis-(vinylsulfonylacetamide), a coating aid aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate, an aqueous polyethylene surfactant solution as an antistatic agent, and a fluorine-containing compound having the following structure. A coating solution was prepared by adding an aqueous solution of . C8F17SO2N(C3H7)CH2COOK and C8F17SO2N(C3H7)(CH2CH2O)
15H

(4) Preparation of back coating solution Add 1 kg of a 10 wt % aqueous gelatin solution heated to 40°C, a thickener sodium polystyrene sulfonate aqueous solution, and the following back dye aqueous solution (5 x 10 -2 mol/l). )50cc,
A coating solution was prepared by adding an aqueous solution of N,N'-ethylenebis-(vinylsulfonylacetomide) as a hardener and an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid.

[0059]

[Chemical formula 9]

(5) Preparation of coating solution for surface protective layer of back layer A 10 wt % gelatin aqueous solution heated to 40°C, a thickener polystyrene sulfonate aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3) .0
μm), an aqueous solution of sodium t-octylphenoxyethoxyethanesulfonate as a coating aid, an aqueous polyethylene surfactant solution as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the following structure were added to prepare a coating solution. C8F17SO2N(C3H7)CH2COOK and C8F17SO2N(C3H7)(CH2CH2O)1
5H

(6) Preparation of coating sample The above-mentioned back layer coating solution was coated on one side of a polyethylene terephthalate support together with the back layer surface protective layer coating solution so that the gelatin coating amount was 4 g/m 2 . Subsequently, on the opposite side of the support, coat the emulsion coating solution containing the near-infrared sensitizing dye mentioned in (2) and the surface protective layer coating solution for this so that the amount of silver is 2.6 g/m2. The amount of hardening agent in the surface protective layer coating film was adjusted so that the swelling percentage of the coating film was 120%.

(7) Swelling rate measurement method a) Incubate the coated sample at 38°C and 50% relative humidity, b) Measure the layer thickness, c) Immerse in distilled water at 21°C for 3 minutes, and d) measuring the percentage change in layer thickness compared to the layer thickness measured in step b).

Next, the formulations of the developing concentrate and the fixing concentrate will be shown. Developer concentrate (2.5 times concentrated) Potassium hydroxide

43g sodium sulfite

100g potassium sulfite

126g diethylenetriaminepentaacetic acid

5g boric acid


20g hydroquinone

85g 4-hydroxymethyl-4-methyl-1-phenyl-3-
Pyrazolidone

4g diethylene glycol

75g 5-methylbenzotriazole
0.2g potassium bromide

Make up to 1 liter with 10g water (pH 10.
65) The above concentrated solution was diluted as follows to obtain a working solution. 400 ml of developer concentrate + 600 ml of water = working solution (pH 1
(adjust to 0.35)

Fixing concentrate (4 times concentrated) Ammonium thiosulfate

500g Ethylenediaminetetraacetic acid disodium dihydrate
0.1g Sodium thiosulfate pentahydrate

50g sodium sulfite

60g
Sodium hydroxide

25g acetic acid

100
g The concentrate was made up to 1 liter with water (adjusted to pH 5.1) and used as a working solution by diluting the above concentrated solution as follows. 250 ml of fixing concentrate + 750 ml of water = working solution (pH 5
．． (adjust to 0)

[0065] Next, using the above-mentioned developing solution (working solution),
Samples similar to developer samples No. 1 to 4 of Example 1 were prepared, and a roller conveyance type automatic processor (path length = 1550
mm), the following development treatment was performed. Treatment process Temperature Time
Replenishment amount development 3
5℃ 6.5 seconds 25ml/10
x12 inch fixing 35℃
7 seconds 25ml/10 x 12 inches Washing with water 20℃ 6 seconds 3L/1 minute squeeze drying 55℃ 10.5 seconds Total
As a result of the 30 second running test, results showing almost the same tendency as in Example 2 were obtained.

[0066]

【Effect of the invention】

By using the compound of the present invention in a developer, silver staining can be significantly improved without adversely affecting the photographic properties of silver halide photosensitive materials. Therefore, maintenance of the automatic processing machine becomes very easy and contamination of the photosensitive material can be eliminated. Furthermore, even during rapid processing, stable and high-quality images can always be provided.

Claims (1)

[Claims] 1. In a method for developing a silver halide photosensitive material in which a silver halide photosensitive material is exposed and then developed, the developer used in the development process contains the following general formula (
A method for developing a silver halide photosensitive material, characterized in that at least one compound represented by I) is added. General formula (I) [Image Omitted] In the formula, Z represents an atomic group necessary to form a ring, and X represents a substituent. n represents 0 or an integer of 1 to 5.