JP2684236B2 - Development processing method of silver halide photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to development processing, particularly rapid processing, of a silver halide photographic light-sensitive material.

(Prior Art) In recent years, there has been an increasing demand for rapid processing in the development processing of silver halide photosensitive materials. For rapid processing, it is generally known that the development temperature is raised to shorten the development time. However, in the case of high-temperature processing (for example, 40 ° C or higher), the air oxidation reaction of the developer is accelerated. In addition, the composition of the developer changes greatly due to evaporation and concentration, and it becomes difficult to maintain the photographic characteristics of the new solution, and this method is not very suitable.

In order to perform rapid processing, other methods of increasing the developing activity include increasing the amount of the developing agent and increasing the pH of the developing solution. The method of increasing the amount of the developing agent requires a large amount of sulfite which stabilizes the developing solution containing the developing agent, and also requires a large amount of the solvent which dissolves the developing agent. The capacity will also be larger. Furthermore,
This method is naturally limited because of the high cost. On the other hand, the method of increasing the pH of the developer sacrifices the stabilization of the developer.

For the above reasons, it is desired to accelerate the developing speed and increase the effective sensitivity of the developed light-sensitive material without sacrificing the solution stability without increasing the developing temperature, the cost and the concentrated solution concentrate. For this purpose, various development accelerators have been conventionally known.

A thioether compound is known as an example. For details, see LFA Mason Photographic Processing Ch.
page 44 of emistry (London, Focal Press, 1975), JP-A-58-221843, JP-A-51-90822, JP-A-51-897
32, JP-A-49-90536 and JP-A-53-30331. The thioether compound has an effective development-accelerating action, but since it utilizes so-called dissolution physical development by dissolving silver halide, it results in a large amount of silver stains in the developing solution, resulting in automatic development. Practically preferable because it promotes dirt on the developing rack and rollers of the developing machine (hereinafter referred to as the automatic processor), damages or contaminates the photosensitive material, or requires frequent maintenance inspections of the automatic processor. Absent.

(Problems to be Solved by the Invention) An object of the present invention is to provide a development processing method which enables rapid processing and is excellent in stability of a developing solution.

(Means for Solving Problems) Nitrogen-containing heterocyclic mercapto compounds are known in the art as antifoggants or stabilizers. That is,
It is used for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage, or during photographic processing, or for maintaining stable photographic performance. As a result of intensive studies aimed at rapid processing, the present inventors found that the compound represented by the general formula (I) among the nitrogen-containing heterocyclic mercapto compounds was excellent in having a high maximum image density and a low minimum image density. It was discovered that it can contribute to providing a gradation image stably in a short time. This effect was specific to the compound of the general formula (I) and was an unexpected phenomenon.

That is, the present invention relates to a development processing method characterized in that a silver halide photosensitive material is processed with a developer containing at least one compound represented by the following general formula (I); (In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions, L represents an alkylene group, n represents 0 or 1, and when n is 1, X is alkyl-substituted. Represents an optionally substituted amino group or an alkyl-substituted ammonio group, and when n is 0, X represents a heterocyclic group).

 Hereinafter, the general formula (I) will be described in detail.

General formula (I) In the formula, M is a hydrogen atom or an alkali metal atom (K, Na, Li
Etc.), an ammonium group or a group (such as an acetyl group) which is cleaved under alkaline conditions. L represents an alkylene (preferably having a carbon number of 1 to 10) group. This alkylene group may have a substituent (for example, a carboxy group, a sulfo group, an alkylthio group (preferably having a carbon number of 1 to 10), a group represented by X). n represents 0 or 1. When n is 1, X represents an amino group (including alkyl-substituted one) or an ammonio group (including alkyl-substituted one). The alkyl substituent is preferably an alkyl group having 1 to 10 carbon atoms, and this alkyl group may be substituted with a hydrophilic substituent such as a hydroxyl group, a carboxy group or a sulfo group. When n is 1, X represents a heterocyclic group, and the heterocyclic group is preferably a saturated or unsaturated heterocyclic ring containing a 5- or 6-membered nitrogen atom, for example, And the like. Examples of the substituent for the heterocyclic group include a hydroxy group, a carboxy group, a sulfo group, an alkyl group (preferably having 1 to 10 carbon atoms), and a halogen atom. A preferable example of X is an amino group which may be substituted with alkyl.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to this.

An example of the synthesis of the compound of general formula (I) is described below.

Synthesis of Compound (3) Hydrazine hydrate (6.3 ml) was added to a solution of N, N-dimethylglycine methyl ester (15 g) in ethanol (150 ml), and the mixture was stirred at room temperature for 12 hours. Carbon disulfide (15 ml) was added to the reaction solution, and a solution of potassium hydroxide (8.5 g) in ethanol (150 ml) was further added, followed by heating and stirring for 6 hours. After cooling, concentrated hydrochloric acid (11 ml) was added, and the generated crystals were filtered and recrystallized from water (100 ml) to obtain compound (3).

Yield 12.3g Yield 60% Other compounds can be similarly synthesized.

The preferred concentration of the compound of the general formula (I) in the developer (use solution) is 0.01 mmol / -50 mmol /,
It is more preferably 0.05 mmol / ~ 10 mmol /, particularly preferably 0.1 mmol / ~ 5 mmol /.

The developing agent used in the developer of the present invention is mainly composed of hydroquinones, but from the viewpoint of easily obtaining good performance, a combination of hydroquinones and 1-phenyl-3-pyrazolidones, or hydroquinones and p-aminophenol. Good combination with other types.

The hydroquinone-based developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-
There are dimethylhydroquinone, hydroquinone monosulfonate, 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, N- (4-hydroxyphenyl). Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc. are available, but among them N-methyl-p
-Aminophenol is preferred.

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

Hydroquinone-based developing agent is usually 0.01 mol / ~ 1.5
Mol /, preferably in an amount of 0.05 mol / -1.2 mol /.

In addition to this, the p-aminophenol type developing agent or the 3-pyrazolidone type developing agent is usually 0.0005 mol / ~.
0.2 mol /, preferably 0.001 mol / -0.1 mol /
Used in amounts.

Examples of the sulfite used in the developing solution of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and meta (potassium bisulfite). Also, the upper limit is 2. concentrated developer.
It is preferably up to 5 mol /.

The pH of the developer used in the development processing of the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters.

Buffers such as JP-A-62-186259 (borate), JP-A-60-93433 (e.g., saccharose, acetoxime, 5-sulfosalicylic acid), phosphate, carbonate and the like may be used.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more for iron ions.

Here, the chelate stability constant is LGSillen ・ AEMa
rtell, H “Stabillity Constants of Metal−ion Comp
lexes ", The Chemical Society, London (1964). S.Cha
by Berek AEMartell, “Organic Sequeutering Agen
ts ", Wiley (1959). Means a constant generally known by et al.

In the present invention, examples of the chelating agent having a chelating stability constant for iron ions of 8 or more include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent, and a polyhydroxy compound. In addition, the said iron ion means ferric ion (Fe3 ⁺ ).

Specific compound examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more in the present invention include:
The following compounds are exemplified, but not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetramine hexaacetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, Hydroxyethyliminodiacetic acid, 1,3-diamino-2-propanoltetraacetic acid, transcyclofuxanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N, N, N ', N' tetrakismethylenephosphone Acid, nitrilo-N, N, N-trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid,
2-phosphonobutane-1,2,4-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 a bisulfite adduct thereof is used in the developer, and specific examples thereof include glutaraldehyde and bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, benz such as 5-methylbenztriazole Anti-foggants such as triazole compounds may be included in Research Disclos
ure, Vol. 176, No. 17643, Section XXI (December Issue, 1978) and, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hard water softener, It may contain an amino compound described in JP-A-56-106244.

In the developing treatment of the present invention, a silver stain preventing agent other than the silver stain preventing agent of the present invention, such as the compounds described in JP-A-56-24347, can be used in the developing solution.

The developer of the present invention, European Patent Publication 136582,
UK Patent No. 958678, U.S. Patent No. 3232661, JP-A-56
An amino compound such as alkanolamine described in JP-A-106244 can be used for the purpose of promoting development, increasing contrast and other purposes.

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

The fixing solution is an aqueous solution containing a thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 7.0.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, and is generally about 0.1 to about 6 mol /.

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

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

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent having a water softening property, The compounds described in JP-A-62-78551 can be included.

In the present invention, the term "development step time" or "development time" refers to the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the time when it is immersed in the next fixing solution, the "fixing time" What is the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution) "Washing time"
The time during which it is immersed in the washing tank liquid.

The "drying time" is usually 35 ° C to 100 ° C for automatic machines.
A drying zone to which hot air of 40 ° C., preferably 40 ° C. to 80 ° C. is blown is provided, and it refers to a time in the drying zone.

In the developing treatment of the present invention, the developing time is 5 seconds to 1 minute, preferably 5 seconds to 30 seconds, and the developing temperature is preferably 25 ° C to 50 ° C, more preferably 25 ° C to 40 ° C.

The fixing temperature and time are preferably about 20 ° C to about 50 ° C for 5 seconds to 1 minute, and more preferably 25 ° C to 40 ° C for 5 seconds to 30 seconds.

Washing or stabilizing bath temperature and time is 0 to 50 ° C for 5 seconds to 1
Minutes are preferred, and more preferably 5 to 30 seconds at 15 ° C to 40 ° C.

According to the method of the present invention, the developed, fixed and washed (or stabilized) photographic material is dried through a squeeze roller which squeezes the washing water. The drying is carried out at about 40 ° C to about 100 ° C, and the drying time is appropriately changed depending on the ambient conditions, but it is usually about 5 seconds to 1 minute, and particularly preferably 40
It is about 5 to 30 seconds at 80 to 80 ° C.

According to the development processing method of the present invention, the Dry to Dry time (the time from the insertion of the tip of the photosensitive material into the developing machine until the tip of the photosensitive material comes out of the drying section of the developing machine) is 30 to 60. Can be in seconds.

A preferable light-sensitive material for applying the developer of the present invention is
There is no particular limitation, and a general black-and-white light-sensitive material is mainly applied, and it can also be used as a first developing solution for a color reversal light-sensitive material, for example. In particular, light-sensitive materials for laser printers and printing scanners, which record medical images, and direct X-ray light-sensitive materials for medical use, indirect X-ray light-sensitive materials, CRT light-sensitive materials, light-sensitive materials for X-ray cinema photography, black and white negative film for photography. , Black and white photographic paper, microfilm, etc.

The 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. Further, the silver halide emulsion layer can be coated not only on one side of the support but also on both sides. Of course, it may have a back layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer), etc., if necessary.

The silver halide emulsion is obtained by dispersing silver halide such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide in a hydrophilic colloid. The silver halide emulsion is
Usually, a water-soluble silver salt (for example, silver nitrate) and a water-soluble halogen salt are mixed with water and a hydrophilic colloid by a method well known in the art (for example, single jet method, double jet method, control jet method, etc.). Mix with
It is manufactured through physical ripening and chemical ripening such as gold sensitization and / or sulfur sensitization. The emulsion thus obtained contains
Cubes, octahedrons, spheres, etc. Research Disclosure 22534
The tabular silver halide grains having a high aspect ratio described in (January 1983) can be used.

The silver halide emulsion may be used in the course of its production process or immediately before coating, at the time of spectral sensitizer (for example, cyanine dye, merocyanine dye or a mixture thereof), stabilizer (for example, 4-hydroxy-6-methyl-1,3,3a). , 7-tetrazaindene), sensitizers (e.g., compounds described in U.S. Pat. No. 3,619,198), antifoggants (e.g., benzotriazole,
5-Nitrobenzimidazole, polyethylene oxide, a hardener, a coating aid (for example, saponin, sodium lauryl alphate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide) and the like can be added.

The silver halide emulsion thus produced is applied to a support such as a cellulose acetate film or a polyethylene terephthalate film by a dip method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method or the like and dried.

The development processing method of the present invention is particularly suitable for use in a surface latent image type silver halide photographic light-sensitive material. Here, the surface latent image type means the sensitivity obtained by the surface development (A) when the photosensitive material is developed by the surface development (A) and the internal development (B) shown below after exposure for 1 to 100 seconds. Internal development (B)
It is defined to be greater than the sensitivity obtained in. Here, the sensitivity is given as follows.

Sensitivity = 100 / Eh Here, Eh represents the exposure amount required to obtain a density (Dmax + Dmin) × 1/2 which is exactly in the middle of the maximum density (Dmax) and the minimum density (Dmin).

Surface image (A) Develop in a developer having the following formulation at 20 ° C. for 10 minutes.

N-methyl-p-amiphenol (hemisulphate) 2.5g Ascorbic acid 10.0g Sodium metaborate tetrahydrate 35.0g Potassium bromide 1.0g Add water 1 Internal development (B) Red blood salt 3g / and pheno It is treated in a bleaching solution containing 0.0125 g of safranine at about 20 ° C. for 10 minutes, washed with water for 10 minutes, and then developed at 20 ° C. for 10 minutes in a developer having the following formulation.

N-methyl-p-amiphenol (hemisulphate) 3.5g Ascorbic acid 10.0g Sodium metaborate tetrahydrate 35.0g Potassium bromide 1.0g Sodium thiosulfate 3.0g Add water 1 Especially in X-ray treatment It is preferable to use tabular silver halide grains.

In the case of the tabular grains described above, the preferable grain morphology is an aspect ratio of 4 or more and less than 20, more preferably 5 or more.
It is less than 10. Further, the thickness of the particles is preferably 0.3 μm or less, particularly preferably 0.2 μm or less.

Here, the aspect ratio of tabular grains is given by the ratio of the average value of the diameters of circles having the same area as the projected area of each tabular grain and the average value of the grain thickness of each tabular grain.

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

The tabular silver halide emulsion has a spectral sensitizer (for example, a cyanine dye, a merocyanine dye or a mixture thereof), a stabilizer (for example, 4-hydroxy-6-methyl-1,3) during the production process or immediately before coating. , 3a, -7-Tetrazaindene), sensitizers (for example, compounds described in US Pat. No. 3,619,198), antifoggants (for example, bendtriazole, 5-nitrobenzimidazole, polyethylene oxide, hard film). Agents, coating aids (eg saponin,
Sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide) and the like can be added.

The tabular silver halide emulsion thus produced is applied 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, or the like. .

Next, the method of the present invention will be described with reference to examples, but the present invention is not limited thereto.

(Example) Next, the present invention will be specifically described.

Example-1 Preparation of emulsion 5 g of potassium bromide, 0.05 g of potassium iodide and 30 g of gelatin in water 1
g, 5 of the thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
Aqueous solution containing 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide are added to the solution kept at 73 ° C. in 45 seconds by a double jet method while stirring and adding 2.5 cc of a 2.5% aqueous solution. did. Subsequently, after adding 2.5 g of potassium bromide, 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 start of the addition. after this
By adding 25% ammonia solution _{20cc, 50% NH 4 NO 3} 10cc
After physically aging 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 over 40 minutes by the control double jet method while maintaining the potential at pAg8.2. The subsequent flow rate was accelerated so that the flow rate after the end of addition was 9 times the flow rate at the start of addition. After the addition is completed, 2N potassium thiocyanate solution 15cc
Then, 25 cc of 1% potassium iodide aqueous solution was added over 30 seconds. After that, the temperature was lowered to 35 ° C, and soluble salts were removed by a sedimentation method.
And 2 g of phenol are added, and caustic soda is added with potassium bromide.
The pH was adjusted to 6.40 and pAg to 8.10.

After raising the temperature to 56 ° C, the sensitizing dye of the following structure
0 mg and 150 mg of stabilizer were added. Ten minutes later, 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 emulsion was solidified by rapid cooling. The obtained emulsion consists of grains having an aspect ratio of 3 or more in 98% of the total projected area of all grains. The average projected area diameter of all grains having an aspect ratio of 2 or more is 1.4 μm, standard deviation is 22%, and thickness is The average was 0.187 μm and the aspect ratio was 7.5.

Preparation of Emulsion Coating Solution A coating solution was prepared by adding the following chemicals per mole of silver halide to the emulsion.

・ Gelatin silver / binder ratio (gelatin + polymer)
The amount added was adjusted so that the ratio was 0.7. ・ Water-soluble polyester 20% (wt% vs. gelatin) ・ Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 25.0g ・ Hardener 1,2-bis ( Sulfonylacetamido) ethane 8 mmol / gel.100 g of emulsion layer of surface protective layer ・ Phenoxyethanol 2 g ・ 2,6-Bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80mg ・ Sodium polyacrylate (average molecular weight 41,000) 4.0g ・ Potassium polystyrene sulfonate (average molecular weight 600,000)
1.0g Thickness of the above coating solution is 1275 μm at the same time as the surface protection layer coating solution
On a transparent PET support.

The coated silver amount was 3.2 g / m ^{2 in} total on both sides.

The surface protective layer was prepared such that each component had the following coating amount.

Contents of surface protective layer Coating amount ・ Gelatin 1.15 g / m ²・ Polyacrylamide (average molecular weight 45,000) 0.25 ・ Sodium polyacrylic acid (average molecular weight 400,000) 0.02 ・ Pt-octylphenoxydiglyceryl butyl fulfuronide sodium Salt 0.02 ・ Poly (degree of polymerization: 10) Oxyethylene cetyl ether 0.03
5 ・ Poly (degree of polymerization 10) Oxyethylene-poly (degree of polymerization 3)
Oxyglyceryl-p-octylphenoxy ether 0.
01 ・ C ₈ F ₁₇ SO ₃ K 0.003 ・ Proxel 0.001 ・ Polymethylmethacrylate (average particle size 3.5μm) 0.025
-Poly (methyl methacrylate / methacrylate) C molar ratio 7: 3, average particle size 2.5 μm) 0.020 (2) Preparation of developing solution Formulation of developing solution Part A, Part B, Part C and starter is shown.

Regarding the method of preparing the working solution, water was added and dissolved in about 6 parts A2.5, part B 400 ml, and part C 250 ml with stirring, and finally water was adjusted to 10 and the pH was adjusted to 10.40. This used solution is used as a development replenisher. 20 ml of the starter was added to the replenisher 1. This solution is the developing solution.

The following developer was prepared using the above developer. Then the pH was adjusted to 10.25.

In addition, Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used for fixing.

Next, a roller-conveying automatic developing machine (FPM-9000 manufactured by Fuji Photo Film Co., Ltd.) using the above-described photosensitive material and processing liquid.
Then, the following development processing was performed.

Next, the result of photographic property is shown. The fog value in the photographic properties was measured as a net increase in density with the base density corrected. The gradation is fog +0.25 density and fog +2.0
It was expressed as the slope of a straight line connecting the density points of. The sensitivity was determined as the relative value of the reciprocal of the exposure amount required to obtain the blackened density of the fog value + 1.0. D _m represents the maximum concentration.

From the photographic results, the following can be said. In Test No. 2 in which the treatment for 45 seconds was carried out with the developer not using the compound of the present invention, it was shown that the sensitivity and D _m were greatly reduced as compared with the treatment for 90 seconds. Further, in Test Nos. 3 to 4 in which a treatment for 45 seconds was carried out with a developer using a compound similar to the compound of the present invention but not included in the general formula of the present invention, Test N was used.
The result was almost the same as that of o.2 and showed no development promoting effect. On the other hand, in Test Nos. 5 to 8 in which processing was performed for 45 seconds with the developer using the compound of the present invention, a remarkable development accelerating effect was exhibited as compared with Test No. 2, and the result was equivalent to that of Test No. 1. became.

Further, even when the developing solution containing the compound of the present invention was used for 45 seconds, a silver stain was hardly generated and a constant photographic performance was obtained.

Example-2 (1) Preparation of Ag I microparticles 0.5 g of potassium iodide and 25 g of gelatin were added to water 2, and 40 cc of silver nitrate aqueous solution containing 40 g of silver nitrate was added to a solution kept at 35 ° C. with stirring. 80 cc of an aqueous solution containing potassium iodide was added over 5 minutes. At this time, the addition flow rates of the silver nitrate aqueous solution and the potassium iodide aqueous solution were 8 c each at the beginning of the addition.
The addition flow rate was linearly accelerated so that the addition of 80 cc was completed in 5 minutes.

After the particles were formed in this way, the soluble salts were removed by the precipitation method at 35 ° C.

Next, the temperature was raised to 40 ° C., 10.5 g of gelatin and 2.56 g of phenoxyethanol were added, and the pH was adjusted to 6.8 with a caustic soda. The resulting emulsion has a finished amount of 730 g and an average diameter of 0.015μ.
m of monodispersed Ag I particles.

Preparation of tabular grain emulsion 4.5g potassium bromide, 20.6g gelatin, and 5% aqueous solution of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH in water 1.
While stirring in a solution vessel containing 2.5 Cc and kept at 60 ° C, 33 cc of an aqueous solution containing 37 cc of silver nitrate (3.43 g of silver nitrate), 2.97 g of potassium bromide and 0.363 g of potassium iodide by the double jet method.
Added in 37 seconds. Next, 0.9 g of potassium bromide was added to the solution and the temperature was raised to 70 ° C, and 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of a 25% aqueous ammonia solution was added, the mixture was physically aged at the same temperature for 20 minutes, and then 14 cc of a 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method over 35 minutes while keeping the pAg at 8.5. Next, 0.05 mol% of the total silver amount was added to 10 cc of 2N potassium thiocyanate solution and the above Ag I fine particles. After physical aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total iodine content is 0.31 mol%,
Monodisperse tabular fine particles having an average projected area diameter of 1.10 μm, a thickness of 0.165 μm and a diameter variation coefficient of 18.5% were obtained.

Thereafter, soluble salts were removed by a sedimentation method. Again 40
Heat to 35 ° C and gelatin 35g and phenoxyethanol 2.35g
And sodium polystyrene sulfonate as thickener
Add 0.8 g, pH 5.90, pAg with soluble soda and silver nitrate solution
Adjusted to 8.25.

The emulsion was chemically sensitized while being kept at 56 ° C. with stirring.

First, 0.043 mg of thiourea dioxide was added and held for 22 minutes to effect reduction sensitization. Next, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 20mg and sensitizing dye
A500 mg was added. Furthermore, 1.1 g of calcium chloride aqueous solution was added. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and after 40 minutes, cooled to 35 ° C.

Thus, preparation of the tabular grain emulsion of the present invention was completed.

Preparation of coating sample The following chemicals were added to the above emulsion per mol of silver halide to prepare a coating solution.

・ 2,6-Bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ Gelatin ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 60
10,000g ・ Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 225% Preparation of Coating Solution for Surface Protective Layer The surface protective layer was prepared and prepared such that each component had the following coating amount.

Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball-milled by the method described in JP-A-63-197943.

 Water 434 ml and Triton X-200 Surfactant (TX-20
0 791ml of 6.7% aqueous solution of
Was. 20 g of the dye were added to this solution. Zirconium oxide
(ZrO) bead 400ml (2mm diameter) was added and contents were added for 4 days
While milling. Thereafter, 160 g of 12.5% gelatin was added.
After defoaming, the ZrO beads were removed by filtration. Get
Observation of the dried dye dispersion showed that the ground
The diameter has a wide distribution from 0.05 to 1.15 μm.
Thus, the average particle size was 0.37 μm.

Further, dye particles having a size of 0.9 μm or more were removed by centrifugation.

 Thus, a dye dispersion D-1 was obtained.

(2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and the first undercoat liquid having the following composition was applied so that the coating amount was 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained a dye having the following structure at 0.04% by weight.

First undercoat liquid prescription On the first undercoat layer on both sides of the above, a second
The undercoat liquid was applied to each side so that the application amount was as described below, and applied to both sides by a wire bar coater method at 150 ° C. and dried.

Second undercoat liquid prescription Preparation of photographic material On the transparent support, an emulsion layer and a surface protective layer were coated on both sides by a simultaneous extrusion method. The amount of silver applied per side was 1.7 g / m ² .

 Thus, a photosensitive material was obtained.

The swelling ratio of the hydrophilic colloid layer was measured when the photographic material was aged for 7 days at 25 ° C. and 60% RH. The dry film thickness (a) was determined by a scanning electron microscope of the section. Swelling membrane layer (b)
Was determined by immersing the photographic material in distilled water at 21 ° C. for 3 minutes, freeze-drying with liquid nitrogen, and then observing it with a scanning electron microscope.

Swelling rate It was 225% for this photosensitive material.

The formulations of the developing concentrate and the fixing concentrate used in this example are shown below.

Development concentrate (2.5 times concentrated) The concentrated solution was diluted as follows to prepare a working solution.

Development concentrate 400 ml + water 600 ml = working solution (adjust to pH 10.35) Fixing concentrate (4 times concentrated) The concentrated solution was diluted as follows to prepare a working solution.

Fixing concentrate 250 ml + water 750 ml = working solution (adjusted to pH 5.0) Next, to the above-mentioned developing solution (working solution) and the developing solution,
A sample prepared by adding Exemplified Compound 3 of the present invention (0.16 g /) or Exemplified Compound 8 of the present invention (0.35 g /) was prepared, and three types of developing solution samples were used. The following developing process was performed by a mold developing machine.

(Pass length = 1950mm) Treatment process Temperature Time Replenishment amount Image 35 ℃ 9 seconds 25ml / 10 × 12 inches Fixed 32 ℃ 7 seconds 25ml / 10 × 12 inches Water wash 20 ℃ 5 seconds 3/1 minutes Squeeze dry 55 ℃ 9 seconds Total 30 seconds Photographic results are shown below.

In Test Nos. 3 to 4 in which processing was carried out for 30 seconds with a developer using the compound of the present invention, a remarkable development accelerating effect was exhibited, and
The result is the same as No.-1.

<Example 3> The same experiment (30 seconds) as in Example-2 was carried out with Dry to Dry 30 seconds by increasing the linear velocity of SON-1001 manufactured by KONICA CO., LTD. Results were obtained.

Example-4 (1) Preparation of Silver Halide Emulsion An appropriate amount of ammonia was placed in a container containing gelatin, potassium bromide and water and heated to 55 ° C.
While maintaining the pAg value at 7.60, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing hexachloroiridium (III) at a molar ratio of iridium to silver of 10 ^-7 were added by the double jet method to obtain an average particle size. The size is 0.
Two 70 μm and 0.40 μm monodisperse silver bromide emulsion grains were prepared by changing the amount of ammonia. These emulsion grains had 98% of the total number of grains within ± 40% of the average grain size. In the latter stage of grain formation, 1 × 10 ⁻³ mol of potassium iodide was added per mol of silver. After desalting these emulsions, the pH was adjusted to 6.2 and the pAg was adjusted to 8.6, and gold / sulfur sensitization was performed with sodium thiosulfate and chloroauric acid to obtain desired photographic properties. The (100) face / (111) face ratio of these emulsions was 93/7 when measured by the Kubelka-Munk method.

(2) Preparation of emulsion coating solution 0.5 kg of each of the above two emulsions was weighed in a container at 40 ° C.
After heating the emulsion to dissolve the emulsion, 30 cc of the following infrared sensitizing dye in methanol (9 × 10 ⁻⁴ mol /) and the following supersensitizer in water (4.4 × 10 ⁻³ mol /) are added. 130 cc, methanol solution of the following sensitizing agent preservative improver (2.8 x 10 ^-2 mol /)
5cc, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene aqueous solution, coating aid dodecylbenzene sulfonate aqueous solution, thickener polypotassium-p-vinylbenzene sulfonate compound aqueous solution The emulsion coating solution was added.

(Supersensitizer) 4,4'-bis [2,6-di (2-naphthoxy) pyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt (3) Preparation of coating liquid for surface protective layer of light-sensitive material layer A 10 wt% gelatin aqueous solution heated at 40 ° C., a thickening agent sodium polystyrene sulfonate aqueous solution, a matting agent polymethylmethacrylate fine particles (average particle size 3.0 μm
m), a hardener N, N′-ethylenebis- (vinylsulfonylacetamide), a coating aid t-octylphenoxyethoxyethane sulfonate sodium aqueous solution, a polyethylene-based surfactant aqueous solution as an antistatic agent, and a fluorine-containing compound having the following structure. An aqueous solution of the compound was added to obtain a coating solution.

C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK and C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ —O ₁₅ H (4) Preparation of back coating solution 1 kg of warmed 10 wt% gelatin aqueous solution,
Thickening agent Sodium polystyrene sulfonate aqueous solution, the following back dye aqueous solution (5 × 10 ^-2 mol /) 50 cc, hardener N,
A N'-ethylenebis- (vinylsulfonylacetamide) aqueous solution and a coating aid sodium t-octylphenoxyethoxyethane sulfonate aqueous solution were added to prepare a coating solution.

(5) Preparation of coating liquid for surface protective layer of back layer In 10 wt% gelatin aqueous solution heated at 40 ° C, thickening agent sodium styrene sulfonate aqueous solution, matting agent polymethylmethacrylate fine particles (average particle size 3.0μ
m), a coating aid, a sodium t-octylphenoxyethoxyethane sulfonate aqueous solution, an aqueous solution of a polyethylene-based surfactant as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the following structure were added to prepare a coating solution.

C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK and C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ —O ₁₅ H (6) Preparation of coating sample Back layer described above The coating solution was coated together with the coating solution for the surface protective layer of the back layer on one side of the polyethylene terephthalate support so that the coating amount of gelatin was 4 g / m ^2, and then on the other side of the support (2). The emulsion coating solution containing the near-infrared sensitizing dye described above and the coating solution for the surface protective layer for it are coated so that the silver amount is 3.2 g / m ² and the swelling percentage of the coating film is 110%. Thus, the amount of the hardener in the coating film for the surface protective layer was adjusted for coating.

(7) Method of measuring swelling rate a) Incubating the coated sample at 38 ° C. and 50% relative humidity, b) measuring the layer thickness, c) soaking in distilled water at 21 ° C. for 3 minutes, and d) The percentage change in layer thickness compared to the layer thickness measured in step b) is measured.

<Processing> The same developer and fixer as those used in Example-2 were used.

Next, the developer (use solution) of Example 2 and a sample obtained by adding Exemplified Compound 3 (0.16 g /) of the present invention or a sample added by Exemplified Compound 13 (0.18 g /) of the present invention to the developer. Using the above-mentioned light-sensitive material, a roller-conveying type automatic developing machine was prepared, and the following development processing was performed.

Treatment for 60 seconds Treatment time Temperature Time Replenishment amount Image 35 ℃ 11.5 seconds 50ml / 25.7 × 36.4cm Settlement 35 ℃ 12.5 seconds 50ml / 25.7 × 36.4cm Water wash 20 ℃ 10 seconds 3/1 minute Squeeze dry 50 ℃ 26 seconds Total 60 seconds 30 seconds Treatment process Temperature time Replenishment amount Image 35 ℃ 6 seconds 50ml / 25.7 × 36.4cm Settlement 35 ℃ 6 seconds 50ml / 25.7 × 36.4cm Water wash 20 ℃ 5 seconds 3/1 minute Squeeze dry 50 ℃ 13 seconds Total 30 seconds Photographic results are shown below.

By using the compound of the present invention, photographic results equivalent to those of Test No.-1 were obtained even after 30 seconds of treatment.

(Effects of the Invention) According to the present invention, since the development promoting action in the development processing is achieved, good photographic properties are obtained, and the processing can be made extremely quick. In addition, the stability of the developing solution was excellent, silver stains did not occur, and highly concentrated performance was obtained.

Claims (3)

(57) [Claims] 1. A development processing method, which comprises processing a silver halide photosensitive material with a developer containing at least one compound represented by the following general formula (I). General formula (I) (In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions, L represents an alkylene group, n represents 0 or 1, and when n is 1, X is alkyl-substituted. Represents an optionally substituted amino group or an optionally substituted ammonio group, and when n is 0, X
Represents a heterocyclic group. 2. The development processing method according to claim 1, wherein the silver halide light-sensitive material comprises a surface latent image type silver halide emulsion. 3. The developer (1), wherein the developer contains hydroquinone as a main developing agent.
Alternatively, the development processing method according to (2).