JPH09127656A - Solid processing agent for black-and-white silver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve processing stability in running by incorporating a dihydroxybenzene developing agent and LiOH. SOLUTION: A dihydroxybenzene developing agent represented by the formula and LiOH are incorporated. In the formula, each of R1 and R2 is optionally substd. alkyl, optionally substd. amino or optionally substd. alkylthio, R1 and R2 may bond with each other to form a ring, (k) is 0 or 1, in the case of k=1, X is -CO- or -CS- and each of M1 and M2 is H or an alkali metallic atom. The amt. of the LiOH is 0.1-20wt.% of the amt. of dihydroxybenzene contained in the developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent and processing method for black and white silver halide photographic light-sensitive materials, and more particularly to an improved solid processing agent and processing method for silver halide photographic light-sensitive materials for printing plate making.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is
Processing is carried out by steps such as development-fixing-washing (or rinsing), and such processing is generally carried out using an automatic processor. In the processing by an automatic processor, a method of replenishing with a processing agent is used to keep the activity of the processing solution constant. Under the present circumstances, the replenishing treatment agent is supplied as a concentrated solution and is diluted and dissolved before use. Concentrated liquid supply has been widely used from the viewpoint of space saving, but there are many problems. As one of them, the trend for processing of silver halide photographic light-sensitive materials is toward low replenishment and speeding up, and the kit is further concentrated and concentrated to the solubility limit.
It has many practical problems such as crystal precipitation. Further, since it is in a liquid state, it is difficult to avoid the reaction of the components in the liquid, and it is very difficult to prevent the performance of the replenishment liquid kit from changing due to the restrictions of the compound to be used and the passage of time and heat.

From the standpoint of workability, the concentrate kit is heavy, and the workability of preparation is poor. If you use a solid developer kit, the weight can be reduced, but the hydrazine derivative,
When processing a light-sensitive material containing a contrast-increasing agent such as a pyridinium salt or tetrazolium, there is a problem that running stability deteriorates. Furthermore, it is desired to reduce the amount of replenisher by reducing the amount of waste liquid, but if the amount of replenisher is reduced, running stability deteriorates.

Further, the concentrate kit uses polyethylene or the like typified by a plastic container or a composite material thereof as a packaging material, and its disposal method is complicated and costly at present. is there. Especially in European countries, which are making progress on environmental issues, while shifting from concentrated liquid kits that require plastic containers to solid processing agents such as powder processing agents that can use packaging materials that can be easily discarded, It is the current situation. The seriousness of environmental problems is global, and this problem is a major problem that cannot be ignored.

However, a local reaction occurs due to the inclusion of a trace amount of water, the elimination of hydrated salts, etc., which causes the deterioration of the solubility and the formation of insoluble matter, which also causes the liquid performance to deteriorate with the passage of time and heat. The current situation is that there are problems such as fluctuations.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is that the processing stability during running is remarkably high even when a large amount of running processing is performed in a state where the environment is not deteriorated and the developer replenishment amount is reduced. An object of the present invention is to provide an improved solid processing agent for black and white silver halide photographic light-sensitive materials and a processing method.

[0007]

The above object of the present invention is achieved by the following constitution.

(1) A solid processing agent for a black-and-white silver halide photographic light-sensitive material, which contains a dihydroxybenzene type developing agent and LiOH.

(2) A solid processing agent for a black-and-white silver halide photographic light-sensitive material, which contains a developing agent represented by the following general formula (1) and LiOH.

[0010]

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In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
It represents a substituted or unsubstituted alkylthio group, and R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X represents a -CO- or -CS- group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

(3) LiOH is in a weight ratio of 0.1 to 20 w with respect to dihydroxybenzenes contained in the developer.
The solid developer for black-and-white silver halide photographic light-sensitive materials as described in 1 above, wherein the solid developer contains t%.

(4) A solid processing agent for a black-and-white silver halide photographic light-sensitive material, containing a compound represented by the above general formula (1) and the following general formula (2).

[0014]

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In the formula, one of Y and Z represents a nitrogen atom and the other represents a methine group. R ₀ represents a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group.

(5) The solid processing agent for a black-and-white silver halide photographic light-sensitive material as described in 4 above, wherein the developing agent is a dihydroxybenzene.

(6) The compound represented by the general formula (2) is contained in an amount of 0.1 to 10% by weight with respect to the dihydroxybenzenes contained in the developer. Or the solid developer for black-and-white silver halide photographic light-sensitive material as described in 5 above.

(7) A black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer and / or other constituent layers, 7. A processing method for a black-and-white silver halide photographic light-sensitive material, which comprises processing with a development replenisher prepared from the solid processing agent according to any one of items 1 to 6.

(8) A black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a tetrazolium salt compound in the emulsion layer and / or other constituent layers, 7. A method of processing a black-and-white silver halide photographic light-sensitive material, which comprises processing with a development replenisher prepared from the solid processing agent according to any one of 1 to 6.

(9) A black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a pyridinium salt compound in the emulsion layer and / or other constituent layers, 7. A method of processing a black-and-white silver halide photographic light-sensitive material, which comprises processing with a development replenisher prepared from the solid processing agent according to any one of 1 to 6.

(10) The developer replenishment amount is 10 to 200
10. The method for processing a black-and-white silver halide photographic light-sensitive material described in any one of 7 to 9 above, which is cc / m ² or less.

The present invention will be described in detail below. In the compound represented by the general formula (1), a compound represented by the following general formula [1-a] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0023]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Amide group, sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or NR
Represents ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in formula (1) or [1-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (1) or the general formula [1-a] according to the present invention are shown below.
The present invention is not limited to these.

[0027]

[Chemical 6]

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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These compounds are typically ascorbic acid, erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods. General formula (1)
The compound is used as a replenisher at 0.0004 mol / L or more and 1 mol / L or less.

In the compound represented by the general formula (2),
The lower alkyl group represented by R ₀ may be linear or branched and has 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, an iso-propyl group and a butyl group. Specific representative examples of the compound represented by the general formula (2) are shown below.

2-1 5-nitroindazole 2-2 6-nitroindazole 2-3 5-methylindazole 2-4 6-methylindazole 2-5 indazole 2-6 5-chlorobenzimidazole 2-7 5-methylbenz Imidazole 2-8 5-Ethylbenzimidazole 2-9 5-Nitrobenzimidazole 2-10 6-Nitrobenzimidazole 2-11 5-Chlorobenzimidazole 2-12 Benzimidazole Containing compound represented by general formula (2) The amount is 0.1 by weight with respect to the dihydroxybenzenes contained in the developer.
10 to 10 wt% is preferable, and 0.1 to 3
It is more preferable that the content is wt%.

In the present invention, when LiOH is contained, it is preferably contained in the developer in an amount of 0.1 to 20 wt%, preferably 0.1 to 5 wt% with respect to the dihydroxybenzenes contained in the developer. Is more preferable.

The solid processing agent of the present invention means that a single substance and a plurality of components are mixed to have a granular or tablet form, and each granule and / or tablet can form a single or a plurality of developers. Say something. The components that make up the developer replenisher compose the kit in the form of being separated into 1 to 4 parts, and the preferred form is that it is composed of 1 or 2 parts. It is particularly preferable to be composed of one part from the viewpoint of opening work and reduction of waste packaging material.

As the method for dissolving the solid processing agent of the present invention, it may be carried out manually or mechanically as in the usual liquid preparation method, and the replenishment tank may be inside the automatic processor or externally. May be there. As a method of supplying the treatment agent,
Any form may be used as long as each component of the treating agent does not scatter, for example, a method of wrapping a solid treating agent with a water-soluble polymer film and directly inputting it, packaging with a paper surface-treated with a material such as polyethylene, and scattering of powder agent, There is a method of preventing the residue and adding it to the tank. Considering the solubility of the processing agent in water, the solid form is preferably granules or tablets, but the components of the photographic processing agent often include those which are poorly soluble in water. A sparingly soluble substance may precipitate in the liquid. In order to avoid this, there is a method of adding a solvent separately.

In order to form granules or tablets, it is preferable to use a generally used granulation aid, and a water-soluble or alkali- or acid-soluble polymer is used. Specifically, gelatin, pectin, sorbitol, mannitol, polyacrylic acid, polyacrylic acid salt, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid. Salt, xanthate gum, gum arabic, gum tragacanth,
Karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene alkyl ether such as polyoxyethylene ethyl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenol such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether Ether, or one or two selected from water-soluble binders described in JP-A-4-85535.
More than one species can be used in combination.

Further, in order to increase the preservability of the treating agent in the kit, the treating agent may be enclosed in two or more separate forms in the kit.

In the present invention, the developing agent of the general formula (1) according to the present invention and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl). -4,4-Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol,
2,4-diaminophenol and the like) can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually preferably used in an amount of 0.01 to 1.4 mol per liter of the developing solution.

The solid processing agent of the present invention contains, as a silver sludge-preventing agent, Japanese Patent Application No. 7-130400, paragraph No. 103-
The nitrogen-containing heterocyclic compound described in 119 may be contained. The amount of these compounds used is preferably 10 ⁻⁶ to 10 ⁻¹ mol, and more preferably 10 ⁻⁵ to 10 ⁻² mol, in 1 liter of the developing solution.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

In the present invention, the developer contains an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine). Etc.) are preferably added. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol or more and 1.5 mol or less.
It is in the range of mol or less. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole,
Benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or alkali metal salts thereof, nitrilotriacetate salts, polyphosphate salts etc.), development accelerators (eg US Pat. No. 2,304, No. 025, Japanese Patent Publication No. 47-45541, etc.), a hardener (eg glutaraldehyde or its bisulfite adduct), or an antifoaming agent can be added. The pH of the developer is 7.5 or more 1
It is preferably adjusted to less than 0.5. More preferably, the pH is 8.5 or more and 10.4 or less.

The waste developer can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer,
For example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developing solution, can be additionally added. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

As a special form of development processing, a developing agent is contained in a light-sensitive material, for example, in an emulsion layer or in an adjacent layer thereof, and is used in an activator processing solution for processing the light-sensitive material in an alkaline aqueous solution for development. Good. Further, a light-sensitive material containing a developing agent in a light-sensitive material, for example, an emulsion layer or an adjacent layer thereof may be processed with a developer. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates capable of softening water. Compounds such as agents may be included.

In the present invention, the concentration of ammonium ions in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution.

The ammonium ion concentration is particularly preferably in the range of 0 to 0.05 mol per liter of the fixing solution. As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the concentration of acetate ion in the fixing solution is preferably less than 0.33 mol / liter. The type of the acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates the acetate ion in the fixing solution. However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used, and particularly sodium salt. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less per liter of the fixing solution,
Particularly preferably, it is 0.13 mol or less, whereby the acetic acid gas generation amount can be remarkably reduced. Most preferably, it is substantially free of acetate ions.

The fixing solution of the present invention preferably contains thiosulfate. Examples of the thiosulfate include lithium, potassium, sodium and ammonium salts, preferably sodium salt or ammonium salt. The addition amount of thiosulfate is 0.1 to 5 mol, more preferably 0.5 to 2.0 mol, still more preferably 0.7 to 1.8 mol, per liter of the fixing solution. Most preferred is 0.8 to 1.5 moles.

The fixing solution of the present invention contains salts such as citric acid, tartaric acid, malic acid, succinic acid, and optical isomers thereof. As salts of citric acid, tartaric acid, malic acid, succinic acid, etc., these lithium salts, potassium salts, sodium salts, ammonium salts, etc., such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, potassium potassium tartaric acid, tartaric acid Sodium potassium and the like may be used.

In the present invention, the fixing treatment is followed by washing with water and / or treatment with a stabilizing bath. As the stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkaline agents and salts thereof (for adjusting the pH of the film surface after treatment to 3 to 8) for the purpose of stabilizing the image ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid,
Malic acid, acetic acid, etc. are used in combination), aldehydes (eg formalin, glyoxal, glutaraldehyde etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc.), anti-bacterial agents. Agents (for example, phenol, 4-chlorophenol, cresol, o-phenylphenol, chlorophene, dichlorophene, formaldehyde, p-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one,
Dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjusting agent and / or residual color improving agent (eg mercapto group). A nitrogen-containing heterocyclic compound having as a substituent; specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl -1,
3,4-triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form. In the case of replenishing in solid form, the above-mentioned production method and use method of the solid treatment agent can be used.

In order to reduce the amount of waste liquid, the present invention is processed while supplementing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The developer replenishing amount and the fixer replenishing amount are each 330 ml or less per 1 m ² . It is preferably 10 to 200 ml per 1 m ² , and more preferably 10 to 15 per 1 m ^2.
0 ml. The developer replenishing amount and the fixer replenishing amount herein refer to the amount of replenishing liquid. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquid and the fixing mother liquid, and each concentrating liquid when replenishing with the liquid obtained by diluting the developing concentrated liquid and the fixing concentrated liquid with water. And the total amount of water, the total amount of each solid processing agent and the volume of water when the solid development processing agent and the solid fixing processing agent are replenished with a liquid dissolved in water, and the solid development processing agent. And the total amount of each solid processing agent volume and water volume when the solid fixing processing agent and water are separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as or different from the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine. Especially the developer replenishment rate is 1 per 1 m ^2.
When the amount is 20 ml or less, the developing replenisher is preferably a liquid different from the developing mother liquor in the tank of the automatic processor or a solid processing agent, and the amount of the mercapto group-containing silver sludge inhibitor contained in the developing replenisher is The amount of the compound represented by the general formula (1) of the present invention or the transition metal complex salt contained in the developing replenisher is preferably 1.2 times the amount contained in the developing mother liquor. It is preferable that the amount is four times. Also, the fixer replenishment rate is 15 per 1 m ^2.
When the amount is 0 ml or less, the fixing and developing replenisher is preferably different from the fixing mother liquor in the tank of the automatic processor or a solid processing agent, and the amount of thiosulfate contained in the fixing replenisher is included in the fixing mother liquor. It is preferable that the amount is larger than the amount.

In the present invention, the solid processing agent can be dissolved in water. The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C, and the temperature of each may be adjusted separately.

In the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 100 when the processing is performed by using the automatic developing machine in order to shorten the developing time. It is preferably not more than 10 seconds and not more than 10 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for example, developing, fixing, bleaching, washing with water necessary for the processing,
This is the time including all the steps of the stabilization treatment, the drying, etc., that is, the time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to D
ry) is 15 to 50 seconds. Further, in order to stably run a large amount of light-sensitive material of 10 m ² or more, the developing time is preferably 30 seconds or less and 2 seconds or more.

In order to bring out the effect of the present invention remarkably, the heat transfer material at 60 ° C. or higher (for example, 60 ° C.) is required for the automatic processor.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Heat energy of copper, stainless steel,
Those which transmit infrared rays by transmitting heat to a radiator such as nickel or various ceramics) and have a zone for drying are preferably used.

As the heat transfer material having a temperature of 60 ° C. or higher,
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller and the gear is rotated in the carrying direction by the driving means and the driving transmission means. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

Further, the temperature controller is connected with a thermistor arranged in contact with the outer peripheral surface of the heat roller, and the temperature controller detects the temperature from the thermistor at 60 ° C to 150 ° C, preferably 70 ° C to 130 ° C. Therefore, it is preferable to control the halogen heater on and off.

The following examples can be given as examples of the radiant body emitting a radiant temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, the heat transfer material having a temperature of 60 ° C. or higher and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

The halogen composition of the silver halide in the silver halide emulsion used in the present invention is not particularly limited, but in the case of processing with a small replenishment amount or rapid processing,
Silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, 60
It is preferable to use a silver halide emulsion having a composition of silver chloroiodobromide containing silver chloride of mol% or more.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any one-side mixing method, simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. Gives a silver halide emulsion having a substantially uniform grain size.

In order to remarkably bring out the effect of the present invention, tabular grains can be used, and more preferable results are obtained as the proportion of tabular grains increases from 60% to 70%, and further 80%. . The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. Since tabular grains consisting of 50 mol% or more of silver chloride have (100) as the principal plane, they can be represented by an aspect ratio rather than a scale of aspect ratio, and the ratio is preferably 1.2 to 8. Further, iodide can be contained in the internal nucleation site in the range of 0.001 to 1 mol%. For the tabular grains having a large amount of silver chloride component, the method described in US Pat. No. 5,320,938 can be referred to. 0. inside the silver halide grains.
The presence of 001 mol% or more and less than 10% of high silver iodide sites and the presence of silver nuclei are preferable for improving the pressure resistance of the grains. The larger the aspect ratio or the aspect ratio, the flatter the plate. The thickness of the tabular grains is preferably 0.01 to 0.5 μm, but can be arbitrarily selected by setting the aspect ratio and the average volume grain size. The distribution of tabular grain size is
Coefficient of variation often used (100 times the value S / D obtained by dividing the standard deviation S when the projected area is approximated by a circle by the diameter D)
Is preferably 30% or less, particularly preferably 20% or less. Further, two or more kinds of tabular grains and normal crystal grains can be mixed.

Among these tabular grains, tabular grains having a (100) plane having a silver chloride content of 50 mol% or more as a main plane are preferably used, and these are described in US Pat.
No. 4,337, No. 5,314,798, No. 5,3
No. 20,958, etc., and the target tabular grain can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. Further, in order to control the photosensitizing nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to have a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodide ions. For the preparation of particles, an acidic method, a neutral method, an ammonia method, or the like can be appropriately selected. When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5. Ammonia, thioethers, thiourea compounds, and thione compounds can be used as a silver halide solvent in order to control the growth of tabular grains during grain formation.

During physical aging or chemical aging, metal circles such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. Iridium 10 to obtain high illuminance characteristics
Doping in the range ^-9 to 10 ^-3 is often customary in silver halide emulsions. In the present invention, rhodium, ruthenium, osmium and / or rhenium are preferably doped in the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide in order to obtain a high contrast emulsion.

When the metal compound is added to the particles,
Halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, metal
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A No. 2-20.
No. 82, No. 2-20853, No. 2-20854, No. 2-20855, 6-dentate ligands,
Alkali complex salts include common sodium salts, potassium salts, cesium salts, or primary, secondary, and tertiary amine salts. Also, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these are, for example, K ₂ [RuC
l ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO)
Cl ₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)] and the like. The part of Ru is Rh, Os, R
e, Ir, Pd, and Pt can be used instead.

Rhodium, ruthenium, osmium and /
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there is a method of uniformly distributing the particles, or a method of forming a core-shell structure and localizing a large amount in the core or the shell.

It is often the case that better results are obtained when a large amount is present in the shell portion. In addition, a method of increasing the existing amount may be used as it is continuously outside the particles, in addition to localizing in a discontinuous layer structure. The addition amount can be appropriately selected within the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499 and Japanese Patent Laid-Open No. 50-71325.
JP-A No. 60-150046 and the like can be preferably used.

As the tellurium sensitizer, known tellurium sensitizers can be used. For example, US Pat.
499, 3,772,031, 3,320,0
The compounds described in No. 69 and the like can be preferably used.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of reduction sensitizers include stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The sensitizing effect can be further enhanced by adding these sensitizers in the form of fine particles dispersed therein. Also, Ag
When I particles are finely dispersed and added at the time of chemical sensitization, AgI is formed on the particle surface, and the effect of dye sensitization can be enhanced. When forming tabular grains of AgI, the contribution of the transition line portion ranging from 0 to 1000 is often utilized.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus And a quinoline nucleus. These nuclei may be substituted on carbon atoms. As a core having a ketomethylene structure in the merocyanine dye or composite merocyanine dye,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- to 6-membered heterocyclic ring such as a 2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. Specifically, Research Disclosure Vol. 176 RD
-17643 (December, 1978), pages 2.3, U.S. Pat. Nos. 4,425,425 and 4,425,426 can be used. The sensitizing dye may be dissolved by using ultrasonic vibration described in U.S. Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention and adding it to an emulsion, US Pat. Nos. 3,482,981 and 3,58
5,195, 3,469,987, 3,42
5,835, 3,342,605, British Patent 1,
271,329, 1,038,029, 1,1
21, 174, U.S. Pat. Nos. 3,660,101 and 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Research D
174, 17643 (issued in December 1978), page 23, IV, paragraph J.

The black and white silver halide photographic light-sensitive material used in the present invention preferably contains a hydrazine derivative.

The hydrazine derivative is a compound represented by the following general formula [H].

[0087]

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In the general formula [H], A ₀ is an aliphatic group,
The aromatic group or the heterocyclic group, the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly 1 to 2 carbon atoms.
A linear, branched or cyclic alkyl group of 0 is preferred. Specific examples include, for example, a methyl group, an ethyl group, a t-butyl group,
Octyl group, cyclohexyl group, benzyl group and the like, which are further substituted with appropriate substituents (eg aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido group, etc.). May be.

The aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A ₀ is preferably a monocycle or a condensed ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen atoms, and examples thereof include pyrrolidine, imidazole, tetrahydrofuran and morpholine. , Pyridine, pyrimidine, quinoline, thiazole,
Examples thereof include benzothiazole, thiophene and furan ring.

Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group of A ₀ preferably have a substituent. Preferred groups include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, substituted amino groups, acylamino groups,
Sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfothio group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryl Examples thereof include an oxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxy group and a phosphoric acid amide group, and these groups may be further substituted.

Among these groups, a developing solution having a pH of 10.5 or less was used, and the total processing time (Dryto Dry) was 6
When the treatment is carried out for 0 seconds or less, a substituent having an acidic group of pKa 7 to 11 is preferable, and specific examples thereof include a sulfonamide group, a hydroxyl group and a mercapto group, and particularly preferable examples include a sulfonamide group. .

Further, A ₀ preferably contains at least one diffusion resistant group or silver halide adsorption group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and the ballast group is a photographically inert group having 8 or more carbon atoms, for example, an alkyl group, an alkenyl group, an alkynyl group, Examples include an alkoxy group, a phenyl group, a phenoxy group, and an alkylphenoxy group.

As the silver halide adsorbing group, thiourea,
Examples thereof include a thiourethane group, a mercapto group, a thioether group, a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorption group described in JP-A No. 64-90439.

B ₀ represents a blocking group, preferably -G ₀ -D ₀ G ₀ is -CO- group, -COCO- group, -CS- group, -C.
(= NG ₁ D ₁₎ - represents a group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 1 D} 1). G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - represents a group. D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different.

D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group,
It represents an alkylthio group or an arylthio group.

Preferred G ₀ is --CO-- group, --CO
A CO-group is particularly preferably a -COCO- group. Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (ethoxalyl). Etc.).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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In the present invention, in the case of containing a hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb] in order to effectively promote the contrast enhancement by the hydrazine derivative.

[0106]

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In the general formula [Na], R ₉ , R ₁₀ and R
₁₁ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₉ , R ₁₀ and R ₁₁ can form a ring.

Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

A preferred embodiment of the general formula [Na] is a compound represented by the following general formula [Na-a].

[0110]

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In the general formula [Na-a], R ¹ , R ² ,
R ³ and R ⁴ represent a hydrogen atom, an alkyl group, a substituted alkyl group,
Represents an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group, a substituted aryl group, a saturated or unsaturated hetero ring. These can be linked to each other to form a ring. Further, R ¹ and R ² and each set of R ³ and R ⁴ are not a hydrogen atom at the same time.

X represents an S, Se or Te atom.

L ₁ and L ₂ represent a divalent linking group. Specific examples include combinations of the following groups and groups having appropriate substituents (for example, an alkylene group, an alkenylene group, an arylene group, an acylamino group, and a sulfonamide group).

[0114] _{-CH 2 -, - CH = CH} -, - C 2 H
₄ -, _{pyridiyl, -N (Z 1) - (} Z 1) is a hydrogen atom,
Represents an alkyl group or an aryl group), -O-, -S-,
- (CO) -, - ( SO 2) -, - CH 2 N-, also preferably contains at least one or more of the following structure in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ ).
_{HCH 2 O] -, - [} OC (CH 3) HCH 2 O] -, -
[OCH ₂ C (OH) HCH ₂ ] — Specific examples of the compound represented by the general formula [Na] are shown below.

[0116]

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[0117]

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[0118]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₂ is a hydrogen atom,
It represents an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₁₂ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific examples of the compound of the general formula [Nb] include those shown below.

[0121]

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[0122]

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The black-and-white silver halide photographic light-sensitive material used in the present invention is effective when it contains a tetrazolium compound.

The tetrazolium compound is represented by the following general formula [T].

[0125]

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Substituent R ₁₇ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T],
R ₁₈ and R ₁₉ are preferably hydrogen atoms or those having a negative Hammett sigma value (σp) showing an electron withdrawing degree.

The Hammett sigma value of the phenyl group has been reported in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. It can be found in reports such as C. Hansch and the like, and particularly preferable groups having a negative sigma value include, for example, a methyl group (σp = −0.17 or less, any σp value), an ethyl group (− 0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which is useful as a substituent of the compound of the general formula [T].

N represents 1 or 2, and examples of the anion represented by X _T ^n- are halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid,
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonate anion such as toluene sulfonate anion, higher alkylbenzene sulfonate anion such as p-dodecylbenzene sulfonate anion, higher alkyl sulfate ester anion such as lauryl sulfate anion, boric acid anion such as tetraphenylboron, di- A dialkyl sulfosuccinate anion such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Specific examples of the compound represented by formula [T] are shown below, but the tetrazolium compound is not limited to these.

[0130]

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The above-mentioned tetrazolium compound can be used, for example, in Chemical Reviews 5
The compound can be easily synthesized according to the method described in Vol. 5, pages 335 to 483.

The compound represented by the general formula [T] may be used alone or in combination of two or more kinds at an appropriate ratio.

Next, as the pyridinium salt used in the black-and-white silver halide photographic light-sensitive material used in the present invention,
Examples thereof include a pyridinium salt and a derivative thereof, a quinolinium salt and a derivative thereof, an isoquinolinium salt and a derivative thereof (hereinafter, these pyridinium salt and a derivative thereof are simply referred to as a pyridinium salt derivative).

Examples of the pyridinium salt derivatives include pyridinium salt derivatives represented by the following general formula [N-1], quinolinium salt derivatives represented by the general formula [N-2] and general formula [N-3]. And an isoquinolinium salt derivative.

[0135]

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In the general formula [N-1], R ₂₁ is an amino group, an alkyl-substituted amino group, (N-methylamino group,
(N, N-dimethylamino group, etc.) represents an aromatic group such as a phenyl group or a pyridyl group or -A ₂₁ -Z ₂₁ . A ₂₁ is an alkyl group having 1 to 20 carbon atoms or —CH ₂ CH═CH.
CH ₂ - represents, Z ₂₁ is a hydrogen atom, an optionally substituted phenyl group, a hydroxyl group, an alkoxy group such as methoxy group or an ethoxy group, an acyl group such as benzoyl group or acetyl group,
It represents an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, a cyano group, an N-alkylamide group, an amide group or a group represented by the general formula [N-1a]. X ₂₁ ^- represents an anion.

[0137]

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General formula [N-1] and general formula [N-1a]
In the formula, R ₂₂ is a lower alkyl group (2-hydroxy group, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), a hydroxyl group, an alkoxy group, a lower alkyl group (2-hydroxy group) substituted with an aromatic group such as a phenyl group and a pyridyl group. Ethyl group, 3-
Hydroxypropyl group, 2-methoxyethyl group, 4-ethoxybutyl group, benzyl group, 2-phenylethyl group,
3- (4-pyridyl) propyl group, etc.), amide group (-C
ONH _2, -CONHCH ₃₎ or an optionally substituted amino group _{(-NH 2, -NHSO 2 C 5} H 11, -NHSO 2 P
h, etc.) and n ₂₁ represent 0, 1, 2 or 3. Where R ₂₂
When there are plural numbers, they may be different from each other.
X ₂₂ ⁻ represents an anion such as iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion and methylsulfate ion. However, the general formula [N-
1] has a betaine structure, X ₂₂ ⁻ does not exist.

[0139]

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In the general formula [N-2], R ₂₃ represents a substituted or unsubstituted lower alkyl group, alkenyl group or alkynyl group. Substituents include hydroxyl groups, lower alkoxy groups such as methoxy and ethoxy groups, aromatic groups such as phenyl groups, acyl groups such as acetyl and benzoyl groups, alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups, and amide groups. , Cyano group and the like are preferable. Specific examples of R ₂₃ include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, 2-hydroxypropyl group, 3
-Hydroxypropyl group, 2-methoxyethyl group, 3-
Ethoxypropyl group, 2-phenylethyl group, 3-acetylpropyl group, 2-benzoylethyl group, 2-methoxycarbonylethyl group, 2-cyanoethyl group, 2-carbamoylethyl group, butenyl group, propargyl group, benzyl group, toluyl Group, phenethyl group and the like.

R ₂₄ and R ₂₅ are each independently a halogen atom, a lower alkyl group (eg, methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, etc.), substituted lower alkyl group or lower alkoxy group, (eg methoxy group, ethoxy group etc.). The substituent of the substituted lower alkyl group is preferably a hydroxyl group, a lower alkoxy group, or a substituted or unsubstituted aromatic group (eg, phenyl group, alkyl-substituted phenyl group, etc.). Specific examples of the substituted lower alkyl group include, for example, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, benzyl group, 2-phenylethyl group, A 2-tolylethyl group etc. can be mentioned.

N ₂₂ and n ₂₃ are each independently 0 or 2
Represents When a plurality of R ₂₄ and / or R ₂₅ are present, they may be different from each other or may form a ring between them (for example, a 5-membered ring, a 6-membered ring, a 7-membered ring, etc.).

[0143] X ₂₃ ^- represents iodide ion, bromide ion, chloride ion, p- toluenesulfonate ion, perchlorate ion, an anion such as methylsulfate ion. However,
When the general formula [N-2] has a betaine structure, X ₂₃ ⁻ does not exist.

[0144]

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In the general formula [N-3], R ₂₆ represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.) or a substituted alkyl group.

Further, R ₂₆ and R ₂₈ are a 6-membered ring or 5
A member ring may be formed. R ₂₇ represents a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.), substituted alkyl group or aryl group (phenyl, alkyl-substituted phenyl group, etc.). R ₂₆
Examples of the substitution of the substituted alkyl group for R ₂₇ and R ₂₇ include a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, etc.), an aryl group (phenyl group, alkyl-substituted phenyl group, etc.) and the like. Specific examples of the substituted alkyl include, for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, benzyl group, 3-methoxypropyl group, benzyl group, 2-phenylethyl group. And so on.

R ₂₈ and R ₂₉ are each independently a hydrogen atom,
Lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.) Lower alkyl group substituted with hydroxyl group, alkoxy group, etc. (2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxypropyl group) Represents a group (for example, a methoxy group, an ethoxy group, etc.) or an amide group.

Further, R ₂₈ and R ₂₉ may form a ring such as a 5-membered ring or a 6-membered ring or an aromatic ring. R ₃₀ is a halogen atom (chlorine atom, bromine atom, etc.), an optionally substituted lower alkyl group (methyl group, ethyl group, propyl group,
2-hydroxyethyl group, 3-hydroxypropyl group,
2-methoxyethyl group, benzyl group, etc.), an alkoxy group (methoxy group, ethoxy group, etc.) or an amino group which may be substituted with an alkyl group.

N ₂₄ represents 0, 1 or 2. When a plurality of R ₃₀ 's are present, they may be different from each other. X
₂₄ ^- is an anion such as iodine ion, bromine ion, chlorine ion, p-toluenesulfonate ion, perchlorate ion, and methylsulfate ion. However, general formula [N-3]
But when the betaine structure X ₂₄ ^- does not exist.

The reduction potential of the pyridinium salt derivatives used in the black-and-white silver halide photographic light-sensitive material used in the present invention is a compound of -0.60 V or less, more preferably-.
A compound having a voltage of 0.80 V or less is used.

The value of the reduction potential Ered used here means the potential at which pyridinium salt derivatives are reduced by the injection of electrons at the cathode in voltammetry. The value of the reduction potential Ered can be accurately measured by voltammetry. That is, the supporting electrolyte is tetra-
In acetonitrile containing 0.1 mol of n-butylammonium perchlorate, a voltammogram of 1 × 10 ⁻³ mol to 1 × 10 ⁻⁴ mol of the pyridinium salt derivative was measured and determined as a half-wave potential obtained from this. Further, platinum was used as a working electrode and a saturated calomel electrode (SCE) was used as a reference electrode, and the measurement was performed at 25 ° C. More specifically, U.S. Pat. No. 3,501,307 and P. Delaha.
y) "New Instrumental Methodes in Electrochemistry" (New Instrument)
mental Methods in Electric
hemistry) (Interscience Pu)
Blisters, Inc., 1954).

Typical examples of the pyridinium salt derivative used in the black-and-white silver halide photographic light-sensitive material used in the present invention are shown below, but the present invention is not limited thereto.

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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These pyridinium salt derivatives are described in "Great Organic Chemistry", Vol. 16 (111), p. 7 and 1, edited by M. Otake.
It can be synthesized by the reaction of the corresponding pyridine, quinoline or isoquinoline derivative with an alkyl halide derivative as described on page 29 (1959, Asakura Shoten). A specific synthesis method is described in A. G, E. Ren
Report by Helk. Chim. Acta 37,167
2 (1954); E. FIG. Lyle, E .; F. Perl
wski, H .; J. Trosianiec, G .; G. FIG.
Lyle, J. J. Org. Chem. 20, 17
61 (1955); R. Lamborg, R .; M.
Burton, N.M. O. Kaplan's article J. Am.
Chem. Soc. 79, 6173 (1957);
Ciusa, A .; Report by G. Buccelli Gazze
tta Chimia Italiana 88, 393
(1958).

The hydrazine derivative or pyridinium compound and the nucleation accelerator or tetrazolium compound used in the present invention can be used in any layer on the silver halide emulsion layer side, preferably the silver halide emulsion layer. Alternatively, it is preferably used for the adjacent layer. The particle size of the added amount of silver halide grains, the halogen composition, the degree of chemical sensitization, the optimum amount varies depending on the kind of the inhibitor, generally per mol of silver halide ^{10-6 -} A range of ¹ mol is preferable, and a range of 10 ^-5 to 10 ^-2 mol is particularly preferable.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion according to the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

As one method for remarkably exhibiting the effects of the present invention, it is preferable to include a hydrophilic polymer in at least one constituent layer. Preferred hydrophilic polymers include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan and the like. The molecular weight of the hydrophilic polymer can be appropriately selected from 600 to 1,000,000. The lower the molecular weight is, the better in order to be rapidly eluted into the treatment liquid during the treatment. However, if it is too low, the film strength of the film is deteriorated, so that it is required to be 600 or more. When a hydrophilic polymer is used, the film scratch resistance deteriorates, so
It is preferable to add inorganic colloidal silica, colloidal tin, colloidal zinc, colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite, and the like. Examples of the zeolite include analcite, erionite, mordenite, shabasite, gmelinite, and levinite, and examples of the synthetic zeolite include zeolite A, X, Y, and L. Examples of apatite include hydroxyapatite, fluorospatite, and chlorapatite. A preferable addition amount is 1% to 200% by weight per hydrophilic binder. By treating the above inorganic compound with a silane coupling agent, the inorganic compound hardly aggregates even when added to an emulsion, and can stabilize a coating solution. Further, cracking due to the inorganic compound can be prevented. As a silane coupling agent, triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropylsilanomethacrylic, trimethoxysilanopropylglycidyl, 1-mercapto-3-triethoxysilanopropane, 1-amino-3-triethoxysilanopropane , Triethoxysilanophenyl, triethoxymethylsilane and the like. The properties of the silane coupling agent can be improved by performing a high temperature treatment together with the above-mentioned inorganic compound, compared to the simple mixing. The mixing ratio is preferably selected in the range of 1: 100 to 100: 1.

The black and white silver halide photographic light-sensitive material used in the present invention has at least one hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer and at least one hydrophobic polymer layer on the outside thereof. It is preferable.
Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called back layer. In the present invention, a structure having at least one hydrophobic polymer layer outside the back layer is preferable. In the present invention, the hydrophobic polymer layer is a layer using a hydrophobic polymer as a binder. Specific examples of the binder for the polymer layer include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin,
Phenol resin, epoxy resin, tetrafluoroethylene, fluororesin such as polyvinylidene fluoride, butadiene rubber, chloroprene rubber, rubber such as natural rubber, acrylic acid or methacrylic acid ester such as polymethylmethacrylate and polyethylacrylate, polyethylene Examples thereof include polyester resins such as phthalate, polyamide resins such as nylon 6 and nylon 66, cellulose resins such as cellulose triacetate, water-insoluble polymers such as silicone resins, and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferred binders are copolymers of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymer, styrene-butadiene-
Acrylic acid copolymer (acrylic acid is preferably 5 mol% or less), styrene-butadiene-divinylbenzene-
Methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile-methyl methacrylate-ethyl acrylate-acrylic acid copolymer (acrylic acid 5 mol% or less), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer, and the like. These may be used alone or in combination of two or more.

The hydrophobic polymer layer in the present invention may include a matting agent, a surfactant, a dye, a slip agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica for photographic use, if necessary. Additives may be added. These additives are also described in Research Disclosure Magazine 17
6, 17646 (December 1978).

The hydrophobic polymer layer in the invention may be one layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, if the thickness of the hydrophobic polymer layer is too small, the water resistance of the hydrophobic polymer layer becomes insufficient, and the back layer swells in the treatment liquid, which is inappropriate. Conversely, if the thickness of the hydrophobic polymer layer is too large, the water vapor permeability of the polymer layer becomes insufficient, and the moisture absorption and desorption of the hydrophilic colloid layer of the back layer is inhibited, resulting in poor curl. Of course, the thickness of the hydrophobic polymer layer also depends on the physical properties of the binder used. Therefore, the thickness of the polymer layer needs to be determined in consideration of both. The preferred thickness of the hydrophobic polymer layer depends on the kind of binder of the hydrophobic polymer layer, but is 0.05 to 10 μm.
m, more preferably 0.1 to 5 μm.

The black-and-white silver halide photographic light-sensitive material used in the present invention is not particularly limited in the method of coating the hydrophobic polymer layer. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be simultaneously coated and then dried. The hydrophobic polymer layer may be applied in a solvent system by dissolving in a solvent of a binder of the polymer layer, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

On the surface opposite to the emulsion layer of the black and white silver halide photographic light-sensitive material used in the present invention, an adhesive layer / antistatic layer / a back layer containing a hydrophilic colloid / a hydrophobic polymer layer on a support. Is preferably provided. Further, a protective layer may be provided thereon. As an adhesive layer, a vinylidene chloride copolymer or a styrene-glycidyl acrylate copolymer was applied on a corona-discharged support in a thickness of 0.1 to 1 μm, and then an indium or phosphorus-doped average particle size of 0.
It can be obtained by coating with a gelatin layer containing fine particles of tin oxide and vanadium pentoxide of 01 μm to 1 μm. Further, a styrene sulfonic acid / maleic acid copolymer can be formed by forming a film with the above-mentioned aziridine or carbonyl active type crosslinking agent. A dye back layer may be provided on these antistatic layers. These layers should contain inorganic fillers such as colloidal silica for dimensional stability, silica or methyl methacrylate matting agent for adhesion prevention, silicon-based slip agent or release agent for transportability control, etc. Can be. The back layer may contain a backing dye, and as the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can be fixed as fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

Inorganic or organic hardeners are added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention as a crosslinking agent for hydrophilic colloids such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.) ), Mucohalogen acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activating type hardener, etc., alone or in combination. Can be used. These hardeners are available from Research Disclosure.
loss) 176, 17643 (issued in December 1978), page 26, paragraphs A to C. Among them, preferred are carboxyl group-activated hardeners, and compounds represented by formulas (1) to (7) described in JP-A-5-289219, pp. 3-5, are preferred. Is, for example, H- described in pages 6 to 14 of the same specification.
1-H-39.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aids, antistatic, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

In each layer, in addition to gelatin, dextrins,
The degree of swelling can be controlled by introducing a hydrophilic polymer such as starch or glucose or a hydrophobic latex. The degree of swelling is generally from 120 to 200. For drying each layer, the temperature and time are adjusted according to the evaporation rate of water.
A temperature of 25 ° C. to 200 ° C. and a time of 0.1 second to 200 seconds are generally applied. The degree of swelling can be measured by immersing in water and measuring with a microscope, or by a swelling degree meter. As the degree of swelling, dry film thickness = Ld (23 ° C. 50%
Relative to the relative humidity (film thickness after 24 hours humidity control) to the ratio (Lw / Ld) of the swollen thickness Lw in water at 23 ° C. to 100
The value multiplied by can be used as an index.

The surface tension and the wetting index can be determined by referring to JIS.

The film surface pH on the black-and-white silver halide photographic emulsion layer side used in the present invention is preferably pH 4.5 or higher and pH 5.8 or lower. The film surface pH is a pH measured after coating and drying, and the measurement is 1 per 1 cm ^{2 of the} measured portion.
Deteriorate with cc of pure water and measure with a pH meter. To lower the pH, use an acid such as citric acid, oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or carbonic acid.To raise the pH, use sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium acetate. Alkali agents such as can be used. The same method can be applied when adjusting the pH when using a photographic additive.

Various other additives are used in the light-sensitive material used in the present invention. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

The support of the light-sensitive material used in the present invention is
Either permeable or impermeable, but for the purposes of the present invention, preferably a permeable plastic support. As the plastic support, a support made of a polyethylene compound (eg polyethylene terephthalate, polyethylene naphthalate etc.), a triacetate compound (eg triacetate cellulose etc.), a polystyrene compound etc. is used. Among them, a support (hereinafter abbreviated as SPS) made of a stretched film made of a styrene-based polymer having a syndiotactic structure or a composition containing the same is particularly preferable in order to remarkably exert the effects of the present invention. SPS refers to a homopolymer whose constituent unit is composed of SPS units having syndiotactic stereoregularity, but in a small amount, for example, 20 mol% or less,
It also preferably contains 10 mol% or less, more preferably 5 mol% or less of the SPS modified with the second component. Examples of the second component include olefin monomers such as ethylene, propylene, butene and hexene, diene monomers such as butadiene and isoprene, cyclic olefin monomers, cyclic diene monomers and polar vinyl monomers such as methyl methacrylate, maleic anhydride and acrylonitrile. It includes those including. In general, it is produced by polymerizing styrene or a derivative thereof under an appropriate reaction condition using an organometallic catalyst. Sydiotactic polystyrene is 75% of racemic diad.
As described above, preferably, the stereoregularity is 80% or more, or 30% or more, and preferably 50% or more in racemic pentad. In this case, a general plastic plasticizer can be added as the second component within a range that does not degrade the flexural modulus, and this is performed to obtain an appropriate flexural modulus.

SPS can be synthesized by polymerizing styrene or a derivative thereof at a suitable reaction temperature in the presence of a catalyst of a condensation product of a titanium compound and a trialkylaluminum. These can be referred to the methods described in JP-A-62-187708, JP-A-1-46912 and JP-A-1-178505. The polymerization degree of SPS is not particularly limited, but those having 10,000 to 5,000,000 are preferably used. In order to increase the flexural modulus of the SPS, it is necessary to select optimal stretching conditions. 30 ° C. ± 25 ° C. from the glass transition point of the unstretched film, ie, 1
At 20 ° C. ± 25 ° C., the film is first stretched longitudinally 3.3 ± 0.3 times. Next, it is stretched transversely 3.6 ± 0.6 times under the same temperature conditions. Heat treatment after stretching is performed at 230 ± 18 ° C. Good results can be obtained by performing the heat treatment not only in one stage but also in two stages. Thus, S having a flexural modulus of 350 kg / mm ² or more
A PS film is manufactured.

A film having such a high flexural modulus is
It is difficult to apply the photographic layer as it is and adhere it firmly. There are many patents and literature on how to do this,
This is described in JP-A-3-54551, pp. 3-4, and can be referred to.

For example, regarding the surface treatment, it is described that a corona discharge treatment or an undercoat layer is further applied. Examples of the undercoat layer include vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

In order to further improve the curl and curl of the support, it is preferable to perform heat treatment after film formation. Most preferred is after film formation and after emulsion coating, but it may be after emulsion coating. The heat treatment is preferably performed at a temperature of 45 ° C. or higher and a glass transition temperature of 1 second to 10 days. From the point of productivity 1
It is preferably within the time.

The various photographic additives used in the light-sensitive material used in the present invention may be dissolved in an aqueous solution or an organic solvent, but when they are poorly soluble in water, they are made into a fine-grain crystal state to give water, gelatin or hydrophilicity. It can be used by dispersing it in a hydrophilic or hydrophobic polymer. Dyes, dyes, desensitizing dyes, hydrazines, redox compounds, antifoggants of the present invention,
To disperse the ultraviolet absorber and the like, a known disperser can be used. Specific examples include a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, and a high speed impeller disperser. These photographic additives dispersed in the present invention are
The fine particles have an average particle size of 100 μm or less, but are usually used with an average fine particle size of 0.02 to 10 μm. As a dispersion method, a method of mechanically stirring at high speed (Japanese Patent Laid-Open No. Sho 5
No. 8-105141), a method in which the organic solvent is removed by heating and dissolving it in an organic solvent and dispersing it while adding the gelatin containing a surfactant or antifoaming agent and the hydrophilic polymer described above (JP-A-44-44). No. 22948) Dissolved in acids such as citric acid, acetic acid, sulfuric acid, hydrochloric acid, malic acid, etc.
To 7.5 in a polymer (Japanese Patent Application Laid-Open No. 50-80119), or by dissolving in an alkali such as sodium hydroxide, sodium hydrogen carbonate or sodium carbonate to obtain p.
A method in which crystals are precipitated and dispersed in a polymer such as gelatin having an H4.5 to 7.5 (JP-A-2-15252) can be applied. For example, hydrazine, which is difficult to dissolve in water, can be dissolved by referring to JP-A-2-3033,
This method can be applied to other additives. Also,
Dyes, sensitizing dyes, and inhibitors having a carboxyl group can increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxyl group. That is, it is preferable to add a calcium ion or a magnesium ion to the hydrophilic colloid layer in an amount of 200 to 4000 ppm to form a hardly soluble salt. The use of other salts is not limited as long as a hardly soluble salt can be formed. The method for dispersing the fine particles of the photographic additive can be arbitrarily applied to sensitizers, dyes, inhibitors, accelerators, contrast agents, contrast enhancement auxiliaries and the like according to the chemical and physical properties thereof.

The light-sensitive material used in the present invention can be used for simultaneous coating of a plurality of constituent layers of 2 to 10 layers at a high speed of 30 to 1000 meters per minute in US Pat. No. 3,63.
Known slide hopper type or curtain coating described in Nos. 6,374 and 3,508,947 can be used. In order to reduce unevenness during coating, it is preferable to lower the surface tension of the coating solution or to use the above-mentioned hydrophilic polymer which can impart a thixotropic property in which the viscosity is reduced by a shearing force.

The light-sensitive material used in the present invention includes a crossover cut layer, an antistatic layer, an antihalation layer,
A back coat layer may be provided.

A known method is used for packaging the photographic light-sensitive material used in the present invention. Since silver halide photographic materials are sensitive to heat and humidity, it is preferable to avoid storing them under severe conditions. Generally 5 ° C to 30 ° C
It is good to save in. Humidity is relative humidity 35% to 60
It is good to set it between%. 1 to 200 to protect from humidity
It is common practice to package in 0μ polyethylene. Polyethylene can suppress the permeation of water by improving the regularity of crystals by using a metallocene catalyst. In addition, moisture permeation can be suppressed by coating the surface of polyethylene by vapor deposition with a thickness of 0.1 to 1000 μm.

[0196]

The present invention will be specifically described below with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of support) (SPS synthesis) 1 part of styrene was added to 200 parts by weight of toluene.
The reaction was carried out at 96 ° C. for 8 hours using 00 parts by weight, 56 g of triisobutylaluminum and 234 g of pentamethylcyclopentadienyltitanium trimethoxide. After decomposing and removing the catalyst with a methanol solution of sodium hydroxide,
After washing three times with methanol, the target compound (SPS)
4 parts by weight were obtained.

(Preparation of SPS Film) Obtained SPS
Was melt-extruded from a T-die at 330 ° C. into a film and quenched and solidified on a cooling drum to obtain an unstretched film. At this time, the take-up speed of the cooling drum is set in two stages, and the thicknesses of 1370μ, 1265μ and 1054μ
The unstretched film of μ is preheated at 135 ° C. and longitudinally stretched (3.
After 1 time), the film was transversely stretched (3.4 times) at 130 ° C. and further heat set at 250 ° C. As a result, a biaxially stretched film having a bending elastic modulus of 450 kg / mm ² and a thickness of 100 μm was obtained as a support.

(Undercoating of SPS film) After vapor-depositing silica on the above SPS film, an undercoating layer containing styrene-glycidyl acrylate and tin oxide fine particles and subjected to an antistatic treatment was formed.

(Preparation of Silver Halide Emulsion A) Silver chlorobromide core grains having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which are composed of 70 mol% of silver chloride and the rest are silver bromide, are prepared by the simultaneous mixing method. Prepared. At the time of mixing the core particles, 8 × 10 ⁻⁸ mol of K ₃ RuCl ₆ was added per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ I
3 × 10 ⁻⁷ mol of rCl ₆ was added per mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.25.
μm core / shell monodisperse (variation coefficient 10%) (1
Chloroiodobromide (silver chloride 90
Mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, JP-A-2-280
Modified gelatin described in JP-A-139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, Japanese Patent Laid-Open No. 2-53967).
-280139, Exemplified compound G-8 on page 287 (3))
It was desalted using. EAg after desalting is 190 mv at 50 ° C
Met.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the obtained emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. PH of 5.6 and EAg of 123 mv, chloroauric acid was added in an amount of 2 × 10 ^-5 mol, and then inorganic sulfur was added in an amount of 3 × 10 ^-6 mol, and chemical aging was performed at a temperature of 60 ° C. until maximum sensitivity was obtained. . After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of silver halide emulsion B) 60 mol% of silver chloride, 2.5 mol% of silver iodide, the rest of which is silver bromide by the simultaneous mixing method, the average thickness is 0.05 μm, and the average diameter is 0.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. %, The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
Modified gelatin described in No. 9 (for example, a compound obtained by substituting an amino group in gelatin with phenylcarbamyl, exemplified compound G
It was desalted using -8). EAg after desalination is 18 at 50 ° C
It was 0 mv.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the obtained emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were added. Adjusted to pH 5.6 and EAg123mv, added 2 × 10 ⁻⁵ mol of chloroauric acid, and then added N, N,
3'10 ^-5 mol of N'-trimethyl-N'-heptafluoroselenourea was added and chemical ripening was carried out at a temperature of 60 ° C until maximum sensitivity was obtained. After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate making scanner for HeNe laser light source) On one undercoat layer of the above-mentioned support, a gelatin undercoat layer of the following Formulation 1 was added in an amount of 0.5 g of gelatin. / M ² on top of which silver halide emulsion layer 1 of Formula ² has a silver content of 1.5 g / m ² and a gelatin content of 0.5 g / m ² , and intermediate protection on the upper layer. As a layer, a coating solution of the following Formulation 3 was used so that the amount of gelatin was 0.3 g / m ² , and a silver halide emulsion layer 2 of Formulation 4 was further provided thereon with a silver amount of 1.4 g / m ² and a gelatin amount of 0. so that .4g / m ^2, further amount of gelatin coating solution having the following formulation 5 is simultaneous multilayer coating so as to be 0.6 g / m ^2. The following formulation 6 is applied on the undercoat layer on the opposite side.
So that the amount of gelatin in the backing layer is 0.6 g / m ² , a hydrophobic polymer layer of the following formulation 7 is further provided thereon, and a backing protective layer of the following formulation 8 is further provided thereon with a gelatin amount of 0.4 g / m ^2. A sample was obtained by simultaneous multi-layer coating with the emulsion layer side so as to obtain m ² .

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Dye AD so that the amount of silver becomes 1.5 g / m ² . -8 solid dispersed fine particles (average particle diameter 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² hydrazine derivative H-7 20 mg / m ² redox compound: RE-1 20 mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener g 5 mg / m ² S-1 0. 7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² formulation 3 (intermediate layer composition) gelatin 0.3 g / m ² S -1 2 mg / m ² formulation 4 (composition of silver halide emulsion layer 2) silver halide emulsion B so that the amount of silver becomes 1.4 g / m ² sensitizing dye d-1 3 mg / m ² sensitizing dye d-2 3 mg / m ² hydrazine derivative H-20 20 mg / m ² Nucleation accelerator: Exemplified compound Nb-12 40 mg / m ² Redox compound: RE-2 20 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² latex polymer ^{f 0.5g / m 2 S-1} 1.7mg / m 2 formulation 5 (emulsion protective layer composition) solid dispersion of gelatin 0.6 g / m ² dye AD-5 (average particle size ^{.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator: Example Compound Na-3 40mg / m ² 1,3- vinyl Sulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: K-1 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² sodium polystyrene sulfonate 20 mg / m ² compound i 100 mg / m ² Formulation 7 (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (Bucking) Protective layer) Gelatin 0.4 g / m ² Matting agent: Monodispersed polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / M ² Dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener: K-1 20 mg / m ²

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The surface resistivity of the backing side after coating and drying was 6 × 10 ¹¹ at 23 ° C. and 20% RH, and the film surface pH of the emulsion side surface was 5.5 and the swelling degree was 175. After performing the exposure described below on the obtained sample, at the start, add the use solution of the developer solution, the use solution of the fixer solution of the following composition and the rinse solution to the tank of the automatic processor, and perform the rapid processing. The automatic developing machine (GR-26SR, manufactured by Konica Corp.) was modified to a heat roller system in which the drying section was heated to 60 ° C., and the processing speed was changed to enable rapid processing under the following processing conditions. Processed. It should be noted that the developing solution used is 150 m per 1 m ^{2 of} the light-sensitive material in advance.
1, 180 ml of fixer solution and 250 rinse solution
While replenishing each ml, 100 sheets of large-sized film in which 80% of the area was blackened were processed per day, and this was run for 8 days to process 800 sheets in total. The evaluation is the performance after running 800 sheets. The surface resistivity of the backing side after the treatment was 3 × 10 ¹¹ at 23 ° C. and 20% RH.

<Treatment liquid formulation> 1. Starting developer (HAD-S) Working solution 1 L minute Pure water 224 ml DTPA.5Na 1.45 g Potassium sulfite 12.54 g Sodium sulfite 42.58 g KBr 4 g H ₃ BO ₃ 8 g Potassium carbonate 55 g 8-Mercaptoadenine 0.07 g Diethylene glycol 40 g 5-Methylbenzotriazole 0.21 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 0.85 g Hydroquinone 20 g KOH 18 g Make up to 400 mL with pure water. When used, 600 mL of pure water is mixed to make 1 L. P of the used liquid
H was 10.40.

2. Preparation of replenishment development tablet (HAD-JR) Preparation of granulation A parts (1 L of liquid used) DTPA / 5Na 1.45 g Sodium carbonate (monohydrate) 76.27 g D-mannitol (trade name: Kao) 6.94 g Sodium sulfite 56.58 g KBr 2 g D-sorbitol 2.93 g LiOH Amount shown in Table 1 KOH (or NaHSO ₄ ) pH adjustment amount The above materials were mixed in a commercially available vandal mill for 30 minutes, and further by a commercially available stirring granulator. After granulating at room temperature for 10 minutes, the granulated product is dried in a fluidized-bed dryer at 40 ° C. for 2 hours to be granulated product A.
Got the parts.

Preparation of Granulated B Parts (for 1 L of working solution) Sodium sulfite 56.58 g KBr 2 g H ₃ BO ₃ 4 g 8-mercaptoadenine 0.085 g 5-methylbenzotriazole 0.26 g 1-phenyl-5-mercaptotetrazole 0.06 g Dimezone S 1.25 g Sodium erythorbate Amount shown in Table 1 Hydroquinone 20 g Demol N (trade name: Kao) 5 g D-mannitol (trade name: Kao) 4.77 g N-lauroyltaurine (trade name: Nikko Chemicals) 2 g The above materials were mixed in a commercial vandal mill for 30 minutes, further granulated with a commercial stirring granulator at room temperature for 10 minutes, and then the granulated product was dried with a fluidized-bed dryer at 40 ° C. for 2 hours to granulate. Granule B
Got the parts.

The above-mentioned A part and B part were thoroughly mixed for 10 minutes, and the resulting mixture was used as Masina UD manufactured by Masina Co., Ltd.
・ 9.83 per tablet using DFE30 / 40 tableting machine
g to 1.5 tons / m ² by compression tableting.
25 tablets having a thickness of 10 mm and a thickness of 10 mm were obtained.

3. Comparative development replenisher (HAD-SR) Used solution 1 L minute Pure water 300 ml DTPA.5Na 1.45 g Sodium sulfite 56.58 g KBr 2 g H ₃ BO ₃ 4 g Sodium carbonate (monohydrate) 76.27 g 8-mercaptoadenine 0. 085 g 5-Methylbenzotriazole 0.26 g 1-Phenyl-5-mercaptotetrazole 0.06 g Dimezone S 1.25 g Sodium erythorbate Amount shown in Table 1 Hydroquinone 20 g LiOH Amount shown in Table 1 KOH (or NaHSO ₄ ) pH adjustment amount D-mannitol (trade name: Kao) 11.71 g sorbitol 2.93 g N-lauroyl taurine (trade name: Nikko Chemicals) 2 g Demol N (trade name: Kao) 5 g Make up to 500 mL with pure water. When used, 500 mL of pure water and 500 mL of the above concentrated liquid are mixed and used. The pH of the replenisher was 10.70.

[0215] Starting fixer (HAF-S) 1 L of used solution Pure water 116 ml Ammonium thiosulfate (10% Na salt: Hoechst) 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate / trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate-18 hydrate 18 g Make up to 400 mL with pure water. When used, 600 ml of pure water and the above-mentioned concentrated liquid are mixed and used. The pH of the working solution was 4.83.

5. Preparation of replenishing fixed tablet Preparation of granulated A parts (1 L of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium metabisulfite 7.5 g Sodium acetate 40 g Pineflow (trade name: Matsutani Chemical) 11 0.8 g The above materials were mixed in a commercial vandal mill for 30 minutes, further granulated with a commercial stirring granulator at room temperature for 10 minutes, and the granulated product was dried in a fluidized-bed dryer at 40 ° C. for 2 hours. Granulated product A
Got the parts.

Preparation of Granulated B Parts (1 L of Liquid Used) Boric Acid 10 g Tartaric Acid 3 g Sodium Hydrogen Sulfate 26.5 g Aluminum Sulfate / 18-hydrate 15.8 g D-Mannitol (trade name: Kao) 4.4 g N-Lauroyl taurine (Brand name: Nikko Chemicals) 2 g Demol N (Brand name: Kao) 5 g The above materials are mixed in a commercial vandal mill for 30 minutes, and further granulated by a commercial stirring granulator at room temperature for 10 minutes, and then granulated. The product is dried in a fluidized-bed dryer at 40 ° C. for 2 hours and granulated product B
Got the parts.

[0218] The above-mentioned A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was used as Masina UD manufactured by Masina Co.
・ 1 tablet per tablet using DFE30 / 40 tableting device
Twenty-five tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting with a filling amount of g of 1.5 tons / m ² . At the time of use, 25 tablets are used by dissolving them in pure water so that the volume becomes 1 L. The pH of the working solution was 4.20.

<Self-developing machine> GR-26 manufactured by Konica Corporation was used. Replenisher made from concentrated liquid or tablets,
40 ml of development and 40 ml of fixing were replenished for each sheet of photosensitive material of large size (610 × 508 mm).

Processing conditions Temperature Time Development 35 ° C. 30 seconds Fixing 34 ° C. 20 seconds Washing at room temperature 20 seconds Drying 45 ° C. 20 seconds Line speed (conveying speed) 984 mm / min <Evaluation> Development replenishing concentrated solution (double concentration) and tablets Container made of polyethylene terephthalate (oxygen permeability 45 ml /
atm ・ m ²・ 25 ・ day), the temperature is 5
It was used after being stored at 0 ° C. for 3 days and then opened.

New liquid and photosensitive material (blackening rate 50%) 100
The sensitivity, γ, and dot quality (DQ) after processing 0 sheets were evaluated.

(Relative Sensitivity Evaluation Method) As a substitute evaluation for HeNe laser exposure, exposure was performed through an optical wedge for 10 ⁻⁶ seconds using an interference filter of 633 nm, and then the above treatment was performed. The developed sample thus obtained was measured with a Konica digital densitometer PDA-65 to obtain a concentration of 2.
The relative sensitivity is shown with the sensitivity in 5 being 100.

(Evaluation Method of γ) Gamma is expressed as a tangent of the densities of the above-mentioned processed film of 0.1 and 3.0. When the γ value is less than 6, it is a photosensitive material which cannot be used. Insufficient contrast. When the γ value is 10 or more, a super-high contrast image can be obtained for the first time, indicating that the photosensitive material is sufficiently practical.

(Evaluation method of DQ) Exposure was carried out with a 16-micron random pattern halftone dot (FM screen) using SG-747RU manufactured by Dainippon Screening Co., Ltd., and then the above-mentioned processing was carried out. The middle point of the halftone dot pattern (target 50%) was visually evaluated using a 100-fold loupe to evaluate the rank. The highest rank was 5 and the ranks were evaluated as 4, 3, 2, 1 due to deterioration of halftone dot quality. A rank of 2 or lower is a level that cannot be put to practical use. Table 1 shows the results.

[0225]

[Table 1]

As is clear from Table 1, in the present invention using the replenisher prepared from the solid processing agent, the running stability is remarkably improved and the image quality is also good.

Example 2 The same evaluation as in Example 1 was carried out by changing the composition of the developing solution as follows. The light-sensitive material, the developing machine, and the fixing solution used in Example 1.

<Treatment liquid formulation> 1. Starting developer (HAD-S) Same as in Example 1. Preparation of replenishment development tablet (HAD-JR2) Preparation of granulated A2 parts (for 1 L of liquid used) DTPA / 5Na 1.45 g Sodium carbonate (monohydrate) 76.27 g D-mannitol (trade name: Kao) 6.94 g Sodium sulfite 56.58 g KBr 2 g D-sorbitol 2.93 g LiOH 10 g The above materials were mixed in a commercially available vandal mill for 30 minutes, and further granulated for 10 minutes at room temperature with a commercially available stirring granulator, and then the granulated product was obtained. Granulated product A dried at 40 ° C for 2 hours in a fluidized-bed dryer
I got 2 parts.

Preparation of Granulated B2 Parts (for 1 L of working liquid) Sodium sulfite 56.58 g KBr 2 g H ₃ BO ₃ 4 g 8-mercaptoadenine 0.085 g 5-methylbenzotriazole 0.26 g 1-phenyl-5-mercaptotetrazole 0.06 g Dimezone S 1.25 g Sodium erythorbate Amount shown in Table 2 Hydroquinone 20 g Demol N (trade name: Kao) 5 g D-mannitol (trade name: Kao) 4.77 g N-lauroyltaurine (trade name: Nikko Chemicals) 2 g Compound of general formula (2) Amount shown in Table 2 The above materials are mixed in a commercial vandal mill for 30 minutes, and further granulated for 10 minutes at room temperature with a commercial stirring granulator, and then the granulated product is placed in a fluidized tank. Granulate B dried at 40 ° C for 2 hours in a dryer
I got 2 parts.

[0230] The above A2 part and B2 part were thoroughly mixed for 10 minutes, and the resulting mixture was mixed with 9. 9 pieces per tablet using a Masina UD / DFE30 / 40 tableting machine manufactured by Masina Co., Ltd.
It was filled with 83 g and compressed to 1.5 tons / m ² to obtain 25 tablets having a diameter of 30 mm and a thickness of 10 mm.

3. Comparative development replenisher (HAD-SR2) Working solution 1 L minute Pure water 300 ml DTPA · 5Na 1.45 g Sodium sulfite 56.58 g KBr 2 g H ₃ BO ₃ 4 g Sodium carbonate (monohydrate) 76.27 g 8-mercaptoadenine 0. 085 g 5-methylbenzotriazole 0.26 g 1-phenyl-5-mercaptotetrazole 0.06 g Dimezone S 1.25 g sodium erythorbate Amount shown in Table 2 Hydroquinone 20 g LiOH 10 g D-mannitol (trade name: Kao) 11.71 g sorbitol 2.93 g N-lauryl taurine (trade name: Nikko Chemicals) 2 g Demol N (trade name: Kao) 5 g Compound of general formula (2) Amount shown in Table 2 Pure water is used to make up to 500 mL. When used, 500 mL of pure water and 500 mL of the above concentrated liquid are mixed and used. The pH of the replenisher was 10.70.

[0232]

[Table 2]

As is clear from Table 2, the present invention using the replenisher prepared from the solid processing agent has significantly improved running stability and good image quality.

Example 3 <Preparation of Photosensitive Material> (Preparation of Emulsion) 98 mol% of silver chloride was prepared by the simultaneous mixing method.
Monodisperse, cubic silver chlorobromide grains having an average grain size of 0.15 μm containing 2 mol% of silver bromide were prepared. When mixed, K ₃ Rh (H ₂
O) Br5 was added at 7 × 10 ⁻⁵ mol per mol of silver. In addition, 4-hydroxy-6-methyl-1,3,3a, 7- before the desalting step of removing soluble salts by a conventional method.
0.6 g of tetrazaindene was added per 1 mol of silver (hereinafter, unless otherwise specified, the amount is based on 1 mol of silver).

The temperature of this emulsion was raised to 60 ° C., 60 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 0.75 mg of sodium thiosulfate were added, and 4-hydroxy-6 was added. -Methyl-1,3,3a, 7-
After 60 seconds from the addition of tetrazaindene, 600 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was further added and the temperature was lowered to set.

(Preparation of Emulsion Coating Solution) The coating solution was adjusted to the following amount per 1 m ² .

The above silver halide emulsion so that the amount of silver becomes 3.1 g / m ² 10% gelatin solution 5.26 ml / m ² NaOH (0.5N solution) 4.39 ml / m ² compound (a) 6.53 mg / m ² tetrazolium compound (T-7) 40 mg / m ² Quillaja saponin 107 mg / m ² compound (ii) 18.5 mg / m ² compound (iii) 9.8 mg / m ² of gelatin latex 480 mg / ^{m 2} sodium polystyrenesulfonate 52.2 mg / m ² (protective layer preparation of lower layer coating solution) gelatin 0.5 g / m ² compound (d) 62.0 mg / m ² citric acid 4.1 mg / m ² formalin 1.7 mg / m ² of polystyrene sulphonic acid Sodium 11.0 mg / m ² (Preparation of coating solution for upper layer of protective layer) Gelatin 0.3 g / m ² Compound (e) 18.0 mg / m ² Compound (d) 48. 4 mg / m ² Compound (f) 105.0 mg / m ² Compound (g) 1.25 mg / m ² amorphous silica (average particle 1.63μm) 15.0mg / m ² amorphous silica (average particle size 3.5μm ) 21.0 mg / m ² citric acid 4.5 mg / m ² sodium polystyrene sulfonate 11.0 mg / m ² formalin (with in-line addition) 10.0 mg / m ² (preparation of backing coating solution) compound (h) 170 mg / m ² compound (d) 30 mg / m ² compound (ri) 45 mg / m ² compound (nu) 10 mg / m ² quillaja saponin 111 mg / m ² compound (l) 200 mg / m ² colloidal silica 200 mg / m ² compound (e) 35 mg / m ² compound (Wa) 31 mg / m ² compound (f) 3.1 mg / ^{m 2} of polymethyl methacrylate acid polymer 28.9 mg / m ² (average particle 5.6 [mu] m) glyoxal 10.1 mg / m ² Citric acid 9.3 mg / m ² sodium polystyrenesulfonate 71.1 mg / m additive compound the following ^2-line (yo) 81 mg / m ² Compound (motor) 88. 2 mg / m ² calcium acetate 3.0 mg / m ² formalin 10 mg / m ²

[0238]

Embedded image

[0239]

Embedded image

[0240]

Embedded image

<Treatment liquid formulation> 1. Starting developer (TAD-S3) Working solution 1 L minute Pure water 350 ml DTPA / 5Na 1.45 g Sodium sulfite 15.76 g KBr 2.5 g Potassium carbonate 40 g Potassium hydrogen carbonate 10 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzo Triazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.02 g Dimezone S 1.6 g Elbit N 45 g Sodium hydrogensulfate pH adjustment amount Make up to 400 mL with pure water. When used, 600 mL of pure water and the above concentrated liquid are mixed and used. The pH of the working solution was 9.80.

[0242] 2. Preparation of replenishment development tablet (TAD-JR3) Preparation of granulated A3 parts (for 1 L of liquid used) DTPA / 5Na 1.45 g Potassium carbonate 40 g LiOH Amount shown in Table 3 D-mannitol (trade name: Kao) 4.9 g Above The materials are mixed in a commercial vandal mill for 30 minutes, further granulated with a commercial stirred granulator at room temperature for 10 minutes, and then the granulated product is dried with a fluidized-bed dryer at 40 ° C. for 2 hours to form a granulated product. A
I got 3 parts.

Preparation of Granulated B3 Parts (1 L Used Solution) Sodium Sulfite 15.76 g KBr 2.5 g Potassium Bicarbonate 10 g 8-Mercaptoadenine 0.06 g 5-Methylbenzotriazole 0.4 g 1-Phenyl-5-mercapto Tetrazole 0.02g Dimezone S 1.6g Erbit N 45g Sodium hydrogensulfate pH adjustment amount D-mannitol (trade name: Kao) 5.22g N-lauroyltaurine (trade name: Nikko Chemicals) 1g Demol N (trade name: Kao) 5 g The above materials were mixed in a commercial vandal mill for 30 minutes, further granulated with a commercial stirring granulator at room temperature for 10 minutes, and then the granulated product was dried in a fluidized-bed dryer at 40 ° C. for 2 hours to be granulated. Granule B
I got 3 parts.

The above A3 parts and B3 parts were thoroughly mixed for 10 minutes, and the resulting mixture was used in a Masina UD / DFE30 / 40 tableting machine manufactured by Masina Co., Ltd. at 1.5 tons /
Ten tablets each having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting with m ² . At the time of use, 10 tablets are dissolved in pure water so that the volume becomes 1 L. PH of liquid used
Was 9.80.

3. Comparative development replenisher (TAD-SR3) 1 L portion of working solution Pure water 350 ml DTPA / 5Na 1.45 g Sodium sulfite 15.76 g KBr 2.5 g Potassium carbonate 40 g Potassium hydrogen carbonate 10 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methyl Benzotriazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.02 g Dimezone S 1.6 g Elbit N 45 g sodium hydrogensulfate pH adjustment amount LiOH Amount shown in Table 3 D-mannite 10.11 g N-lauroy taurine (trade name) : Nikko Chemicals) 1g Demol N (trade name: Kao) 5g Make up to 500mL with pure water. When used, 500 ml of pure water and the above concentrated liquid are mixed and used. The pH of the replenisher was 9.80. The fixing agent used was that used in Example 1.

<Automatic machine> GR-26S manufactured by Konica Corporation
R was used. Concentrated liquid or replenisher made from tablets is a photosensitive material of large size (610 x 508 mm).
Replenishment of 60 ml of developing and 80 ml of fixing was performed per sheet.

Processing conditions Temperature Time Development 35 ° C. 15 seconds Fixing 34 ° C. 10 seconds Washing at room temperature 10 seconds Drying 45 ° C. 10 seconds Line speed (conveying speed) 1968 mm / min <Evaluation> Replenishing concentrated liquid (double concentration) and tablets are polyethylene. Container made of terephthalate (oxygen permeability 45 ml / at
m ・ m ²・ 25 ・ day), temperature is 50 ℃
It was stored for 3 days and then opened and used.

The new liquid and the above-mentioned light-sensitive material (blackening rate 20
%) Was used to evaluate the image quality of γ after the 1000 sheets were processed, and the results are shown in Table 3.

(Evaluation Method of Character Quality of Blank Characters and γ Evaluation) A prepared original is brought into close contact with the emulsion surface of a sample of a light-sensitive material and the US Fus.
Bright room printer P6 using the electrodeless discharge tube light source made by ION
Image exposure was carried out at 27 FM, and the image quality of the extracted characters in the above development processing was evaluated by 5 ranks. As for the character quality 5 without characters,
This is the image quality with which characters of 30 μm width can be reproduced when suitable exposure is performed so that the dot area of 50% becomes the dot area of 50% on the light-sensitive material.
The blank character image quality 1 is 150 when the same appropriate exposure is given.
It is an image quality that can reproduce only characters of μm or more, and it is a poor character quality. 3 or more is a level that can withstand practical use.

Γ = (1.0-0.1) / {log (exposure amount giving a density of 1.0) -log (exposure amount giving a density of 0.1)} cannot be used if the γ value is less than 6. The light-sensitive material of No. 6 and less than 6 and less than 10 still have insufficient hardness. γ value is 10
For the first time, a super-high contrast image is obtained, which means that the material is a sufficiently sensitive photosensitive material.

[0251]

[Table 3]

From Table 3, it is understood that according to the processing method of the present invention (replenishment of the developing solution with the solid processing agent), there is almost no image deterioration even when the running developing solution is used.

Example 4 The light-sensitive material described in Example 3 was used and processed with the processing solution described below. The starting developer, the fixer, and the developing machine were the same as in Example 3.

<Treatment liquid formulation> 1. Preparation of replenishment development tablet (TAD-JR4) Preparation of granulated A4 parts (1 L of liquid used) DTPA / 5Na 1.45 g Potassium carbonate 40 g D-mannitol (trade name: Kao) 4.9 g The above materials in a commercial Vandal mill After mixing for 30 minutes with a commercial agitation granulator at room temperature for 10 minutes, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain granulated product A.
I got 4 parts.

Preparation of Granulated B4 Parts (for 1 L of working liquid) Sodium sulfite 15.76 g KBr 2.5 g Potassium hydrogen carbonate 10 g 8-Mercaptoadenine 0.06 g 5-Methylbenzotriazole 0.4 g 1-Phenyl-5-mercapto Tetrazole 0.02g Dimezone S 1.6g Erbit N 45g Sodium hydrogensulfate pH adjustment amount D-mannitol (trade name: Kao) 5.22g N-lauroyltaurine (trade name: Nikko Chemicals) 1g Demol N (trade name: Kao) 5 g Compound of general formula (2) Amount shown in Table 4 The above materials were mixed in a commercially available vandal mill for 30 minutes and further granulated for 10 minutes at room temperature with a commercially available stirring granulator, and then the granulated product was placed in a fluidized tank. Granulate B dried at 40 ° C for 2 hours in a dryer
I got 4 parts.

The above A4 parts and B4 parts were thoroughly mixed for 10 minutes, and the resulting mixture was used in a Masina UD / DFE30 / 40 tableting machine manufactured by Masina Co., Ltd. at 1.5 tons /
Ten tablets each having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting with m ² . At the time of use, 10 tablets are dissolved in pure water so that the volume becomes 1 L. PH of liquid used
Was 9.80.

2. Comparative development replenisher (TAD-SR4) Working solution 1 L minute Pure water 350 ml DTPA / 5Na 1.45 g Sodium sulfite 15.76 g KBr 2.5 g Potassium carbonate 40 g Potassium hydrogen carbonate 10 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methyl Benzotriazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.02 g Dimezone S 1.6 g Elbit N 45 g Sodium hydrogen sulfate pH adjusting amount Compound of general formula (2) Amount shown in Table 4 Mannit 10.11 g N-lauroyl Taurine (product name: Nikko Chemicals) 1 g Demol N (product name: Kao) 5 g Make up to 500 mL with pure water. When used, 500 ml of pure water and the above concentrated liquid are mixed and used. The pH of the replenisher was 9.80.

Evaluation was carried out in the same manner as in Example 3, and the results are shown in Table 4.
Shown in

[0259]

[Table 4]

From Table 4, it can be seen that the method for replenishing the developing solution with the solid processing agent of the present invention is excellent.

Example 5 (Preparation of Silver Halide Emulsion C) A controlled double jet of a silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr was carried out so that the silver halide composition was 80 mol% silver chloride and 20 mol% silver bromide. Method to mix to grow silver halide grains. At this time, the mixture is 36 ° C, pAg 7.8, pH 3.0.
The above conditions were used, and during grain formation, K ₃ RuCl ₆ was added in an amount of 8 × 10 ^-8 mol per mol of silver and K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver. After that, desalting was performed with modified gelatin treated with phenylisocyanate, and ossein gelatin was added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.18 μm and a coefficient of variation of 10%.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the emulsion thus obtained in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and potassium bromide were added. PH of 5.6 with addition of citric acid, EAg12
After adjusting to 3 mV and adding 2 × 10 ⁻⁵ mol of chloroauric acid, 2 × 10 ⁻⁶ mol of N, N, N′-trimethyl-N′-heptafluoroselenourea was added and the maximum temperature was 60 ° C. Chemical ripening was performed until the sensitivity was reached.

After completion of aging, 4-methyl-6-hydroxy-
1,3,3a, 7-Tetrazaindene was added in an amount of 3 × 10 ^-3 mol per mol of silver.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for He-Ne laser light source) On one undercoat layer of SPS support, a gelatin undercoat layer of the following Formulation 1 was prepared with a gelatin content of 1. such that 0 g / m ^2, amount of silver 3.5 g / m ² of silver halide emulsion layers of the formulation 2 thereon, so that the amount of gelatin is 1.5 g / m ^2, further coating the following formulation 3 The solution was applied simultaneously in multiple layers so that the amount of gelatin was 0.6 g / m ² . A backing layer having the following formulation 4 was provided on the opposite side undercoating so that the amount of gelatin was 2.0 g / m ^2, and a backing protective layer having the following formulation 5 was provided at a gelatin amount of 1.0 g / m ^2. A sample was obtained by simultaneous multi-layer coating with the emulsion layer side so as to obtain m ² .

Formulation 1 (gelatin undercoat layer composition) Gelatin 1.0 g / m ² 1-phenyl-5-mercaptotetrazole 1 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 0.4 mg / m ² Formulation 2 (Silver Halide Emulsion Layer Composition) Silver Halide Emulsion C Silver amount 3.5 g / m ² Sensitizing dye d-1 3 mg / m ² Sensitizing dye d-2 3 mg / m ² Pyridinium salt derivative (N-24) 52 0.5 mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² styrene - hydrophilic polymer maleic acid copolymer (thickener) 15 mg / m ² disodium ethylenediaminetetraacetate 30 mg / m ² formulation 3 (emulsion protective layer composition) gelatin 0.6 g / ² S-1 12mg / m ² Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² colloidal silica ( Average particle size 0.05 μm) 20 mg / m ² Hardener K-1 30 mg / m ² Formulation 4 (Backing layer composition) Gelatin 2.0 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 5 (backing protective layer) Gelatin 1.0 g / m ² Matting agent (average particle size 5 μm monodispersed polymethyl ^{methacrylate) 50mg / m 2 S-1} 10mg / m 2 surfactant h 1 mg / m ² dye ^{k 20mg / m 2 H- (OCH} 2 C of _{²⁾ 68} -OH 50mg / m ₂ hardener g 20 mg / m ² processing conditions and evaluation method were the same as in Example 1. (The structures of the compounds used are shown in Chemical formulas 49 to 51). Table 5 shows the results.

[0266]

[Table 5]

From Table 5, it can be seen that the processing method of the present invention exhibits stable performance even in the running processing of a light-sensitive material using a pyridinium salt as a contrast-increasing agent.

Example 6 Using the light-sensitive material of Example 5, the processing conditions and the evaluation method were the same as in Example 1, and the results are shown in Table 6.

[0269]

[Table 6]

From Table 6, it can be seen that the processing method of the present invention exhibits stable performance even in the running processing of a light-sensitive material using a pyridinium salt as a contrast-increasing agent.

[0271]

According to the present invention, a black-and-white silver halide photograph having significantly improved processing stability during running even when a large amount of running processing is performed in a state where the environment is not deteriorated and the developer replenishment amount is reduced. A solid processing agent for a light-sensitive material and a processing method are obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 5/31 G03C 5/31

Claims (10)

[Claims] 1. A dihydroxybenzene developing agent and Li.
A solid processing agent for black-and-white silver halide photographic light-sensitive material, which contains OH. 2. A solid processing agent for a black-and-white silver halide photographic light-sensitive material, which contains a developing agent represented by the following general formula (1) and LiOH. Embedded image In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, and R ₁ and R ₂ are bonded to each other. You may form a ring. k represents 0 or 1, and k is 1
Then X represents a -CO- or -CS- group. M ₁ , M ₂
Each represents a hydrogen atom or an alkali metal atom. 3. A black-and-white silver halide photographic light-sensitive material according to claim 1, wherein LiOH is contained in a weight ratio of 0.1 to 20 wt% with respect to the dihydroxybenzenes contained in the developer. Solid developer. 4. The above general formula (1) and the following general formula (2):
A solid processing agent for a black-and-white silver halide photographic light-sensitive material, comprising a compound represented by: Embedded image In the formula, one of Y and Z represents a nitrogen atom, and the other represents a methine group. R ₀ is a hydrogen atom, a lower alkyl group,
Represents a halogen atom or a nitro group. 5. The solid processing agent for a black-and-white silver halide photographic light-sensitive material according to claim 4, wherein the developing agent is dihydroxybenzenes. 6. The compound represented by the general formula (2) above,
The solid developer for a black-and-white silver halide photographic light-sensitive material according to claim 4 or 5, characterized in that the solid developer is contained in an amount of 0.1 to 10 wt% with respect to the dihydroxybenzenes contained in the developer. 7. A black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer and / or other constituent layers. 7. A processing method for a black-and-white silver halide photographic light-sensitive material, which comprises processing with a development replenisher prepared from the solid processing agent according to any one of items 1 to 6. 8. A black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a tetrazolium salt compound in the emulsion layer and / or other constituent layers. 7. A method of processing a black-and-white silver halide photographic light-sensitive material, which comprises processing with a development replenisher prepared from the solid processing agent according to any one of 1 to 6. 9. A black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a pyridinium salt compound in the emulsion layer and / or other constituent layers. 7. A method of processing a black-and-white silver halide photographic light-sensitive material, which comprises processing with a development replenisher prepared from the solid processing agent according to any one of 1 to 6. 10. A developer replenishing amount is 10 to 200 cc /
The method for processing a black-and-white silver halide photographic light-sensitive material according to any one of claims 7 to 9, characterized in that it is m ² or less.