JP2748059B2 - Developer for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof. (Also referred to as silver sludge), and to facilitate maintenance of the automatic processor.

[0002]

2. Description of the Related Art Generally, in developing processing of a silver halide photographic light-sensitive material, an automatic developing machine (hereinafter referred to as an automatic developing machine) has been increasing in terms of speed, simplicity and handling. In the development processing of a black-and-white photosensitive material, a large amount of sulfite is used in a developing solution in order to maintain the developing activity and to minimize so-called air oxidation of a developing agent. On the other hand, in recent years, demands for rapid processing in the development processing of silver halide photographic materials have been increasing. For rapid processing, it is necessary to increase the activity of the developer. The activity of the developing solution can be increased by increasing the concentration of the developing agent or the pH of the developing solution, but the deterioration due to air oxidation is remarkable, and it is difficult to maintain the activity of the developing solution.

[0003] In general, a sulfite is added to maintain the activity of a developer. However, when processing is performed with a developer containing a compound having a dissolving effect on silver halide such as sulfite, a large amount of silver complex is eluted from the silver halide photographic material in the developer. The silver complex eluted in the developing solution is reduced by the developing agent, and silver is deposited and accumulated in a developing tank, a vat, a developing tank of an automatic developing machine, a roller, and the like. This is also referred to as silver stain or silver sludge, which adheres to the photosensitive material to be processed and stains the image, so that periodic cleaning and maintenance of the equipment is required.

Therefore, if the amount of sulfite added is increased to maintain the activity of the developer, the amount of silver complex eluted into the developer increases, the degree of silver stain increases, and the advantage of rapid processing is reduced. There are drawbacks that cannot be exploited.

Various means have been studied for increasing the speed of photographic light-sensitive materials. One of them is to reduce the total amount of the hydrophilic binder in the non-light-sensitive upper layer above the light-sensitive emulsion layer (also referred to as reducing the PC thickness). However, when the amount of the hydrophilic binder is reduced, the elution of the silver complex from the light-sensitive material into the developer increases, and the silver complex is reduced in the developer and causes silver staining.

[0006] As a method for reducing the silver stain, there is known a method of reducing silver ions eluted and / or reducing silver ions as disclosed in JP-A-56-24347, JP-B-56-46585 and JP-B-62-2849. A method of adding a compound that suppresses reduction to silver is known. However, those compounds act to suppress development itself,
Or it quickly loses its effect due to air oxidation,
It is not fully satisfactory as a silver stain generation inhibitor.

[0007]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for processing silver halide photographic compound materials which can be rapidly processed, firstly in a developing tank and / or a developing rack.
To reduce silver stains on the rollers, second, to facilitate maintenance of self-developing machines and developing equipment, third, to reduce silver stains without affecting photographic characteristics at all, The purpose is to reduce silver contamination without impairing the stability of the developer.

[0008]

The object of the present invention is to provide at least one of the compounds represented by the following general formula (I) and one as a constituent atom of a 5-membered ring represented by the following general formula (II) This has been attained by a developer for a silver halide photographic light-sensitive material, characterized in that the developer contains at least one kind of a 5-membered ring hetero compound having three or less nitrogen atoms and at least one mercapto group.

The general formula (I) will be described below.

[0010]

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In the formula, R ₁ and R ₂ are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, a halogen atom , An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and an alkoxy group. The alkyl group, the aryl group, the aralkyl group, the amino group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the sulfamoyl group, and the alkoxy group may further have a substituent, and these substituents may be R ₁ , R _Two
The groups mentioned in (1) can be similarly exemplified. Also, R ₁ ,
R ₂ may be linked to form a ring structure.

[0012] R ₁ Preferred examples of R _1, R _2, R ₂
Has an alkyl group which may have a substituent having 1 to 10 carbon atoms, an aryl group which may have a substituent having 6 to 12 carbon atoms, or a substituent which has 7 to 12 carbon atoms. And aralkyl, nitro, cyano, and halogen atoms. The sum of carbon numbers of R ₁ and R ₂ is 2 to 20
Are preferred examples. The case where R ₁ and R ₂ are linked to form a saturated 5- or 6-membered ring is also a preferred example.

[0013] R ₁ More preferable examples of R _1, R ₂
A hydrogen atom, or an alkyl group having an amino group or a hetero ring as a substituent, an alkyl group which may have a substituent having 1 to 10 carbon atoms as R ₂ , a substituent having 6 to 12 carbon atoms And a case where R ₁ and R ₂ are connected to each other to form a saturated 5- or 6-membered ring. Specific examples include a dimethylaminomethyl group, a morpholinomethyl group, an N-methylpiperazinylmethyl group as R ₁ ,
Examples thereof include a pyrrolidinylmethyl group. R ₂
Examples thereof include a methyl group, an ethyl group, a phenyl group, and a p-methoxyphenyl group.

The general formula (II) will be described below. General formula (II)

[0015]

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In the formula, X and Y each represent a nitrogen atom or CR ₃ , and Z represents a sulfur atom or NR ₄ . X and Y may be linked to form a condensed ring. However, the number of nitrogen atoms as constituent atoms of the five-membered ring is one or more and three or less. Preferred examples of the constituent atoms of the 5-membered ring include two nitrogen atoms. R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group,
Represents a nitro group, a cyano group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and an alkoxy group. The alkyl group, the aryl group, the aralkyl group, the amino group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the sulfamoyl group, and the alkoxy group may further have a substituent, such as R ₃ , R _The groups mentioned in ₄ can be similarly mentioned.

Preferred examples of R ₃ and R ₄ include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent and a substituent having 1 to 12 carbon atoms. Examples include an aryl group, a pyridyl group, a sulfo group, a carboxy group, and a hydroxy group. X and Y may be linked to form a condensed ring. Preferred examples include a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring and a pyrimidine ring, wherein the sulfo group, carboxy group and hydroxy group are substituted. It may be. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium, or a quaternary phosphonium.

Specific examples of the compound represented by formula (I) include the following compounds, but are not limited thereto.

[0019]

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[0020]

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[0021]

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Specific examples of the compound represented by the general formula (II) include, but are not limited to, the following compounds.

[0023]

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[0024]

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[0025]

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The above compounds can be easily synthesized by generally well-known methods. The following is a reference document. US Patent 2,585,388
No. 2,541,924, No. 3,26
6,897, British Patent 1,275,701, JP-A-56-111846, JP-B-42
No. 21842, Journal of Heterocyclic Chemistr
y Volume 15 Issue 981 (1978) Comprehensive Heterocycli
c Chemistry, Volume 3, pp. 40-56, pp. 106-142, 17
Pages 9-191. The Journal of American Chemical Socie
ty, Volume 67, 2197-2200 (1945).

The preferable addition amount of the compound of the present invention is 0.01 to 100 mmol per liter of the developing solution.
More preferably, it is 0.1 to 10 mmol. The mixing ratio may be any ratio, but is preferably a general formula [I]
100 to 0.01 times (molar ratio) when the compound of formula 1 is 1
And more preferably 10 to 0.1 times (molar ratio).

The developer for developing the light-sensitive material in the present invention can contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, and a chelating agent). . In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used. The developing agent used in the developer used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes, and furthermore, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones in terms of developing ability or Combinations of dihydroxybenzenes and p-aminophenols are preferred. Hydroquinone as a dihydroxybenzene developing agent used in the present invention,
Chlorohydroquinone, isopropylhydroquinone,
There are methylhydroquinone and the like, but hydroquinone is particularly preferred. The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. Among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene developing agent is usually 0.1.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. Dihydroxybenzenes and 1
When a combination of -phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / L to 0.5 mol / L, and the latter is 0.06 mol / L.
It is preferable to use it in an amount of not more than mol / liter.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like.
Sulfite is used in an amount of 0.20 mol / l or more, particularly 0.3 mol / l or more. However, if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is 1.2 mol / l. It is desirable. As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.
Additives other than those described above include development inhibitors such as sodium bromide and potassium bromide; ethylene glycol, diethylene glycol, triethylene glycol,
Organic solvents such as dimethylformamide; alkanolamines such as diethanolamine and triethanolamine;
A development accelerator such as imidazole or a derivative thereof; a mercapto-based compound such as 1-phenyl-5-mercaptotetrazole, an indazole-based compound such as 5-nitroindazole, or a benzotriazole-based compound as an antifoggant or black pepper (black pepper) inhibitor The composition may further contain a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and the like, if necessary. Further, as a development unevenness preventing agent, JP-A-6
The compound described in 2-212651 and the compound described in JP-A-61-267759 can be used as a dissolution aid.

In the developer used in the present invention, boric acid described in JP-A-62-186259, saccharides (eg, saccharose) and oximes (eg, aceto Oximes), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like,
Preferably, boric acid is used. Transport cost of processing liquid,
For the purpose of packaging material cost, space saving, and the like, it is preferable that the treatment liquid is concentrated and diluted at the time of use. For concentration of the developer, it is effective to convert a salt component contained in the developer into potassium salt.

The fixing agent for the fixing solution used in the present invention includes sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of these known fixing agents can be varied as appropriate, and is generally about 0.1 to about 2 mol / l.
The fixing solution may optionally contain a hardener (for example, a water-soluble aluminum compound), a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), or a pH adjuster (for example, ammonia). , Sulfuric acid), chelating agents, surfactants,
It may contain a wetting agent and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
And amphoteric surfactants described in JP-A-6740. In addition, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754, 58-122535, and 5
No. 8-122536, thiourea derivatives, alcohols having a triple bond in the molecule, US Pat.
Thioether compounds described in JP-A-59-59, and compounds described in JP-A-2-44355 may be used. As the pH buffer, for example, acetic acid, malic acid,
Organic acids such as succinic acid, tartaric acid and citric acid, and inorganic buffers such as boric acid, phosphate and sulfite can be used. Preferred are acetic acid, tartaric acid, boric acid and sulfite. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and is 0.01 to 1.0.
Mol / l, more preferably about 0.02 to 0.6 mol / l. Further, a compound described in JP-A-64-4739 can be used for promoting the dissolution of the dye.

As the hardener in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol / l, more preferably 0.03 to 0.08 mol / l. The effects of the present invention are exhibited regardless of the presence or absence of a hardener. The fixing temperature and time are preferably from about 20 ° C. to about 50 ° C. for 5 seconds to 1 minute. The replenishment rate of the fixing solution is 600 ml / m ² or less, and particularly preferably 450 ml / m ² or less.

The photosensitive material which has been subjected to development and fixing is then washed or stabilized. The washing or stabilizing treatment can be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide photosensitive material. In other words, not only water saving processing becomes possible,
It is possible to eliminate the need for piping for installing the automatic processing machine. When washing with a small amount of water, JP-A-63-18350, 6
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in 2-287252 and the like. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in As described in JP-A-235133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing tank to prevent contamination by the dye eluted from the photosensitive material. In some cases, a stabilization treatment may be performed after the water washing treatment.
No. 1357, No. 2-132435, No. 1-1255
No. 3, a bath containing the compound described in JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, an ammonium compound, Bi, A
Metal compounds such as l, optical brighteners, various chelating agents, films
pH adjusters, hardeners, fungicides, fungicides, alkanolamines and surfactants can also be added. Water used in the washing or stabilization process is sterilized by tap water, deionized water, halogen, ultraviolet germicidal lamp, various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use water, and washing water containing the compound described in Japanese Patent Application No. 2-147076 may be used.

In the development processing of the present invention, the development time is 60 seconds or less, preferably 6 seconds to 30 seconds, and the development temperature is 25 ° C.
-50 ° C is preferred, and 30-40 ° C is more preferred.
The fixing temperature and time are preferably from about 20 ° C to about 50 ° C for 60 seconds or less, more preferably from 30 ° C to 40 ° C for 6 seconds to 30 seconds. Water washing or stabilizing bath temperature and time are more preferably 0 to 50 ° C. According to the method of the present invention, the developed, fixed and washed (or stabilized) photographic material is squeezed out of the washing water, i.e., dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions.

The silver halide emulsion used in the present invention is a silver halide emulsion such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver bromoiodide or silver chloroiodobromide. It is distributed in. Silver halide emulsions are usually prepared by adding a water-soluble silver salt (for example, silver nitrate) and a water-soluble halogen salt to water and water by a method well known in the art (for example, a single jet method, a double jet method, a control jet method, etc.). It is mixed in the presence of a hydrophilic colloid, and is produced through physical ripening and chemical ripening such as gold sensitization and / or sulfur sensitization. There are no particular restrictions on the grain shape of the silver halide used in the present invention, and in addition to cubic, octahedral and spherical shapes, Resear
Any of tabular silver halide grains having a high aspect ratio described in Ch Disclosure 22534 (January 1983) can be used.

In the case of an X-ray photographic material, a tabular silver halide emulsion is preferably used. In this case, silver bromide or silver iodobromide is preferred.
-5 mol% is preferred, and a highly sensitive one is obtained, and it is suitable for rapid processing. The tabular silver halide emulsion preferably has an aspect ratio of from 4 to less than 20, more preferably from 5 to less than 10. Further, the thickness of the particles is preferably 0.3 μm or less, particularly preferably 0.2 μm or less. Here, the aspect ratio of the tabular silver halide emulsion is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain. . The tabular grains are preferably present in an amount of preferably 80% by weight, more preferably 90% by weight or more of all grains in the tabular silver halide emulsion. By using a tabular silver halide emulsion, the photographic stability during running processing according to the present invention can be further enhanced. Further, since the amount of coated silver can be reduced, the load on the fixing step and the drying step is particularly reduced, and rapid processing can be performed from this point as well.

The tabular silver halide emulsion was prepared from Knack (Cu
gnac) and Chateau, "Evolution of Morphology of Silver Bromide Crystals during Physical Ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Ripping)" Science・ E-Industrie Photography, 3
3, No.2 (1962), pp. 121-125, Duffin, Photographic emulsion chemistry
Focal Press, New York, 1966, p. 66 to p. 72, APH Tribvlli, WF Smith, Photographic Journal, 80, 28
5 (1940), etc.
127, 921, JP-A-58-113,927, JP-A-58-113,928, etc., and can be easily prepared. In addition, pBr is relatively p of 1.3 or less.
It is obtained by forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere having a Br value, and growing the seed crystal while simultaneously adding silver and a halogen solution while maintaining the same pBr value. It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

The silver halide emulsion used in the present invention may be a polydisperse emulsion or a monodisperse emulsion having a uniform particle size distribution. In particular, the photographic material for printing has a dispersion coefficient of 2 representing the particle size distribution.
Monodispersed emulsions of 0% or less are preferred. Here, the monodisperse emulsion means a silver halide emulsion having a grain size distribution having a coefficient of variation of 20% or less, particularly preferably 15% or less. Here, the coefficient of variation is defined as: coefficient of variation (%) = (standard deviation of particle size / average value of particle size) × 100.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture. Further, the latent image may be a particle mainly formed on the surface of the particle, or a particle mainly formed inside the particle. Further, the particles may be particles whose surface is previously covered.

The silver halide emulsion used in the present invention contains a cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof during the formation of silver halide grains or physical ripening. They may coexist. In particular, when the purpose is to enhance the contrast and to improve the reciprocity failure property, 10 ^-8 to 10 ^-8 mol per mol of silver halide is required.
It is preferred to prepare silver halide in the presence of 10 ^-3 moles of the iridium salt. The silver halide emulsion of the present invention may be an emulsion containing at least one of iron, rhenium, ruthenium and osmium compounds. Addition amount is silver 1
10 ^-3 mol or less, preferably 10 ^-6 mol, per mol.
10 to 10 ^-4 mol.

The emulsion of the present invention may or may not be chemically sensitized. As the method of chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and they are used alone or in combination. The preferred chemical sensitization method is sulfur sensitization. As a sulfur sensitizer, in addition to sulfur compounds contained in gelatin,
Various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. Specific examples are described in U.S. Pat. Nos. 1,574,944 and 2,278,
947, 2,410,689, 2,728,6
No. 68, No. 3, 501, 313, No. 3, 656, 95
No.5. Preferred sulfur compounds are
Thiosulfate, thiourea compound, pA during chemical sensitization
g is preferably 8.3 or less, more preferably
It is in the range of 7.3 to 8.0. Moisar, Klein G
elatione. Proc. Symp. 2nd, 301-309 (197
0) et al. Also use polyvinylpyrrolidone and thiosulfate in combination to give good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. An example is U.S. Pat.
448,060 and British Patent 618,061. Examples of the reduction sensitizer include stannous salts, amines, sulfinoformamidine, dialkylaminoborane, and silane compounds. Specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,518, 6
No. 98, 2,983,609, 2,983,610
No. 2,694,637.

The silver halide grains used in the present invention are preferably spectrally sensitized with a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. Particularly, carbocyanine sensitizing dyes are preferable. Specifically, Research Disclosure Vol. 170, RD-17643 (December 1978
Monthly page 23, U.S. Pat. Nos. 4,425,425 and 4,425,426 can be used. The sensitizing dye used in the present invention is generally added to the emulsion before the emulsion is coated on a suitable support, but may be a chemical ripening step or a silver halide grain forming step.

The emulsion layer of the photographic light-sensitive material of the present invention may contain a plasticizer such as a polymer or an emulsion such as an alkyl acrylate latex or a polyol such as trimethylolpropane in order to improve pressure characteristics.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification dispersion, an adhesion prevention and an improvement in photographic properties (for example, development acceleration). For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amino oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings.

The silver halide photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer on a support. 127921, 59-90841, 5
As described in JP-A Nos. 8-111934 and 61-201235, those having at least one silver halide emulsion layer on both sides of a support are preferred.
The photographic material of the present invention may further include, if necessary, an intermediate layer,
It can have a filter layer, an antihalation layer and the like.

The silver content of the light-sensitive material used in the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 1 g / m ^{2 to} 4 g / m ² (on one side). It is. Preferably, the suitability for rapid processing does not exceed 5 g / m ² . Further, in order to obtain a constant image density and a constant contrast, 0.5 g / m ² or more is preferable.

As a binder or protective colloid of the photographic emulsion, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

It is particularly preferable for the X-ray sensitive material to contain an organic substance which flows out in the development step in the emulsion layer or in the hydrophilic colloid layer. When the substance to be washed away is gelatin, a gelatin species which is not involved in the crosslinking reaction of gelatin by the hardener is preferable, for example, acetylated gelatin or phthalated gelatin, and a material having a small molecular weight is preferable. On the other hand, as a polymer substance other than gelatin, US Pat. No. 3,271,1
Polyacrylamide as described in No. 58, or alternatively, polyvinyl alcohol, a hydrophilic polymer such as polyvinylpyrrolidone can be effectively used,
Sugars such as dextran, saccharose and pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. The amount of the effluent in the processing is preferably 10% or more and 50% or less of the total weight of the coated organic substance other than the silver halide grains, and is preferably 15% or less.
% Or more and preferably 30% or less. The layer containing the organic substance flowing out in the treatment of the present invention may be either an emulsion layer or a surface protective layer.However, when the total amount of the organic substance applied is the same, the layer containing the organic substance is more effective than the layer containing only the emulsion layer. It is preferable that the compound is contained in the emulsion layer, and it is more preferable that the compound is contained only in the surface protective layer. In the case of a light-sensitive material in which the emulsion layer has a multilayer structure, when the total coating amount of the organic substance is the same,
It is preferable that a larger amount be contained in the emulsion layer closer to the surface protective layer.

In the present invention, US Pat. Nos. 2,929,101, 2,701,245, and 41428 as matting agents are used as matting agents.
No. 94, No. 4,396,706 It is possible to use fine particles of a homopolymer of polymethyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, or an inorganic compound such as silica, titanium dioxide or strontium barium sulfate as described in JP-A Nos. it can. The particle size is preferably from 1.0 to 10 μm, particularly preferably from 2 to 5 μm.

The silver halide photographic light-sensitive material of the present invention has a purpose of absorbing light in a specific wavelength range, that is, performing halation or irradiation, or providing a filter layer to adjust the spectral composition of light to be incident on the photographic emulsion layer. The photographic emulsion layer or other layers may be colored with a dye for control or the like. In a double-sided film such as a direct medical x-ray film, a layer for crossover cut may be provided below the emulsion layer. Such dyes include oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus, azo dyes, azomethine dyes, anthraquinone dyes,
Examples include arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, and cyanine dyes.

When these dyes are used, it is an effective technique to mordant an anionic dye onto a specific layer in a light-sensitive material using a polymer having a cation site. In this case, it is preferable to use a dye which irreversibly decolorizes during the development-fixing-washing step. The layer in which the dye is mordanted by using a polymer having a cation site may be the emulsion layer, the surface protective layer may be on the side opposite to the emulsion layer and the support, but preferably between the emulsion layer and the support. For the purpose of crossover cutting of medical X-ray double-sided films, it is ideal to mordant into the undercoat layer.

As a coating aid for the undercoat layer, a polyethylene oxide-based nonionic surfactant can be preferably used in combination with a polymer having a cationic site. As the polymer providing the cation site, an anion conversion polymer is preferable. Various known quaternary ammonium salt (or phosphonium salt) polymers can be used as the anion conversion polymer. Quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers in the publications listed below. JP-A-59-166940, U.S. Pat. No. 3,958,99
5, JP-A-55-142339, JP-A-54-126,
027, JP-A-54-155835, JP-A-53-3
0328, a water-dispersed latex described in JP-A-54-92274; a polyvinylpyridinium salt described in U.S. Pat. Nos. 2,548,564, 3,148,061 and 3,756,814; U.S. Pat. , 709, 69
Water-soluble quaternary ammonium salt polymer described in US Pat. No. 3,898,088; and the like. Further, a monomer having at least two (preferably 2 to 4) ethylenically unsaturated groups is copolymerized because it moves from the desired layer to another layer or into the processing solution and does not have a photographically unfavorable effect. It is particularly preferable to use a crosslinked aqueous polymer latex.

As a method for immobilizing a dye, JP-A-55-1
The solid dispersion method described in 55350, WO88 / 04794, etc. is also effective.

The light-sensitive material used in the present invention may be one which is designed to exhibit ultra-high contrast photographic characteristics using a hydrazine nucleating agent. This system and the hydrazine nucleating agent used are described in the following documents. This system is particularly preferably used for graphic arts. RESEARCH DISCLOSURE I tem 23516 (19
November 1983, p. 346) and references cited therein, U.S. Pat. Nos. 4,080,207 and 4,26.
9,929, 4,276,364, 4,27
8,748, 4,385,108, 4,45
9,347, 4,560,638, 4,47
No. 8,928, British Patent 2,011,391B, JP-A-60-179834, JP-A-62-270,948, JP-A-63-29,751, JP-A-61-170,733.
No. 61-270,744, No. 62-948, E
P217,310, JP-A-63-32538, 6
3-104,047, 63-121,838, 63-129,337, 63-234,245,
63-234,246, 63-223,744
Nos. 63-294,552 and 63-306,43
No. 8, No. 64-10,233 or US 4,68
No. 6,167, JP-A-62-178,246, 63-63
JP-A-234,244, JP-A-64-90,439, JP-A-1-276,128, JP-A-1-283,548, JP-A-1
-280,747, 1-283549, 1-2
No. 85,940, No. 2-2541, No. 2-139,5
No. 38, No. 2-177,057, No. 2-198, 44
No. 0, 2-198, 441, 2-198, 442
Nos. 2-196, 234 and 2-196, 235
No. 2-220,042, 2-221, 953
No. 2-221, 954 and the like.

When a hydrazine nucleating agent is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-light-sensitive hydrophilic colloid layers (for example, a protective layer, an intermediate layer and a filter layer) , An antihalation layer, etc.). The amount of the hydrazine nucleating agent to be added is from 1 × 10 ^-6 mol to 5 × 10 ⁶ per mol of silver halide.
^-2 mol is preferable, and in particular, 1 × 10 ^-5 mol to 2 × 1
A range of 0 ^-2 mol is preferred.

Examples of development accelerators suitable for use in this super-high contrast system or accelerators for nucleation and infectious development include JP-A-53-77616, JP-A-54-37732, and JP-A-53-17332.
37,133, 60-140,340, 60-14
959, and various compounds containing an N or S atom are effective. The optimum amount of these accelerators varies depending on the type of the compound.
× 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ⁻³ to
It is desirable to use in the range of 0.1 g / m ² .

Further, in a super-high contrast system, a redox compound which releases a development inhibitor can be used in combination. As this redox compound, JP-A-2-293
No. 736, No. 2-308, 239, Japanese Patent Application No. 1-154.
No. 060, No. 1-205885 and the like. Its use amount is from 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, especially from 1 × 10 ⁻⁵ mol per mol of silver halide.
It is preferable to use it in the range of 1 × 10 ^-2 mol.

The light-sensitive material of the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro Benzotriazoles, etc .; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaidenes (especially 4-hydroxy-substituted (1,3,3
3a, 7) Tetraazaindenes, pentaazaindenes and the like; addition of many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. it can. Among these, benzotriazole (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole) are preferred. Further, these compounds may be contained in the treatment liquid. Further, a compound capable of releasing an inhibitor during the development described in JP-A-62-30243 can be contained for the purpose of stabilizing or preventing black spots.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl) -Hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, etc.), etc. Can be used alone or in combination.

The photographic light-sensitive material of the present invention contains a hydroquinone derivative (so-called DIR-hydroquinone) which releases a development inhibitor in a photographic emulsion layer or another hydrophilic colloid layer in accordance with the density of an image during development. You may. Specific examples thereof are described in U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, and U.S. Pat.
No. 634, U.S. Pat. No. 4,332,878,
9-129,536, JP-A-54-67,419,
JP-A-56-153,336, JP-A-56-153,
No. 342, JP-A-59-278853, and JP-A-59-9.
Nos. 0435, 59-90436, 59-1388
No. 08 and the like.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. be able to.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid,
A polymer or copolymer having an acid monomer such as maleic acid or phthalic acid as a repeating unit can be given. These compounds are disclosed in JP-A-61-2238.
No. 34, No. 61-228443, No. 62-25745
And the records of JP-B-62-55642 can be referred to. Particularly preferred among these compounds is ascorbic acid as the low molecular weight compound,
The polymer compound is a water-dispersible latex of a copolymer comprising an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene.

The silver halide emulsion thus produced is coated and dried on a support such as a cellulose acetate film or a polyethylene terephthalate film by a dipping method, an air knife method, a bead method, an extrusion doctor method, a double-side coating method, or the like. You.

The present invention can also be used for color light-sensitive materials. In this case, various color couplers can be used. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17
643 (December 1978), Sections VII-D and 187
17 (November 1979). Various photographic additives that can be used in the present invention are described, for example, in Research Disclosure No. 1764 described above.
No. 3, pages 23-28 and No. 18716, 648-6.
It is described on page 51. The types of these additives and the places where they are described in detail are shown below.

Additive type RD17643 RD18716 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648 right column to supersensitizer 649, right column 4 Brightener page 24 5 Antifoggant page 24-25 page 649 right column and stabilizer 6 light absorber, ph 25-26 page 649 right column to filter dye 650 page left column Ultraviolet absorber 7 stain inhibitor page 25 Right column, page 650, left to right column 8 Dye image stabilizer, page 25 9 Hardening agent, page 26, page 651, left column 10 Binder, page 26 Same as above

[0068]

The present invention will be specifically described below with reference to examples.

Example 1 [1] Preparation of Emulsion Preparation of Emulsion A 1 solution water 1.0 l gelatin 20 g sodium chloride 20 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 liquids water 400 ml sodium chloride 27.1 g potassium bromide 21 g potassium hexachloroiridate (III) (0.001% aqueous solution) 15 ml ammonium hexabromorhodate (III) (0.001% aqueous solution) 1.5 ml 38 ° C, pH 4.5 Solution 2 and solution 3 were added simultaneously to solution 1 while stirring over 10 minutes.
m of core particles were formed. Subsequently, the following liquids 4 and 5 were added over 10 minutes. 0.15g of potassium iodide
Was added to terminate the particle formation. Fourth liquid 400 ml Silver nitrate 100 g Five liquid 400 ml Sodium chloride 27.1 g Potassium bromide 21 g Potassium hexacyanoferrate (III) (0.1% aqueous solution) 5 ml After that, water was washed by flocculation according to a conventional method, and 30 g of gelatin was added. .

The pH was adjusted to 5.3 and the pAg to 7.5,
2.6 mg of sodium thiosulfate, 1.0 mg of N, N-dimethylselenourea and 6.2 mg of chloroauric acid are added, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenesulfinate are added, and optimum sensitivity is obtained at 55 ° C. Chemical sensitization to become. 4-hydroxy-6-methyl- as a stabilizer
200 mg of 1,3,3a, 7-tetraazaindene and phenoxyethanol as a preservative were added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and having an average grain size of 0.2 μm was obtained. (Variation coefficient 9%)

Preparation of Coated Sample Orthosensitizing dye (the following compound) was added to the above emulsion at 5 × 10 ^-4.
Orthosensitization was performed by adding mol / mol Ag. As antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole each in an amount of 2.5 g per mol of Ag,
50 mg, a polyethyl acrylate latex as a plasticizer, a gelatin binder ratio of 25%, 2-bis (vinylsulfonylacetamide) ethane as a hardening agent, and a colloidal silica at a gelatin binder ratio of 40% were further added. .0g / m ^2, was coated so as to gelatin 1.0 g / m ^2. A lower protective layer and an upper protective layer having the following composition were simultaneously coated thereon.

[0072]

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<Lower Layer of Protective Layer> Gelatin 0.25 g / m ² Sodium benzenethiosulfonate 4 mg / m ² 1,5-dihydroxy-2-benzaldoxime 25 mg / m ² Polyethyl acrylate latex 125 mg / m ²

<Upper layer of protective layer> Gelatin 0.25 g / m²  2.5 μm average silica matting agent 50 mg / m²  Compound (gelatin dispersion) 30 mg / m²  Colloidal silica having a particle size of 10 to 20 μm 30 mg / m²  Compound 5mg / m²  Sodium dodecylbenzenesulfonate 22mg / m²

[0075]

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The base used in this example has a back layer and a back protective layer having the following compositions. Sodium dodecylbenzenesulfonate 80 mg / m ² Compound - 70 mg / m ² Compound - 85 mg / m ² Compound - 90mg / m ² 1,3- divinyl sulfone-2-propanol 60 mg / m ²

[0077]

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[Back protective layer] Gelatin 0.5 g / m ² polymethyl methacrylate (particle size 4.7 μm) 30 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ^{2 The} above compound 2 mg / m ^{2 The} above compound (gelatin dispersion ) 100mg / m ²

Next, the composition of the developer is shown below. 1,2-dihydroxybenzene-3,5-disulfonic acid sodium 0.5 g diethylenetriamine-pentaacetic acid 2.0 g sodium carbonate 5.0 g boric acid 10.0 g potassium sulfite 85.0 g sodium bromide 6.0 g diethylene glycol 40.0 g 5 -Methylbenzotriazole 0.2 g Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g Potassium hydroxide was added, and water was added to make 1 liter. Adjust to Based on this developer, test developers as shown in Table 1 were prepared.

[0080]

[Table 1]

The obtained sample was interposed with an interference filter having a peak at 488 nm and a continuous wedge, and emitted for 10 minutes.
Exposure with xenon flash light for ^-6 sec, and using an automatic developing machine FG-710NH manufactured by FUJIFILM Corporation,
Sensitometry was performed at the temperature and time shown below, and a running experiment was performed. Current image 38 ° C 14 seconds Fixed 37 ° C 9.7 seconds Rinse 26 ° C 9 seconds Squeeze 2.4 seconds Dry 55 ° C 8.3 seconds Total 43.4 seconds Treat 200 sheets of paper size (50.8cm x 60.1cm) and rest it for 3 consecutive days and 4 days rest. (During this 4 day rest, silver stains are more likely to occur than during operation. 5 times worse) as one round. The replenishment amount was 50 ml per large paper size. Here, the normal running refers to a running with a six-day operation and a one-day rest. The fixer used was LF-308 manufactured by Fuji Photo Film Co., Ltd.
The replenishment amount was 100 ml per large piece. Table 2 shows the results of photographic properties and silver stains by the running experiment.

[0082]

[Table 2]

The photographic properties were evaluated as follows. The gradation is a value obtained by dividing the difference between the density of 3.0 and the density of 1.0 by the logarithm of the exposure amount giving the density of 3.0 and the logarithm of the exposure amount giving the density of 0.1. The sensitivity was calculated by calculating the reciprocal of the exposure required to obtain a density of 1.5 when the photosensitive material was processed with the new developer No. 1 as 10
It was relatively indicated as 0.

The following can be said from Table-2. No change in photographic properties was observed between the developer containing the compound of the present invention and the developer containing the compound of Comparative Example. In the case of silver stains, in the developer Nos. 1 and 3 of the comparative examples, silver stains occurred in the middle of one round, and in No. 2, the silver stains occurred in the third round. Developer No.
In the case of 5, 6, and 8, silver stains were finally generated in the fifth round, and in the developer Nos. 4, 7, and 9, no silver stains were observed. Regarding the stain on the photosensitive material, in the comparative example, although the stain was attached, no attachment of silver stain was observed in the compound of the present invention.

Example 2 (First Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion A 0.37 M silver nitrate aqueous solution and 1 × 10 5 per mol of silver
^-7 mol of (NH ₄ ) ₃ RhCl ₆ and 5 × 10 ^-7 mol of K ₃ Ir
The halogen salt aqueous solution containing sodium chloride potassium bromide and 0.27M of Cl ₆ 0.11 M, sodium chloride,
To the aqueous gelatin solution containing 1,3-dimethyl-2-imidazolidinethione was added by stirring by a double jet method at 45 ° C. for 12 minutes while stirring, and the average particle size was 0.20.
Nucleation was carried out by obtaining silver chlorobromide particles having a particle diameter of 70 μm and a silver chloride content of 70 mol%. Subsequently, a 0.63 M silver nitrate aqueous solution, 0.19 M potassium bromide, 0.4
A halogen salt aqueous solution containing 7M sodium chloride was added by a double jet method over 20 minutes. Then one
A conversion was carried out by adding a KI solution of × 10 ^-3 mol, followed by washing with water by a flocculation method according to a conventional method, adding 40 g of gelatin, adjusting to pH 6.5 and pAg 7.5, and further adding 5 mg of sodium thiosulfate per mol of silver. , 8 mg of chloroauric acid and 7 mg of sodium benzenethiosulfonate, heated at 60 ° C. for 45 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl-1,
150 mg of 3,3a, 7-tetrazaindene, proxel and phenoxyethanol were added. The resulting grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Variation coefficient 9%)

Coating of First Photosensitive Emulsion Layer These emulsions were divided and used as sensitizing dyes in an amount of 1 × 10 ⁻³ mol of 5- [3- (4-sulfobutyl)-per mol of silver.
5-chloro-2-benzoxazolidylidene] -1-hydroxyethoxyethyl-3- (2-pyridyl) -2-
Add thiohydantoin potassium salt and add 2 × 10
^-4 mol of 1-phenyl-5-mercaptotetrazole, 5 × 10 ^-4 mol of short-wave cyanine dye of compound (a) represented by the following structural formula, polymer of compound (b) (200 mg / m ² ), hydroquinone ( 50mg / m
² ) and a dispersion of polyethyl acrylate (200 m
g / m ² ), 1,3-bisvinylsulfonyl-2-propanol (200 mg / m ² ) as a hardening agent and the following hydrazine compound (c) were added, and the coated silver amount was 3.6 g / m ^2.
m ² and gelatin at 2.0 g / m ² .

[0087]

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(Coating of Intermediate Layer) Gelatin 1.0 g / m ² 1,3-bisvinylsulfonyl-2-propanol 4.0 wt% to gelatin

(Second Photosensitive Emulsion Layer) Preparation of Photosensitive Emulsion B A 1.0 M silver nitrate aqueous solution and 3 × 10 ^-7 per mol of silver were used.
An aqueous halide solution containing molar (NH ₄ ) ₃ RhCl ₆ , containing 0.3 M potassium bromide and 0.74 M sodium chloride, containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione Added to the aqueous gelatin solution by double jet method at 45 ° C. for 30 minutes while stirring,
Average grain size 0.28 µm, silver chloride content 70 mol%
Of silver chlorobromide particles were obtained. Thereafter, it was washed with flocculation according to a conventional method, and 40 g of gelatin was added.
6.5 and pAg 7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver were added.
The mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. The resulting grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

Coating of Second Photosensitive Emulsion Layer Photosensitive emulsion B was re-dissolved, and at 40 ° C., 1.0 × 10 ⁻³ mol of 5- [3- (4-
Sulfobutyl) -5-chloro-2-benzooxazolidylidene] -1-hydroxyethoxyethyl-3- (2-
Pyridyl) -2-thiohydantoin potassium salt and 1.0
A KI solution of × 10 ⁻³ mol was added, and 2 × 10 ^{−4 was} further added.
50 mg / m ² of a dispersion of 1-phenyl-5-mercaptotetrazole and polyethyl acrylate in moles, 1,3-bisvinylsulfonyl-2-propanol as a hardener was 4.0 wt% based on gelatin, and the following redox compound 1.0 × 10 ⁻⁴ mol / m ^{2 was} added, and coating was performed so that the coated silver amount was 0.2 g / m ² and the gelatin was 0.3 g / m ² .

[0091]

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(Application of protective layer)
Gelatin 1.0 g / m ² and polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g / m ² were coated using the following surfactants.

[0093]

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The back layer and the back protective layer were applied according to the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / mg

[0095]

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Dye, mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0097]

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[Back protective layer] Gelatin 0.8 g / m²  Polymethyl methacrylate fine particles (average particle size: 4.5μ) 30mg / m²  Dihexyl-α-sulfosacnate sodium salt 15 mg / m²  Dodecylbenzenesulfonic acid sodium salt 15mg / m²  Sodium acetate 40mg / m²

[0099]

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On a polyester film (100μ) support, a first photosensitive emulsion layer was formed as a lowermost layer, a second photosensitive emulsion layer containing a redox compound via an intermediate layer, and a protective layer were simultaneously coated on this layer. A sample was prepared.

Next, the composition of the developer is shown below. Image solution Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 18.0 5-Sulfosalicylic acid 55.0 Potassium sulfite 124.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-methylbenzotriazole 0.4 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Nn-butyldiethanolamine 15.0 Sodium toluenesulfonate 8.0 1 liter by adding water 1 liter pH = 11. Adjust to 6 (add potassium hydroxide)
pH 11.6 Based on this developer, a test developer as shown in Table 3 was prepared.

[0102]

[Table 3]

The obtained film sample was exposed to tungsten light at 3200 ° K through an optical wedge for sensitometry, and an automatic developing machine FG-7 manufactured by Fuji Photo Film Co., Ltd. was used.
Processing was performed using 10F. The development was carried out at 34 ° C. and 30 ″, and the replenishment of the developing solution was carried out in the same running experiment as in Example 1 except that 75 ml per large paper sheet was used. The fixing solution was GR-F1 manufactured by Fuji Photo Film Co., Ltd. The amount of replenishment was 100 ml per sheet, and a running experiment was conducted using these developing solutions and photosensitive materials. It was found that the combination use of the compound (1) had a high ability to prevent silver stain without affecting the photographic properties.

[0104]

[Table 4]

Example 3 (1) Preparation of silver halide emulsion 40 g of gelatin was dissolved in 1 liter of H ₂ O,
6 g of sodium chloride, 0.4 g of potassium bromide, and compound I

[0106]

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After adding 60 mg of the solution, 600 ml of an aqueous solution containing 100 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride are added by a double jet method to form a core portion of 20 mol% of silver chloride. ,
Thereafter, 500 ml of an aqueous solution containing 100 g of silver nitrate and 500 ml of an aqueous solution containing 40 g of potassium bromide, 14 g of sodium chloride, and potassium hexachloroiridium (III) (10 ⁻⁷ mol / mol silver) were added by a double jet method. A so-called core / shell type cubic monodispersed silver chlorobromide particle having a shell portion of 40 mol% of silver chloride and an average particle size of 0.35 μm was prepared. After desalting this emulsion, 40 g of gelatin was added, and the pH was 6.0 and the pAg was
8.5 to match triethylthiourea 2mg and chloroauric acid 4
mg and 4-hydroxy-6-methyl-1,3,3a,
0.2 g of 7-tetrazaindene was added and subjected to chemical sensitization at 60 ° C.

(2) Preparation of Emulsion Coating Solution A container in which 850 g of the emulsion was weighed was heated to 40 ° C., and additives were added by the following method to prepare an emulsion coating solution. (Emulsion coating liquid formulation A) Emulsion 850 g b. Spectral sensitizing dye [II] 1.2 × 10 ^-4 mol c. Supersensitizer [III] 0.8 × 10 ^-3 mol d. Preservability improver [IV] 1 × 10 ^-3 morpho. To 7.5 g of polyacrylamide (molecular weight 40,000). Trimethylolpropane 1.6 g g. 2.4 g of sodium polystyrene sulfonate h. Latex of poly (ethyl acrylate / methacrylic acid) 16 g N-N'-ethylenedibis- (vinylsulfonacetamide) 1.2 g

Spectral sensitizing dye II

[0110]

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Supersensitizer III

[0112]

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Storage stability improving agent IV

[0114]

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(3) Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution. (Formulation of coating liquid for surface protective layer of emulsion layer) a. Gelatin 100g b. Polyacrylamide (molecular weight: 40,000) 10 g c. Sodium polystyrene sulfonate (molecular weight: 600,000) 0.6 g d. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.5 g e. 2.2 g of polymethyl methacrylate fine particles (average particle size: 2.0 μm) t- octyl phenoxy ethoxy ethanesulfonic acid sodium 1.2g _{preparative. C 16 H 33 O- (CH} 2 CH 2 O) 10 -H 2.7g Chi. sodium polyacrylate 4g Li. C ₈ F ₁₇ SO ₃ K 70 mg nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -SO ₃ Na 70 mg ru. NaOH (1N) 4 ml ヲ. Methanol 60 ml

(4) Preparation of Back Layer Coating Solution The container was heated to 40 ° C., and additives were added according to the following formulation to prepare a back layer coating solution. (Formulation of coating solution for back layer) a. Gelatin 80g b. Dye V 3.1 g c. Polystyrene sodium sulfonate 0.6 g d. Poly (ethyl acrylate / methacrylic acid) latex 15 g e. 4.3 g of N, N'-ethylenebis- (vinylsulfoneacetamide)

Dye [V]

[0118]

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(5) Preparation of Coating Solution for Back Surface Protective Layer The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a coating solution. (Formulation of coating solution for back surface protective layer) a. Gelatin 80 g c. Polystyrene sodium sulfonate 0.3 g d. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.7 g e. Polymethyl methacrylate fine particles (average particle size 4.0 μm) 4 g f-Na-tert-octylphenoxyethoxyethane sulfonic acid 3.6 g NaOH (1N) 6 ml Li. Sodium polyacrylate 2g _{Li. C 16 H 33 O- (CH} 2 CH 2 O) 10 -H 3.6g _{j. C 8 F 17 SO 3 K} 50mg Le. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 N a 50mg Wo. Methanol 130ml

(6) Preparation of Coating Sample The coating solution for the back layer described above was coated on the side of the polyethylene terephthalate support together with the coating solution for the surface protective layer of the back layer so that the total coating amount of gelatin was 3 g / m ² . Subsequently, on the opposite side of the support, the above-mentioned emulsion coating solution and surface protective layer coating solution were applied so that the coating amount of Ag was 2.5 g / m ² and the gelatin amount of the surface protective layer was 1 g / m ² . It applied so that it might become.

Next, the formulation of the developing concentrate will be described. Developed concentrate (2.5-fold concentrated) Potassium hydroxide 43 g Sodium sulfite 100 g Potassium sulfite 126 g Diethylenetriaminepentaacetic acid 5 g Boric acid 20 g Hydroquinone 85 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 15 g Diethylene glycol 30 g 5- Methylbenzotriazole 0.2 g Potassium bromide 10 g Make up to 1 liter with water (adjust to pH 10.65) The concentrated solution was diluted as follows to obtain a working solution. 400 ml of developing concentrate + 600 ml of water = working solution (adjusting to pH 10.35) Based on this developing solution, a developing solution as shown in Table 5 was prepared.

[0122]

[Table 5]

Next, the roller transport type automatic developing machine FPM-20
00 (Fuji Photo Film Co., Ltd.) for 30 seconds (Dry to D
ry) and modified using the coated sample described above.
The same running test as in Example 1 was performed. The fixing solution used was RF-10 manufactured by FUJIFILM Corporation. The replenishing amount was 20 ml per 10 × 12 inches for both the developing solution and the fixing solution. In addition, as a photographic test method, the applied sample was heated at 25 ° C
It is kept at 0% temperature and humidity and left for 7 days after coating.
Scanning exposure was performed for ^10-7 seconds using a semiconductor laser of nm.

The running results were as shown in Table 6, and it was found that by using the compound of the present invention together with Examples 1 and 2, the ability to prevent silver stain was high without affecting the photographic properties.

[0125]

[Table 6]

Example 4 AgNO was added to an aqueous solution containing 72 g of gelatin and 16 g of NaCl.
An aqueous solution of ₃₁ kg and an aqueous solution of 161 g of KBr and 205 g of NaCl were simultaneously added at a constant rate for 32 minutes. (Br = 23 mol%)
At this time, rhodium chloride and K ₃ IrCl ₆ were added in the first half of the first 10 minutes so as to be 5 × 10 ⁻⁷ mol / Ag mol. Next, the soluble salts were removed and gelatin was added. Then p
After adjusting the H to 6.0 and the pAg to 7.5, chloroauric acid and hypo were added to carry out chemical sensitization at 60 ° C. The time of chemical sensitization was chosen to give the highest sensitivity. This emulsion was added with 4-hydroxy-6-methyl-1,3,3 as a stabilizer.
3a, 7-Tetrazaindene was added, and phenoxyethanol was added as a preservative.

To 1 kg of the emulsion thus obtained, 110 ml of a 0.05% solution of the sensitizing dye (I) was added, and 100 mg / m ^{2 of} hydroquinone, a polyethyl acrylate latex as a plasticizer, a gelatin binder ratio of 25%, and a hardener were added. 85 mg / m ² of 2-bis (vinylsulfonylacetamide) ethane was added as a film agent, and the mixture was coated on a polyester support so that silver became 3.7 g / m ² . Gelatin 2.0
g / m ² .

[0128]

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On this, gelatin 0.8 g / m ² and polymethyl methacrylate 4 having an average particle size of 2.5 μm as a matting agent
0 mg / m ² , 30 mg / colloidal silica having an average particle size of 4 μm
m ² , silicone oil 80 mg / m ² , dodecylbenzenesulfonic acid sodium salt 80 mg / m ² as a coating aid, a surfactant having the following structural formula, polyethyl acrylate latex 150 mg / m ² and 1,1′-disulfobutyl-3 ,
6 mg / m ² of 3,3 ′, 3′-tetramethyl-5,5′-disulfoindotricarbocyanine potassium salt was applied as a protective layer. These samples have a back layer and a back protective layer having the following composition on the opposite side of the polyester support.

(Back layer) Gelatin 2.4 g / m ² Dodecylbenzenesulfonic acid sodium salt 60 mg / m ² Dye 80 mg / m ² ３０ 30 mg / m ² 1,1′-Disulfobutyl-3,3,3 ′, 3 ′ -Tetramethyl-5,5'-disulfoindotricarbocyanine potassium salt 80 mg / m ² 1,3-divinylsulfonyl-2-propanol 60 mg / m ² potassium polyvinyl-benzenesulfonate 30 mg / m ² (back protective layer) Gelatin 0.75 g / m ² Polymethyl methacrylate (average particle size 3.5 μ) 40 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Surfactant 2 mg / m ² Silicone oil 100 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) −CH ₂ COOK

[0131]

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The thus obtained sample was subjected to scanning exposure using a semiconductor laser emitting at 780 nm. Next, a running experiment was carried out using an automatic developing machine FG-710NH (manufactured by Fuji Photo Film Co., Ltd.) in the same manner as in Example 1 using the developing solution and the fixing solution used in Example 1. As a result, the result was the same as that of Example 1, and it was found that the developer using the compound of the present invention in combination had a high ability to prevent silver stain without being affected by photographic properties.

Example 5 Emulsions A and B were prepared by the following method. 0.5M silver nitrate aqueous solution, 0.1M potassium bromide and 0.44M
An aqueous solution of a halogen salt containing sodium chloride, potassium hexachloroiridate (III) and ammonium hexabromorhodium (III) is prepared by adding sodium chloride, 1,3-dimethylimidazolidin-2-thione and benzenethiosulfonic acid to a pH of 4. The mixture was added to an aqueous gelatin solution adjusted to 0.02 with stirring by a double jet method at 38 ° C. for 10 minutes to obtain silver chlorobromide particles having an average particle size of 0.16 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Was done. Subsequently, similarly, a 0.5 M silver nitrate aqueous solution,
A halogen salt aqueous solution containing 0.1 M potassium bromide, 0.44 M sodium chloride and potassium ferrocyanide was added for 10 minutes by a double jet method, thereby completing the grain formation. The obtained particles had an average particle size of 0.2 μm, a silver chloride content of 70 mol%, and an Ir of 3.8 × 1 per mol of silver.
0 ^-7 mol, Rh is 6.1 × 10 ^-8 mol, Fe is 2.3 ×
The particles were silver chlorobromide cubic grains containing 10 ^-5 mol (coefficient of variation: 10%). Thereafter, it was washed with water by a flocculation method according to a conventional method, and 30 g of gelatin was added. This emulsion was divided into two equal parts, and Emulsions A and B were prepared by the following method.

Emulsion A: The pH of the emulsion was adjusted to 5.6, the pAg was adjusted to 7.5, and 3.2 mg of sodium thiosulfate and 4.3 mg of chloroauric acid were added so that the optimum sensitivity was obtained at 65 ° C. Was subjected to a chemical sensitization treatment, and 75 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added as a stabilizer. Emulsion B: The pH of the emulsion was adjusted to 5.1, the pAg was adjusted to 7.5, 2.2 mg of sodium thiosulfate, 0.85 mg of N, N-dimethylselenourea, 3.4 mg of sodium benzenethiosulfonate and benzene. 0.85 mg of sodium sulfinate and 4.3 mg of chloroauric acid were added, and the ripening time was adjusted at 55 ° C. so that the emulsion sensitivity would be the same by the evaluation method described later. As an agent, 4
75 mg of -hydroxy-6-methyl-1,3,3a, 7-tetraazaindene were added.

Dyes having the following structures were added to the obtained emulsions A and B. Further, disodium salt of 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid was added in an amount of 234 mg / mol of silver.
25 mg of phenyl-5-mercaptotetrazole were added. Further, hydroquinone 150 mg / m ² and polyethyl acrylate latex were mixed with a gelatin binder ratio of 30.
%, 0.01 μm colloidal silica at a gelatin binder ratio of 30%, and 2-bis (vinylsulfonylacetamido) ethane as a hardener at 70 mg / m ² , and a silver coating amount of 3.2 g / m ² on a polyester support. ^2. Coating was performed so that the coated gelatin amount was 1.4 g / m ² . At this time, 0.5 g of gelatin was applied to the upper layer of the emulsion layer as a protective layer.
m ^2, dye 70 mg / ^{m 2} of the following structural formula, and 60 mg / ^{m 2} of polymethyl methacrylate having a particle diameter 2.5μm as a matting agent, colloidal silica having a particle size of 10 millimicrons 70 mg / ^{m 2,} and as coating aids adding a fluorine-containing surfactant 1.5 mg / ^{m 2} and chelating agent 20 mg / ^{m 2} sodium salt of dodecylbenzenesulfonic acid and the following structural formula were applied simultaneously with and adjusted to pH5.5 with the emulsion layer.

[0136]

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The base used in this example has a back layer and a back protective layer having the following compositions. (Back layer) Gelatin 2.0 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ²

[0138]

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1,3-divinylsulfone-2-propanol 60 mg / m ² (back protective layer) gelatin 0.5 g / m ² polymethyl methacrylate (particle size 4.7 μm) 30 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² Fluorosurfactant containing m ² (as described above) 2 mg / m ² Silicone oil 100 mg / m ²

Evaluation of photographic performance The obtained sample was exposed to xenon flash light having an emission time of 10 ^-5 seconds through an interference filter having a peak at 633 nm and a continuous wedge, and was automatically developed by Fuji Photo Film Co., Ltd. Sensitometry was performed using the FG-710NH machine at the temperature and time shown below.

Current image 38 ° C. 14 seconds Fixing 37 ° C. 9.7 seconds Washing 26 ° C. 9 seconds Squeeze 2.4 seconds Drying 55 ° C. 8.3 seconds Total 43.4 seconds Linear velocity 2800 mm / min Developer used The fixing solution used in Example 1 was used. As a result of the running experiment, the results were the same as those in Example 1, and it was found that the compound using the compound of the present invention had a high ability to prevent silver stain without affecting the photographic properties.

[0142]

The developer using the compound of the present invention in combination has a small amount of silver in the developer even under severe running conditions, and shows no silver stain attached to the film. Is also a small developer.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II): Developer. Embedded image (Wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, a halogen atom, an alkoxycarbonyl R ₁ and R ₂ may be linked to form a ring, provided that the sum of the carbon numbers of R ₁ and R ₂ is 2 20) (Wherein X and Y represent a nitrogen atom or CR ₃ , Z represents a sulfur atom or NR _4. X and Y may be linked to form a condensed ring, provided that the constituent atoms of the 5-membered ring are The number of nitrogen atoms is at least one and no more than _3. R ₃ and R ₄ are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group,
Mercapto group, carboxy group, sulfo group, phosphono group,
Represents an amino group, a nitro group, a cyano group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxy group.
M is a hydrogen atom, an alkali metal atom, a quaternary ammonium,
Represents quaternary phosphonium. )