JP2002072394A - Silver halide photographic sensitive material and developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material which ensures no unevenness in density and satisfactory sensitivity even in a processing system in which a small amount of a developing solution is replenished. SOLUTION: In the silver halide photographic sensitive material with at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloidal layer on the base, the average amount of iodine contained in silver halide grains is 0-0.45 mol% and a surfactant of the formula Rf-Rc-Z [where Rf is a perfluoroalkyl; Rc is a >=1C alkylene; and Z is a group having an anionic group, a cationic group or a nonionic polar group required to impart surface activity] is contained.

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 material (hereinafter simply referred to as a "photosensitive material") and a developing method thereof. The present invention relates to a photosensitive material which is excellent in photographic quality.

[0002]

2. Description of the Related Art In a photosensitive material, particularly a medical X-ray film, reducing the replenishing amount of a developing solution leads to a reduction in a waste liquid amount, and has been greatly focused on from the viewpoint of environmental problems. Further, rapid development processing is also strongly desired. However, in conventional photosensitive materials, the amount of replenishment is reduced,
When rapid processing is performed, sufficient sensitivity and gradation cannot be obtained, and furthermore, an image to which a uniform density is to be provided is not practical, for example, density unevenness occurs. Therefore, development of a photosensitive material which can be processed quickly and has sufficient sensitivity even in a processing system in which the replenishment amount of the developer is small has been awaited.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art.
That is, an object of the present invention is to provide a photosensitive material which can provide sufficient sensitivity without density unevenness even in a processing system in which the replenishment amount of the developer is small. In particular, an object of the present invention is to provide a photosensitive material which requires a small amount of a replenisher of a developer and can be processed quickly.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic layer are provided on a support. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer, by limiting the amount of iodine contained in silver halide grains to a certain range and using a certain surfactant, an excellent halogenation exhibiting a desired effect can be obtained. They have found that a silver photographic light-sensitive material can be provided, and have completed the present invention. That is, according to the present invention, in a silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, the silver halide grains are contained in silver halide grains. A silver halide photographic light-sensitive material characterized by having an average iodine content of 0 mol% or more and 0.45 mol% or less and containing a surfactant represented by the following general formula (F). You. General formula (F): Rf-Rc-Z [wherein, Rf represents a perfluoroalkyl group, Rc represents an alkylene group having 1 or more carbon atoms, Z represents an anionic group necessary for imparting surface activity, It represents a group having a cationic group or a nonionic polar group. ]

According to another aspect of the present invention, the silver halide photographic light-sensitive material according to the present invention as described above is provided with S × T ≦ 1000.
(Here, S represents the replenishment amount of the developer per 4 slices of the photosensitive material (ml / 4 cut), and T represents the processing time (second) of Dry to Dry). A development processing method is provided, wherein the processing is performed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method and an embodiment of the present invention will be described in detail. In this specification, "~"
Indicates a range including the numerical values described before and after it as the lower limit and the upper limit. First, the compound represented by formula (F) used in the present invention will be described in detail. General formula (F)
In Rf represents a perfluoroalkyl group having 3 to 20 carbon atoms, and specific examples, C ₃ F ₇ - groups, C ₄ F ₉ - groups, C
₆ F ₁₃ - groups, C ₈ H ₁₇ - group, C ₁₂ F ₂₅ - group, C ₁₆ F ₃₃ - like group. Rc represents an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 2 to 20 carbon atoms. Specifically, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, 1,6-hexylene group,
2-octylene group and the like.

Z represents a group having a cationic group, an anionic group or a nonionic polar group necessary for imparting surface activity. As long as these groups are contained, the method of linking to Rc is not limited. Examples of anionic groups necessary for imparting surface activity include a sulfonic acid group and its ammonium or metal salt, a phosphonic acid group and its ammonium or metal salt, a sulfate group and its ammonium or metal salt, and a phosphate group. And its ammonium or metal salts.

Examples of the cationic group include quaternary alkyl ammonium groups such as trimethyl ammonium ethyl group and trimethyl ammonium propyl group, and aromatic ammonium groups such as dimethyl phenyl ammonium alkyl group and N-methyl pyridinium group. These groups have an appropriate counter ion, and include a halogen atom, a benzenesulfonate anion, a toluenesulfonate anion, and the like, with a toluenesulfonate anion being preferred. Examples of the nonionic polar group include a polyoxyalkylene group and a polyhydric alcohol group, and preferably a polyoxyalkylene group such as polyethylene glycol and polypropylene glycol.

In the general formula (F), Rf is preferably a perfluoroalkyl group having 4 to 16 carbon atoms, and more preferably a perfluoroalkyl group having 6 to 16 carbon atoms. Rc is preferably an alkylene group having 2 to 16 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. Particularly preferred is an ethylene group. The Rc group and the group required for imparting surface activity may be bonded in any manner, and may be bonded by, for example, an alkylene chain or an arylene. These groups may contain an oxy group, a thio group, a sulfonyl group, a sulfoxide group, a sulfonamide group, an amide group, an amino group, or the like in the main chain or in the measurement. Hereinafter, specific examples of the surfactant represented by Formula (F) that can be used in the present invention will be shown, but the present invention is not limited thereto.

[0010]

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[0011]

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The surfactant represented by formula (F) may be used alone or in combination of two or more. The surfactant represented by the formula (F) may be added to any layer in the light-sensitive material. Examples of the constituent layer to which the surfactant represented by the general formula (F) is added include a photosensitive layer, an intermediate layer, a surface protective layer, a back layer, and a back surface protective layer. It is particularly preferable to use it for the back surface protective layer. The amount of the surfactant represented by the general formula (F) is 0.1% on each of the front and back surfaces of the photothermographic material.
The range is preferably from 200 to 200 mg / m ² , more preferably from 0.5 to 50 mg / m ² , and still more preferably from 1 to 30 m / m ² .
g / m ² .

The photosensitive silver halide used in the present invention may be silver chloride, silver chlorobromide, silver bromide, silver iodobromide, or silver iodochlorobromide. The amount must be such that the average iodine content is greater than or equal to 0 mol% and less than or equal to 0.45 mol%. Incidentally, the average of the iodine content contained in the silver halide grains means an average value of the iodine content obtained from the halogen composition of each silver halide grain. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed in steps, or may be changed continuously. Also,
Silver halide grains having a core / shell structure can also be used. In the silver halide photographic light-sensitive material of the present invention, as described in British Patent No. 635,841 and US Patent No. 3,622,318,
So-called halogen conversion type (conversion type) particles can also be usefully used. The method of halogen conversion is usually carried out by adding an aqueous halogen solution having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion. For example, an aqueous potassium bromide and / or potassium iodide solution is added to silver chloride or silver chlorobromide tabular grains, and an aqueous potassium iodide solution is added to silver bromide or silver iodobromide tabular grains. To convert. The concentration of the aqueous solution to be added is preferably light,
%, More preferably 10% or less. Further, it is preferable to add the converted halogen solution at a rate of 1 mol% or less per minute per mol of silver halide before halogen conversion. Further, at the time of halogen conversion, a part or all of the sensitizing dye and / or the silver halide-adsorbing substance may be present, and instead of the converted halogen aqueous solution, silver bromide or
Silver iodobromide or silver iodide fine particles of silver halide may be added. The size of these fine particles is usually 0.2 μm or less,
Preferably 0.1 μm or less, particularly preferably 0.05 μm
m or less. The halogen conversion method that can be used in the present invention is not limited to the method described above, and can be used in an appropriate combination according to the purpose. Methods for forming photosensitive silver halide are well known in the art, for example, in JP-A-2-68539, U.S. Pat. No. 3,700,458, and Research Disclosure No. 17029, June 1978. Can be prepared by using the method described in

The emulsion sensitizing method and various additives used in the silver halide photographic light-sensitive material of the present invention are not particularly limited. For example, those described in JP-A-2-68539 can be used. it can. Hereinafter, the emulsion sensitizing method and various additives used in the silver halide photographic light-sensitive material of the present invention will be described.

(1) Chemical sensitization method The chemical sensitization method is described in JP-A-2-68539, page 10, line 13 in the upper right column to line 16 in the lower left column.
The methods described in JP-A-313282 and JP-A-6-110144 can be used. As a method of chemically sensitizing a silver halide emulsion, specifically, a sulfur sensitization method, a selenium sensitization method,
Known methods such as reduction sensitization and gold sensitization can be used, and these are used alone or in combination.

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.
No. 448,060 and British Patent No. 618,061. Examples of the sulfur sensitizer include sulfur compounds contained in gelatin, and various sulfur compounds such as thiosulfates, thioureas, thiazoles,
Rhodanins and the like can be used. Specific examples are described in U.S. Pat. Nos. 1,574,944 and 2,278,947.
No. 2,410,689, No.2,72
8,668, 5,501,313,
No. 3,656,955. Further, as a selenium sensitizer, JP-A-6-11014
No. 4 publication. Combination of sulfur sensitization with thiosulfate and selenium sensitization and gold sensitization is useful. Stannous salts, amines, formamine disulfide acid, silane compounds and the like can be used as the reduction sensitizer.

(2) Antifoggant / stabilizer Examples of the antifoggant / stabilizer that can be used in the present invention are described in JP-A-2-68539, page 10, lower left column, 17
7th line from page 11 to the upper left column on page 11 and lower left column 2 from page 3
From the line, the source described in the lower left column of page 4 can be used.

Specifically, azoles (for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, chromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.) Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, etc.); thioketo compounds such as oxadrinethione; azaindenes (For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc.) Benzenethiosulfonate benzenesulfinate, can be added to known compounds as antifoggants or stabilizers such as benzenesulfonic acid amide.

[0019] In particular, JP-A-60-76743 and JP-A-6-76743.
0-87322, a nitrone and a derivative thereof, a mercapto compound described in JP-A-60-80839, a heterocyclic compound described in JP-A-57-164735, and a complex salt of a heterocyclic compound and an acid (Eg 1
-Phenyl-5-mercaptotetrazole) and the like can be preferably used.

Further, purines or nucleic acids, or JP-B-61-36213, and JP-A-59-9084.
For example, a polymer compound described in JP-A No. 4 and the like can be used. Of these, azaindenes, purines, and nucleic acids can be particularly preferably used. The addition amount of these compounds is 0.5 to 5.0 mmol, preferably 0.5 to 3.0 mmol, per 1 mol of silver halide.

(3) Color tone improver The color tone improver usable in the present invention is described in
No. 276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; and JP-A-3-94249, page 6, lower left column, line 15 to page 11, upper right column, line 19 Things. Specifically, the covering power of the silver halide photographic emulsion layer is 60 or more, and a dye having a maximum absorption wavelength between 520 to 560 nm and a dye having a maximum absorption wavelength of 570 to 700 nm are contained in the silver halide photographic emulsion layer and / or other layers. And a dye having a maximum absorption wavelength between the dyes, so that the increase in the optical density due to the dye containing the unexposed portion transmission density after the development processing becomes 0.03 or less.

Typical examples of the emulsion having a covering power of the silver halide photographic emulsion layer of 60 or more include a tabular emulsion and a fine grain emulsion. Particularly, when the silver halide photographic emulsion is composed of tabular silver halide grains having a grain thickness of 0.4 μm or less, or a mixed emulsion of a high iodine surface-sensitive emulsion and an emulsion composed of fine grains covered inside. The effect of color tone improvement is great when is used. Dyes that can be used in the present invention include dyes having a maximum absorption wavelength between 520 and 560 nm, preferably 530 to 555 nm, and 570 to 700 nm, preferably 580 to 650 nm.
In combination with a dye having a maximum absorption wavelength. The maximum absorption wavelength means the maximum absorption wavelength in a state where the dye is present in the photosensitive material.

The dyes used in the present invention include, for example, anthraquinone dyes, azo dyes, azomethine dyes,
A dye having a predetermined maximum wavelength is selected from among indoaniline dye, oxonol dye, carbocyanine dye, styryl dye, triphenylmethane dye and the like. Considering the effects on photographic performance such as stability to development processing, light fastness, desensitization, fog and stain, preferred ones are used from anthraquinone dyes, azo dyes, azomethine dyes and indoaniline dyes. Preferred compounds are described in JP-A-62-276538, page 3, upper left column, line 5 to page 9, upper left column, line 9. Such a dye can be dispersed in an emulsion layer or other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods. Japanese Patent Laid-Open No. 62-276538 No. 9
It is described from line 14 in the upper left column of the page to line 20 in the lower left column of the page 10.

(4) Spectral Sensitizing Dyes The spectral sensitizing dyes usable in the present invention are described in JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. That have been included. Specifically, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a horoporacyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention are described, for example, in US Pat.
17,197, 3,713,828, 3,615,643, 3,615,6
No. 32, No. 3,617,293, No. 3,
628,964, 3,703,377, 3,666,480, 3,667,9
No. 60, 3,679,428, 3,
672,897, 3,769,026, 3,556,800, and 3,615,6
No. 13, No. 3,613, 638, No. 3,
615,635, 3,705,809, 3,632,349, 3,677,7
No. 65, No. 3,770,449, No. 3,
770,440, 3,769,025, 3,745,014, 3,713,8
No. 26, 8,567,458, 3,
625,698, 2,526,632, 2,503,776, JP-A-48-76.
525, Belgian Patent No. 691,807 and the like. The amount of the sensitizing dye to be added is 0.5 mmol or more and less than 4 mmol, preferably 0.5 mmol or more and less than 1.5 mmol per 1 mol of silver halide. Specific examples of the sensitizing dye include JP-A-2-68539.
Nos. II-1 to II-8 described on page 5 to page 8
II-47.

(5) Surfactant / Antistatic Agent Examples of the surfactant / antistatic agent that can be used in the present invention include JP-A-2-68539, page 11, upper left column, 1
Those described from the fourth line to the ninth line in the upper left column on page 12 of the same document are exemplified. Specific examples of the surfactant include, for example, saponin (steroid type) and alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Nonionic surfactants such as polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, silicone polyethylene oxide compounds) and sugar alkyl esters; alkyl sulfonates, alkyl benzene sulfonates, Alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N
-Anionic surfactants such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers; amphoteric surfactants such as alkyl betaines, alkyl sulfo betaines;
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts can be used.

Among them, saponin, sodium dodecylbenzenesulfonate, sodium di-2-ethylhexyl α-sulfosuccinate, sodium p-octylphenoxyethoxyethanesulfonate, sodium dodecyl sulfate, sodium triisopropylnaphthalenesulfonate , Anions such as N-methyl-oleoyltaurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N ',
Cations such as N ′, N′-trimethylammoniodiaminopropane bromide and dodecylpyridium chloride; betaines such as N-dodecyl-N, N-dimethylcarboxybetaine; N-oleyl-N, N-dimethylsulfobutylbetaine; (Average degree of polymerization n-10) oxyethylene cetyl ether, poly (n = 25) oxyethylene p-nonylphenol ether, bis (1-poly (n = 15) oxyethylene-oxy-2,4-di-t)
Nonionics such as -pentylphenyl) ethane can be particularly preferably used.

[0027] Specific examples of the antistatic agent are disclosed in
JP-A-80848, JP-A-61-112144, JP-A-62-172343, JP-A-62-1734.
No. 59, etc., a nonionic surfactant, a nitrate of an alkali metal, conductive tin oxide, zinc oxide, vanadium pentoxide, or a composite oxide obtained by doping them with antimony or the like can be preferably used.

(6) Matting Agent / Sliding Agent / Plasticizer The matting agent / sliding agent / plasticizer which can be used in the present invention is described in JP-A-2-68539, page 12, upper left column, line 10 to upper right. Column 10, line 10, and page 14, lower left column, line 10 to lower right column, line 1 are listed. Specifically, as a matting agent, US Pat.
No. 101, No. 2701245, No. 414
Nos. 2894 and 4396706, homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, sulfuric acid,
Fine particles of an inorganic compound such as strontium barium can be used. 1.0 to 10μ as particle size
m, particularly preferably 2 to 5 μm. In the surface layer of the photographic light-sensitive material of the present invention, U.S. Pat.
In addition to the silicone compounds described in JP-A-89576 and JP-A-4047958 and the colloidal silica described in JP-B-56-23139, paraffin wax, higher fatty acid esters, starch powder derivatives and the like can be used.

For the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer. The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics. For example, UK Patent No. 738,618 discloses a heterocyclic compound,
No. 8,637 describes an alkyl phthalate,
No. 8,639, alkyl esters, U.S. Pat. No. 2,960,404, polyhydric alcohols,
No. 3,121,060 discloses a method using carboxylalkyl cellulose, Japanese Patent Application Laid-Open No. 49-5017 uses paraffin and carboxylate, and Japanese Patent Publication No. 53-28086 uses alkyl acrylate and organic acid. And the like, and these methods can also be used in the present invention.

(7) Hydrophilic colloid Gelatin is advantageously used as a binder or protective colloid which can be used in the emulsion layer, intermediate layer and surface protective layer of the silver halide photographic light-sensitive material of the present invention. And other hydrophilic colloids can also be used.
As the hydrophilic colloid that can be used in the present invention,
JP-A-2-68539, page 12, page 11, upper right column, line 11 to lower left column, line 16 are mentioned.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate, dextran and starch derivatives. Saccharide derivatives; various kinds of synthetic hydrophilicity such as single or copolymer of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and hydrolyzate or enzyme-decomposed product of gelatin can also be used. Among these, it is preferable to use dextran or polyacrylamide having an average molecular weight of 100,000 or less together with gelatin. JP 6
The methods described in JP-A-3-68837 and JP-A-63-149641 are also effective in the present invention.

(8) Hardener The photographic emulsion and the non-photosensitive hydrophilic colloid used in the present invention may contain an inorganic or organic hardener. Hardening agents that can be used in the present invention include those described in JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6; Specifically, 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 compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl)
Methyl ether, N, N′-methylenebis- (β- (vinylsulfonyl) propionamide) and the like, active halogen compounds (2,4-dichloro-6-hydroxy-s-)
Triazines, etc.), mucohalic acids (mucochloric acid,
Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-41221, JP-A-53-57257, and JP-A-59-162546.
The active vinyl compounds described in JP-A Nos. 60-80846 and 60-80846 and the active halides described in U.S. Pat. No. 3,325,287 are preferred.

In the present invention, a polymer hardener can be effectively used as a hardener. Examples of the polymer hardener used in the present invention include dialdehyde starch, polyacrolein, a polymer having an aldehyde group such as an acrolein copolymer described in US Pat. No. 3,396,029, and US Pat. No. 3,623,878, polymers having epoxy groups, US Pat.
No. 2,827, a polymer having a dichlorotriazine group described in Research Disclosure, 17333 (1978), and the like, JP-A-56-6684.
No. 1, JP-A-56-142524, U.S. Pat. No. 4,161,407, and JP-A-54-65033.
Gazette, Research Disclosure Magazine 16725
(1978), a polymer having an active vinyl group or a group which is a precursor thereof, and the like, and a polymer having an active vinyl group or a group which is a precursor thereof is preferable. -14252
Particularly preferred are polymers in which an active vinyl group or a group which is a precursor thereof is bonded to a polymer main chain by a long spacer, as described in JP-A No. 4 (1994) -208. The hydrophilic colloid layer in the silver halide photographic light-sensitive material of the present invention has a swelling ratio in water of 300 due to these hardeners.
% Or less, particularly 230% or less.

(9) Support The support used in the present invention is described in JP-A-2-68539, page 13, upper right column, lines 7 to 20. Specifically, the support is preferably a polyethylene terephthalate film or a cellulose triacetate film. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment or an ultraviolet irradiation treatment on the surface thereof in order to improve the adhesive force with the hydrophilic colloid layer, or a styrene-butadiene-based latex, a vinylidene chloride-based latex or the like. An undercoat layer may be provided, and a gelatin layer may be further provided thereon. Further, an undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion to the hydrophilic colloid layer can be further improved.

(10) Crossover cut method In the present invention, the crossover cut method described in JP-A-2-264944, page 4, upper right column, line 20 to page 14, upper right column, can be applied. it can. It is well known in the art that crossover light significantly reduces sharpness. Means for keeping the crossover light of the photographic material at 12% or less are described in U.S. Pat. No. 4,130,429 and JP-A-61-11635.
No. 4 discloses a method of absorbing light having a wavelength that matches the emission wavelength of an X-ray fluorescent screen using a sensitizing dye or dye.

Further, US Pat. No. 4,803,150 discloses a technique in which a dye is present between a support and an emulsion layer in the form of a microcrystalline dispersion so that the crossover light is 10% or less. It has been disclosed. Also, JP-A-63-3
JP-A-05345 discloses a technique of fixing an anionic dye to a specific layer using a cationic polymer latex, and JP-A-1-16631 discloses a technique of using a fixing layer of a dye as an undercoat layer of a support. Have been. In the light-sensitive material of the present invention, any of these methods can be used. However, the coloring layer formed by the dye is preferably an undercoat layer, and the dye is fixed by the method described in JP-A-1-16631. In particular, the dye is disclosed in U.S. Pat.
It is preferable that the particles are fixed to the undercoat layer in the form of a microcrystal dispersion described in JP-A-803,150. In the present invention, these methods can be appropriately combined.
Dyes that can be preferably used in the present invention include those described in JP-A-2-264944, page 4, lower left column to page 9, upper right column. As the mordant layer, those described in JP-A-2-264944, page 9, lower right column to page 14, upper right column can be used.

(11) Dyes / mordanting agents Dyes / mordanting agents which can be used in the present invention are described in JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9; JP-A-3-24537, page 14, lower left column to page 16, lower right column. That is, 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 control the spectral composition of light to be incident on the photographic emulsion layer. For example, the photographic emulsion layer or other layers may be colored with a dye. 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, for example, GB 506,385,
177,429, 1,311,884, 1,338,799, 1,385,3
No. 71, No. 1,467,214, No. 1,
433,102, 1,553,516, JP-A-48-85130, and 49-1144.
No. 20, No. 52-117123, No. 55-1
Nos. 61233, 59-11640, JP-B-39-22069 and 43-13168, U.S. Pat. Nos. 3,247,127 and 3,4.
Oxonol dyes having a pyrazolone acid or barbituric acid nucleus described in, for example, 69,985 and 4,078,933, and U.S. Pat. Nos. 2,533,472 and 3,379, 533, other oxonol dyes described in British Patent No. 1,278,621, and the like, British Patent No. 575,691,
No. 680,631, No. 599,623, No. 786,907, No. 907,125, No. 1,045,609, U.S. Pat.
Azo dyes described in JP-A-255-326, JP-A-39-211043 and the like;
Azomethine dyes described in US Pat. No. 2,862, JP-A Nos. 54-118247, British Patent Nos. 2,014,598 and 750,031;
Anthraquinone dyes described in US Pat. No. 5,752,
U.S. Pat. Nos. 2,538,009 and 2,68
8,541, 2,538,008,
British Patent Nos. 584,609 and 1,210,2
No. 52, JP-A-50-40625, 51
Nos. 3623, 51-10927, 54
JP-A-118247, JP-B-48-3286,
Ariden dyes described in JP-A-59-37303, JP-B-28-3082 and JP-A-44-16594.
Styryl dyes described in JP-A-59-28898 and the like, British Patent No. 446,583,
335,422, JP-A-59-228250, and the like, and triarylmethane dyes described in British Patent No. 1,075,653, and 1,153,341.
Nos. 1,284,730, 1,47
No. 5,228, 1,542,807, etc., merocyanine dyes described in US Pat.
And cyanine dyes described in 3,486 and 3,294,539.

When using a dye, it is an effective technique to mordant an anionic dye onto a specific layer in a light-sensitive material using a polymer having cationic sites. In this case, it is preferable to use a dye which irreversibly decolorizes during the development-fixing-washing step. The layer for mordanting the dye using a polymer having a cation site, even in the emulsion layer, even in the interfacial protective layer, may be on the side opposite to the emulsion layer and the support, preferably between the emulsion layer and the support, Particularly, for the purpose of crossover cutting of a medical X-ray double-sided film, it is ideal to mordant into an undercoat layer.
As a coating aid for the undercoat layer, a polymer in which a polyethylene oxide-based nonionic surfactant has a cation site can be preferably used in combination.

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 following publications and the like.

That is, JP-A-59-166940,
U.S. Pat. No. 3,958,995, JP-A-55-1
No. 42339, Japanese Patent Application Laid-Open No. 54-126027,
JP-A-54-155835, JP-A-53-303
No. 28, JP-A-54-92274, an aqueous dispersion latex; U.S. Pat. No. 2,548,564.
No. 3,148,061 and 3,75
No. 6,814, polyvinyl pyridinium salt; U.S. Pat. No. 3,709,690; water-soluble quaternary ammonium salt polymer; U.S. Pat.
No. 088, water-insoluble quaternary ammonium salt polymers and the like. However, since it moves from a desired layer to another layer or a processing solution and does not exert a photographically unfavorable effect, it is disclosed in JP-A-1-166031, JP-A-1-201655, and JP-A-1-30738. It is desirable to apply the method described in (1). Others
Japanese Patent Laid-Open Publication No. 3-24537, page 14
The technique described in the lower right column on page 6 can also be used.

(12) Polyhydroxybenzenes Polyhydroxybenzenes usable in the present invention are described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and EP Patent No. 452772A. One. Specifically, Japanese Patent Application Laid-Open No. 3-399
No. 48, page 11, upper left column, compounds of the general formula (III), specific compounds of which are (III) -1 to 25, from page 11, lower left column to page 12, lower left column. Is mentioned. The addition amount of these polyhydroxybenzene compounds is 5 × 10 ⁻¹ per mol of silver halide.
The amount is preferably less than 1 mol, and more preferably 1 × 10 ^-1 to 5 × 10 ^-3 mol per mol of silver halide.

(13) Developing Method The developing method of the silver halide photographic light-sensitive material of the present invention is described in JP-A-2-103737, p.
From line 15 to line 15 in the lower left column of page 19, see JP-A-2-115.
No. 837, page 3, lower right column, line 5 to page 6, upper right column, 1
0th line, and JP-A-2000-112078, No. 34
The method described in page 42, left column, line 42 to page 35, left column, second line can be employed.

Examples of the developing agent for processing the photographic light-sensitive material of the present invention include polyhydroxybenzene compounds represented by hydroquinone and ascorbic acid which have been conventionally used in processing systems for medical silver halide light-sensitive materials. Alternatively, ersorbic acid (a diastereomer of ascorbic acid) and alkali metal salts thereof such as lithium salt, sodium salt and potassium salt are preferably used.

In the present invention, it is preferable to use an auxiliary developing agent exhibiting superadditivity together with the developing agent. As an auxiliary developing agent showing superadditivity, 1-phenyl-3-
There are pyrazolidones auxiliary developing agents. 1-phenyl-3
1-phenyl- as a pyrazolidone auxiliary developing agent
3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenol-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4 -Methyl-4-hydroxymethyl-3-pyrazolidone and the like.

The pH of the developing solution using these developing agents is preferably 7 or more and less than 11, and more preferably 8 or less.
It is more preferably at least 10.5. The sulfite ion concentration in one liter of these developing solutions is preferably 0.01 mol or more and 0.6 mol or less.

In the method for processing the photographic light-sensitive material of the present invention, the processing time of Dry to Dry is preferably from 20 seconds to 200 seconds, more preferably from 25 seconds to 150 seconds. Further, the replenishment amounts of development and fixing are preferably 5 ml or more and 200 ml or less, more preferably 25 ml or more and 160 ml or less per m ² of the photographic light-sensitive material.

Dry with the photosensitive material / processing system of the present invention
When performing development processing of 70 seconds or less in dry to dry processing, Japanese Patent Application Laid-Open No.
A roller made of a rubber material as described in JP-A-3-151943 may be applied to a roller at the outlet of a developing tank, or a developer in a developer tank may be used as described in JP-A-63-151944. The discharge flow rate for stirring was increased to 10 m / min or more.
As described in JP-A-15537, it is more preferable to perform stronger stirring at least during the development processing than during standby. Further, for the rapid processing as in the present invention, particularly, the constitution of the roller of the fixing solution tank is to increase the fixing speed, and to accelerate the elution of the dye in a photosensitive material containing a sensitizing dye. More preferably, it is a facing roller. By using the opposing rollers, the number of rollers can be reduced, and the processing tank can be reduced.
That is, it is possible to make the self-developing machine more compact.

A compound known as a developer component can be added to the developer. For example, an antifoggant can be used in the developer. As an antifoggant,
Any of an indazole-based, benzimidazole-based, benzotriazole-based or mercaptoazole-based antifoggant can be used. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole,
1-methyl-5-nitroindazole, 6-nitroindazole, 9-methyl-5-nitroindazole, 5-
Nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4- (2-mercapto-1,3,4-thiadiazol-2-yl-thio) butanesulfonate, 5
-Amino-1,3,4-thiadiazole-2-thiol and the like. In the present invention, an antifoggant having a nitro group is particularly preferred. Among the above antifoggants, 5-nitroindazole, 5-nitrobenzimidazole, and 5-nitrobenzotriazole are preferable, and 65-nitroindazole is particularly preferable from the viewpoint of safety. The amount of the antifoggant used is usually 0.1 per liter of developer.
It is from 02 to 3 mmol, preferably from 0.1 to 2 mmol.

In the present invention, it is preferable to add a preservative to the developer. Preservatives include sulfites, bisulfites,
There are metabisulfite and the like, and specifically, sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite, potassium bisulfite, potassium metabisulfite, ammonium sulfite and the like are used.

In the present invention, various organic or inorganic chelating agents can be used in the developer. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametasilicate and the like can be used. As the organic chelating agent, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, and aminophosphonic acids can be used. As organic carboxylic acids, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pinolinic acid, succinic acid, atelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, Itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, triethylenetriaminepentaacetic acid, triethyltetraminehexaacetic acid, and glycoletherdiamine. Tetraacetic acid, hydroxyethyliminodiacetic acid, 1,
2-diaminopropanetetraacetic acid and others
No. 632, No. 55-67747, No. 57-10262
No. 4, JP-B-53-40900 and the like. As the organic phossonic acid, there are known compounds such as hydroxyalkylidene diphosphonic acid described in U.S. Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication No. 22,27639, and Research Disclosure No. 18170.

As aminophosphonic acid, aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and the like are known, and others are described in Research Disclosure No. 18170, JP-A-57-2065.
No. 54, 54-81125, 55-29
The compounds described in JP-A-883-88 and JP-A-56-97347 can be exemplified. Examples of the organic phosphonic acid include JP-A-52-102726 and JP-A-53-102726.
-42730, 54-127127, 55-4024, 55-4025, and 5
5-126241, 55-65555,
Compounds described in JP-A-55-89556 and Research Disclosure No. 18170 can be exemplified. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The chelating agent is preferably 1 × 10 ^-9 to 1 × 10 ^-1 mol, particularly 1 × 10 ^-1 mol per liter of the developer.
It is used in the range of 10 ^{-5 to} 2 × 10 ^-2 mol.

A hardener may be used in the developer. As the hardener, a dialdehyde-based hardener or a bisulfite adduct thereof is preferably used. Specific examples thereof include glutaraldehyde and bisulfite adduct thereof. Additives other than the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and methanol. Organic solvent such as: 1-phenyl-5-
Mercaptotetrazole, a mercapto-based compound such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, an indazole-based compound such as 5-nitroindazole, and a benztriazole-based compound such as 5-methylbenztriazole and the like. Well, R
essearch Disclosure Vol. 176, N
o. 17643, Section XXI (December Issue, 1978) and, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hard water softener, and JP-A-56-10624.
It may contain an amino compound described in JP-A No. 4 (Kokai) No. 4 and the like.

In the developing treatment, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used in the developing solution. The developer is disclosed in JP-A-56-1.
Amino compounds such as alkanolamines described in JP-A-06244 can be used. In addition, L. F. A
Mason, Photographic Processing Chemistry, Focal Press (1966) 2
26-229, U.S. Pat. Nos. 2,193,015 and 2,592,362, JP-A-48-64.
No. 933 may be used.

If necessary, a buffer (eg, carbonate, boric acid, borate), an alkaline agent (eg, hydroxide or carbonate), a dissolution aid (eg, polyethylene glycols and esters thereof) may be added to the developer. PH adjusters (eg, organic acids such as acetic acid), development accelerators (eg, US Pat.
604, 3171247, and JP-B-44-9503, cationic dyes such as various pyrimidium compounds and other cationic compounds such as phenosafuranyl, mediums such as thallium borate and potassium nitrate. Sex salt, JP-B-44-9304,
U.S. Pat. Nos. 2,533,990 and 2,531,183
No. 2, No. 2,950,970, No. 257
No. 7127, polyethylene glycol and derivatives thereof, nonionic compounds such as polythioether, JP-B-44-9509, Belgian Patent No. 68
No. 2,862), an auxiliary developing agent other than the above (for example, p-aminophenols), a surfactant, a dispersant for a silver colloid that elutes (for example, a mercapto compound), and the like. . A developer composed of these components is usually composed of one or more chemical parts. That is, it consists of several powders and / or liquids.

Further, in the present invention, a solution part prepared by dissolving a water-soluble bromide salt, a water-soluble iodide salt and a silver halide solvent in one is prepared. Good. When the developing solution is used as a replenisher for the processing in an automatic processor, a developing initiator composed of an acid and a water-soluble halide may be used. It is preferable to use a thioether compound described in JP-A-57-63530 in addition to the acid and the water-soluble halide in order to improve the balance between sensitivity and gradation from the beginning of development. The development processing temperature and time are interrelated and determined in relation to the total processing time, but are usually about 20 ° C to 5 ° C.
10 seconds to 3 minutes at 0 ° C.

The photosensitive material that has been developed with a developing solution is usually subsequently subjected to a fixing process. The fixer is an aqueous solution containing a thiosulfate, and if necessary, a hardener (such as a water-soluble aluminum salt) and a liquid (such as tartaric acid, citric acid, gluconic acid, boric acid, or salts thereof). 3.8 ~
7.0 (20 ° C.). In the present invention, a stop step can be provided between the development and the fixing, but the stop step is generally omitted in the automatic developing machine. As a result, the developer may be brought into the fixer and the pH of the fixer may rise. Therefore, when an aluminum compound is used for the fixing solution, the pH of the fixing solution is set to about 3.
It is desirable to adjust to 8 to 5 (20 ° C.).

The fixing agent contains, as an essential component, thiosulfate ions such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, but is generally about 0.1 to 5 mol / l. The aqueous aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. The amount of the compound used is usually 10 ⁻³ to 2 × 10
^-1 mol / l (in terms of aluminum).

The amount of the acid or salt thereof used in the fixing solution is usually from 0.005 mol / l to 0.05 mol / l. If necessary, the fixing solution may contain a preservative (for example, a hardening salt or bisulfite), a pH buffer (for example, boric acid or borate), a chelating agent (as described above), or the like. it can. The fixing temperature and time can be changed as appropriate, but usually from about 20 ° C to 50 ° C.
C. for 10 seconds to 3 minutes is preferred.

The developed and fixed photosensitive material is washed (or stabilized) with water and dried. Rinsing is carried out sufficiently to remove almost completely the silver salt dissolved by fixing, and about 2 times.
The temperature is preferably from 0 ° C to 50 ° C for 10 seconds to 3 minutes. The replenishment rate of the washing water (or stabilizing solution) may be 1200 ml / m ² or less (including 0). The case where the replenishment amount of the washing water (or the stabilizing solution) is 0 means a method by a so-called hot water washing method. As a method for reducing the amount of replenishment, a multi-stage countercurrent system (for example, two-stage or three-stage) has been known for a long time.

To solve the problem that occurs when the replenishing amount of the washing water (or the stabilizing solution) is small, good processing performance can be obtained by combining the following techniques. The washing water (or stabilizing solution) contains R.I. T. Kremmn, "J. ImageTech," Vol. 6,24
2 pages (1984), Research Disclosure 205
Isothiazoline compounds described in JP-A-61-115154 and JP-A-62-22845.
Compounds described in JP-A-20-95532 can be used as a bacteriostatic agent (Microbiocide). In addition, "The Chemistry of Bacterial Prevention and Protection", Hiroshi Higuchi, Sankyo Publishing (Showa 57), "Handbook of Bacterial Prevention and Protection Technology"
Japan Society of Antibacterial Prevention and Protection, Hakuhodo (1986) E. FIG.
"Water Quality Write" by West
ria "(Photo. Sci, Eng, Vol. 9, N
o. 6 (1965); W. Beach, "Micr
obiological Growths in Mo
Tion Picture Processing ”
(SMPTE Journal Vol. 85, (19
76); O. Deegan, “Photo Pro
cessing Wash Water Biocid
es "(J. Imaging Tech 10, No.
6 (1984) may be used.

When treating with a small amount of washing water (or a stabilizing solution), it is preferable to provide a squeezing roller or crossover roller washing tank described in JP-A-62-287252. Further, part or all of the overflow liquid from the washing (or stabilizing) bath generated by replenishing the washing water (or the stabilizing solution) with the water subjected to the deodorizing means according to the treatment is disclosed in 23
As described in JP-A Nos. 5133 and 63-129343, it can be used for replenishment of a fixing solution which is a preceding processing step. Further, a water-soluble surfactant and / or a water-soluble surfactant may be used to prevent water bubble unevenness, which is likely to occur when treating with a small amount of washing water (or a stabilizing solution), and / or to prevent a treatment component adhering to a squeeze roller from being transferred to a film. An antifoaming agent may be added.

In order to prevent contamination by the dye eluted from the light-sensitive material, a dye adsorbent described in JP-A-63-163456 may be provided in a washing tank. Drying is performed at about 40 ° C. to 100 ° C., and the time varies depending on the surrounding conditions, but may be about 5 seconds to 3 minutes 30 seconds. The developing solution of the present invention is particularly effective when processing using an automatic developing machine.

In the present invention, the silver halide photographic light-sensitive material described in the present specification can be prepared by the following formula: S × T ≦ 1000 (where S is the replenishing amount of the developing solution per 4 pieces of the photosensitive material (ml / 4 pieces) ), And T represents a processing time (second) of Dry to Dry.) Also, the present invention relates to a development processing method characterized in that the development processing is performed under the condition of: By performing the development processing under such conditions, it is possible to simultaneously reduce the replenishment amount of the developer and the rapid processing. The present invention will be specifically described with reference to the following examples, but the present invention is not limited thereto.

[0065]

EXAMPLE 1 (Preparation of silver halide emulsion T-1) 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and 37 ml of an aqueous silver nitrate solution (silver nitrate 4 .
38 g of an aqueous solution containing 5.9 g of potassium bromide and 5.9 g of potassium bromide
Was added by the double jet method in 37 seconds. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C., and 89 ml of an aqueous silver nitrate solution (9.8 g of silver nitrate) was added over 22 minutes. Here, 7 ml of a 25% aqueous ammonia solution was added, and the mixture was physically ripened at the same temperature for 10 minutes.
6.5 ml of a 0% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added to pAg8.
While maintaining at 5, the addition was performed over 35 minutes by the control double jet method. Next, pBr2.
After adjustment to 8, 15 ml of a 2 mol / L potassium thiocyanate solution was added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. Average projected area diameter 1.10 μm, thickness 0.165 μm, diameter variation coefficient 1
8.5% monodispersed pure silver bromide tabular grains were obtained. After this,
Soluble salts were removed by sedimentation. The temperature was raised again to 40 ° C., and 30 g of gelatin and 2.35 g of phenoxyethanol were obtained.
Then, 0.8 g of sodium polystyrene sulfonate was added as a thickener, and sodium hydroxide and silver nitrate solution were added.
H 5.90 and pAg 8.25 were adjusted. This emulsion was chemically sensitized while being kept at 56 ° C. while stirring. However, AgI fine particles were added before and during chemical sensitization in an amount of 0.05 mol% with respect to 1 mol of monodispersed pure silver bromide tabular grains. First, 0.043 mg of thiourea dioxide was added,
Reduction sensitization was performed by holding the mixture for 22 minutes. Next, 4
20 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 400 mg of sensitizing dye A were added. Further, 0.83 g of calcium chloride was added. Subsequently, as a sensitizer, 1.5 mg of sodium thiosulfate, 2.2 mg of selenium sensitizer B, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added.
Cooled to ° C. Thus, a tabular silver halide emulsion T-
1 was prepared. The average amount of iodine contained in the silver halide grains of the silver halide emulsion T-1 is 0.1 mol%.

(Preparation of Silver Halide Emulsion T-2) AgI
Silver halide emulsion T-2 was prepared in the same manner as for silver halide emulsion T-1, except that the amount of fine particles was changed to 0.5 mol% before and during chemical sensitization. The average amount of iodine contained in the silver halide grains of the silver halide emulsion T-2 is 1.0 mol%.

[0067]

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(Preparation of Coating Sample) A coating sample for an emulsion layer was prepared as a coating solution by adding the following chemicals per mole of silver halide. Gelatin (including Gel in emulsion) 65.6 g Trimethylolpropane 9 g Dextran (average molecular weight 39,000) 18.5 g Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g Hardener: 1,2-bis (Vinylsulfonylacetamide) ethane Adjust the amount of swelling to 230%

[0069]

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The surface protective layer was prepared and prepared such that each component had the following coating amount. Content of surface protective layer Coating amount Gelatin 0.966 g / m ² Sodium polyacrylate (average molecular weight 400,000) 0.023 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0 .015 g / m ²

[0071]

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Polymethyl methacrylate (average particle size: 3.7 μm) 0.087 g / m ² Proxel (adjusted to pH 7.4 with NaOH) 0.0005 g / m ²

Further, as surface active agents, compounds FS-6 and FS-11 and comparative compounds FS-C and FS-D were added in amounts shown in Table 2 to form a surface protective layer.

[0074]

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

[0076]

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434 ml of water and 791 ml of a 6.7% by weight aqueous solution of Triton X-200 surfactant (TX-200)
Were placed in a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO) were added and the contents were ground for 4 days. Thereafter, 160 g of 12.5% by mass gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm. Furthermore, it is 0.9 μm
The dye particles having the above sizes were removed. Thus, a dye dispersion D-1 was obtained.

(2) Preparation of Support A corona discharge treatment was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoating solution having the following composition was applied in an amount of 5.1 ml / m ² . And apply it with a wire bar coater.
Dried for minutes. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained a dye having the following structure at 0.04% by mass.

[0079]

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Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 ml * In the latex solution, a surfactant having the following structure as an emulsion dispersion is added to latex solids. It is contained in an amount of 0.4% by mass.

[0081]

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20.5 ml of a 4% by weight solution of 2,4-dichloro-6-hydroxy-s-triazine sodium salt 900.5 ml of distilled water

A second undercoat layer having the following composition was coated on the first undercoat layer on both sides by a wire bar coater method on each side such that the coating amount was as described below. Coated and dried at ℃. Gelatin 160 mg / m ² Dye dispersion D-1 (26 mg / m ² as a solid dye)

[0084]

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Matting agent (polymethyl methacrylate having an average particle size of 2.5 μm) 2.5 mg / m ²

(Preparation of photographic material) The emulsion layer and the surface protective layer were coated on both sides of the prepared support by a simultaneous extrusion method. The amount of silver applied per side was 1.75 g / m ² . (Evaluation of photographic performance) 0.05% from both sides using X-ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd.
A second exposure was given to evaluate the sensitivity. The automatic machine used in this experiment was an automatic machine FPM-90 manufactured by Fuji Photo Film Co., Ltd.
It is a modification of Type 00 and its processing steps are shown in Table 1 below.
It is as follows.

[0087]

[Table 1]

The processing liquid is as follows. Development Treatment Preparation of Concentrate <Developer> (Parts A) Potassium hydroxide 270 g Potassium sulfite 1125 g Sodium carbonate 450 g Boric acid 75 g Diethylene glycol 150 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamino) ethyl-5-mercaptote torazole 1 0.5g Hydroquinone 405g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 30g Water was added to add 4500ml

(Parts B) Tetraethylene glycol 750 g 3,3′-dithiobishydrocinnamic acid 3 g Glacial acetic acid 75 g 5-nitroindazole 4.5 g 1-phenyl-3-pyrazolidone 67.5 g Agent C) Glutaraldehyde (50 mass / mass%) 150 g Potassium bromide 15 g Potassium metabisulfite 120 g Water is added to 750 ml

<Fixing Solution> Ammonium thiosulfate (70% by mass / volume) 3000 ml Ethylenediaminetetraacetic acid disodium dihydrate 0.45 g sodium sulfite 225 g boric acid 60 g 1- (N, N-dimethylamino) -ethyl-5 -Mercapto tetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (18 mol / L) 58.5 g Aluminum sulfate 150 g Add water 6000 ml pH 4.68

(Preparation of Processing Solution) The above-mentioned developer concentrated solution was filled in the following containers for each part. In this container, the respective partial containers of the parts agents A, B and C are connected together by the container itself. The above-mentioned fixer concentrate was also filled in the same type of container.

First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was placed in a developing tank as a starter.
Was added. Insert the processing agent container upside down and insert it into the perforation blade of the processing liquid stock tank mounted on the side of the automatic processing machine, break the sealing film of the cap, and transfer each processing agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and the fixing tank of the automatic processing machine at the following ratios by operating the pumps respectively installed in the automatic processing apparatus. Here, replenishment of development and fixing was carried out with the following replenishers.

(Replenisher) (Developer) Parts agent A 60 ml Parts agent B 13.4 ml Parts agent C 10 ml water 116.6 ml pH 10.50

(Fixing solution) Concentrated solution 80 ml Water 120 ml pH 4.62 The washing tank was filled with tap water.

[0095] Here, the running amount was changed by changing the replenishing amount to a value other than that of Sample No. 4, and the running process was performed. Sample N
The blackening ratio of o.4 was 35%. Amount of replenisher for developer Amount of replenisher for fixer Condition (a) 25 ml / quarter 25 ml / quarter Condition (b) 18 ml / quarter 18 ml / quarter Condition (c) 12 ml / quarter 12 ml / quarter

After the developing / fixing solution reached a sufficiently equilibrium state, the exposed sample No. The photographic properties of 1 and 2 were evaluated. Here, the sensitivity was set to 1 for each sample.
It is assumed to be 00, and is shown by the reciprocal of the ratio of the exposure amount necessary to give an optical density of fog +1.0. The gradation is fog +0.2
5 and fog +2.0. Fog +
Expose the entire four-section size uniformly with an exposure of 1.0
Development was performed under the conditions (a) to (c) to evaluate the density unevenness. The evaluation was performed on the obtained image by the following five steps visually. 1. Very poor 2. Inferior Normal 4. Good 5. Very good

Table 2 summarizes the evaluation results. Sample No. of the present invention It is understood that the sample No. 4 has a small decrease in sensitivity under conditions (a) to (c), has a high contrast, and has good density unevenness.

[0098]

[Table 2]

Example 2 The light-sensitive material of Example 1 was processed in the same manner as in Example 1, except that glutaraldehyde was removed from the parts agent C of the developing solution, and the same results were obtained.

Example 3 Processing was carried out in the same manner as in Examples 1 and 2, except that the developing solution, the fixing solution and the replenishment thereof were changed as follows, and the processing time was 45 seconds. Developing solution (Part A) Potassium hydroxide 28.0 g Potassium sulfite 75.0 g Diethylenetriaminepentaacetic acid 2.0 g Sodium carbonate 30.0 g Hydroquinone 18.0 g 1- (Diethylamino) -ethyl-5-mercaptote torazole 0.1 g Potassium bromide 1.0 g Add water 300 ml (Part B) Triethylene glycol 6.0 g 5-Nitroindazole 0.3 g Acetic acid 40.0 g 1-Phenyl-3-pyrazolidone 3.5 g 3,3'-Dithiobishydrocinnamic acid 0 .2g Add water 50ml Add water 1 liter of water (adjust to pH 10.30) Replenishment ratio Part A 300ml Part B 50ml water 650ml COD about 50,000 in this state

Fixing solution Part A Sodium thiosulfate 96.4 g Disodium ethylenediaminetetraacetate dihydrate 0.025 g Sodium metabisulfite 22.0 g Water is added and adjusted to pH = 5.0 with 500 ml NaOH. Replenishment ratio Part A 500ml water 500ml COD about 40,000 in this state

[0102] Table 3 shows the results.

[0103]

[Table 3]

In the same manner as in Examples 1 and 2, the sample No.
4 is effective for sensitivity, gradation, and density unevenness.

Example 4 (Preparation of silver halide emulsion T-3) 40 g of gelatin was dissolved in 1 liter of water, and 3 g of potassium bromide and compound [I] were placed in a vessel heated to 55 ° C.

[0106]

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After adding 60 mg of the aqueous solution, while maintaining the pAg value in the reaction vessel at 7.0, an aqueous solution 1 containing 200 g of silver nitrate was added.
000 ml and 1080 ml of an aqueous solution of 140 g of potassium bromide containing potassium hexachloroiridate (III) in a molar ratio of 10 ^-7 mol / mol of silver by double jet method were added to give an average particle size of 0.20 μm. Was prepared. After desalting this emulsion, 71 g of gelatin was added, pH 6.0, and pAg 8.5.
Sodium thiosulfate 3mg and chloroauric acid 4mg and 4
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (0.2 g) was added to prepare a silver halide emulsion T-3 sensitized at 60 ° C. The average amount of iodine contained in the silver halide grains of the silver halide emulsion T-3 is 0 mol%.

(Preparation of emulsion coating solution) Silver halide emulsion T
A container in which 850 g of -3 was weighed was heated to 40 ° C., and additives were added by the following method to prepare an emulsion coating solution.

(Formulation of Emulsion Coating Solution) Emulsion T-3 850 g b. Spectral sensitizing dye [II] 1.2 × 10 ^-4 mol c. Supersensitizer [XVI] 0.8 × 10 ^-3 mol d. Preservability improver [VI] 1 × 10 ^-3 morpho. 7.5 g of polyacrylamide (molecular weight: 40,000) Trimethylolpropane 1.6 g g. 2.4 g of sodium polystyrene sulfonate h. Poly (ethyl acrylate / methacrylic acid) latex 16 g N, N'-ethylenebis- (vinylsulfoneacetamide) 1.2 g

[0110]

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(Preparation of Dye Emulsion Dispersion) As an antihalation dye for infrared semiconductor laser light, see JP-A-2-2-2.
Using compound 8 described on page 4 of JP-A-0774, 10 kg each of dye No. 4 described on page 3 of JP-A-3-23138 as a color tone adjusting dye was weighed, and individually weighed.
It was dissolved at 55 ° C. in a solvent consisting of 12 liters of tricresyl phosphate and 85 liters of ethyl acetate. This is called an oil-based solution. On the other hand, 1.35 kg of an anionic surfactant (W-1 below) was dissolved in 270 ml of a 9.3% gelatin aqueous solution at 45 ° C. This is called an aqueous solution. While the oil-based and water-based solutions were placed in a dispersion vessel, and the liquid temperature was controlled to be maintained at 40 ° C., the high-speed rotating propeller 1 in the dispersion vessel was rotated at 6,500 revolutions / minute while the pressure in the dispersion vessel was maintained. Was gradually reduced from 760 mmHg to 100 mmHg over 60 minutes, and then dispersion was continued under the same conditions for 20 minutes. 8 g of the following additive (a) and 35% of phenoxyethanol methanol were added to the obtained dispersion.
After adding 1.2 liters of the solution and water to make up to 240 kg, the mixture was cooled and solidified.

[0112]

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The area average particle diameters of the obtained dispersions were all in the range of 0.08 to 0.10 μm. The resulting emulsified dispersions are referred to as (antihalation dye emulsified dispersion) AH-8 and (color tone adjusting dye emulsified dispersion) S-6, respectively.

(Preparation of Back Layer Coating Solution) A container was heated to 40 ° C., and additives were added according to the following formulation to prepare a back layer coating solution. I. Gelatin 80g b. Antihalation dye emulsified dispersion AH-8 42 g c. 1.0 g of color tone adjusting dye emulsified dispersion S-6 d. 0.6 g of sodium polystyrene sulfonate e. Poly (ethyl acrylate / methacrylic acid) latex 15 g f. N, N'-ethylenebis- (vinylsulfoneacetamide) 5.0 g

(Preparation of Back Surface Protective Layer Coating Solution) A container was heated to 40 ° C., and an additive was added according to the following formulation to form 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. 4 g of polymethyl methacrylate fine particles (average particle size: 4.0 μm) Sodium t-octylphenoxyethoxyethanesulfonate 3.6 g g. NaOH (1 mol / L) 6 ml 2 g of sodium polyacrylate _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.6g j. 130 ml of methanol. Compounds FS-11 and FS-2 for use in the present invention as surfactants and FS used in Example 1 as a comparative compound.
-D and FS-E were added in the amounts shown in Table 4 to prepare three types of back surface protective layer coating solution formulations.

[0117]

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(Preparation of Coating Sample) The above-mentioned back layer coating solution was applied to the transparent polyethylene terephthalate support side together with 1 g / m ² of the surface protective layer coating solution of the back layer so that the total coating amount of gelatin was 3.5 g / m ² . It applied so that it might become. Subsequently, the above-mentioned emulsion coating solution and surface protective layer coating solution were coated on the opposite side of the support, with a coating amount of 2.5 g / m ² and a gelatin coating amount of the surface protective layer of 1 g / m ² . Sample Nos. 6 to 8 were prepared. The amount of the hardener N, N'-ethylenebis- (vinylsulfone acetamide) was adjusted to 2.6% by mass based on the total gelatin amount.

(Method of Sensitometry) Samples Nos. 6 to 8 thus prepared were applied at a temperature and humidity of 25 ° C. and a relative humidity of 60%, allowed to stand for 10 days, and cut into a size of 25.7 × 36.4 cm. For each sample, use Fuji Photo Film FCR70
780nm infrared semiconductor laser scanner for 00 (C
(R-LP414 type). The automatic development process is C
The conveyance speed was doubled by exchanging the gear head at the self-developing part of the R-LP414 type.

The CR-LP414 type double speed remodeling machine takes a time from the moment when the tip of the photosensitive material is inserted into the automatic processing machine to the time when it is processed and the same tip comes out from the automatic processing machine (so-called "Dry"). "to Dry" is 33.4 seconds. The detailed specifications of the modified machine are shown below.

The developer and the fixing solution were prepared by adding water to each of the commercially available developer and fixing solution of CE-DF-1 kit manufactured by Fuji Photo Film Co., Ltd. so as to have a volume of 15 liters. Fuji RD- manufactured by Fuji Photo Film Co., Ltd.
III A starter to which 300 ml was added was used. The developer temperature is 35 ° C. ± 0.2 ° C. and the fixing temperature is 32 ° C.
The temperature was adjusted to 0.2C.

(Evaluation of Roller Transfer Failure of Antihalation Dye Drying Section) Sample Nos. 6 to 8 were treated with the processing conditions A to G shown in Table 4.
After the continuous processing, the roller in the drying section was stained by the antihalation dye, and the occurrence of a failure to be transferred to the photosensitive material was evaluated. At the same time, density unevenness was also evaluated. The density unevenness was evaluated by performing uniform exposure at an output at which each sample had a density fog of +1.0. Evaluation is visually 5
A grade was given. 1. Very poor 2. Inferior Normal 4. Good 5. Very good

[0123]

[Table 4] Table 5 shows the evaluation results.

[0124]

[Table 5]

As is clear from Table 5, Sample 8 of the present invention
However, it is understood that the transfer of the antihalation dye to the roller in the drying section is small, and the density unevenness is small.

[0126]

According to the present invention, it has become possible to provide a photosensitive material which can provide sufficient sensitivity without density unevenness even in a processing system in which the replenishment amount of the developing solution is small, and which can be processed rapidly at the same time.

Claims (2)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, the amount of iodine contained in silver halide grains. Is an average of 0 mol% or more and 0.45 mol% or less, and further contains a surfactant represented by the following general formula (F). General formula (F): Rf-Rc-Z [wherein, Rf represents a perfluoroalkyl group, Rc represents an alkylene group having 1 or more carbon atoms, Z represents an anionic group necessary for imparting surface activity, It represents a group having a cationic group or a nonionic polar group. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein S × T ≦ 1000 (where S is a 1
It represents the replenishment amount of the developer per sheet (ml / 4 cut), and T represents the processing time (second) of Dry to Dry. A developing method, wherein the developing process is performed under the condition represented by ()).