JPH0968769A - Silver halide photographic sensitive material, its developing method, drying method and storing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent quality of voide characters and to decrease color contamination by doping silver halide particles with specified metal atoms of the platinum group and in the 4th period in the periodic table or also with a specified rare earth compd. SOLUTION: This photosensitive material contains one element selected from the platinum group and one element selected from metal atoms in the 4th period in the periodic table, or one element selected from the platinum group and one element selected from rare earth elements. The platinum group includes 6 elements of rhodium, ruthenium, palladium, osmium, iridium and platinum, and the silver halide particles contain one of these 6 elements. Rhodium, ruthenium and osmium are preferable among these 6 elements. The metal atoms in the 4th period of the periodical table are potassium (atomic number 1) to selenium (atomic number 34), and iron, cobalt, nickel and vanadium are preferable. Further, the rare earth elements are scandium (atomic number 21), yttrium and 17 lanthanoids (atomic number 57 to 71).

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 for printing plate making and a processing method thereof.
In particular, the present invention relates to a silver halide photographic light-sensitive material for printing plate making which is excellent in character quality and residual color (color contamination) due to a contrast-increasing agent and a contrast-increasing aid in a processing method of processing with a low pH developer, and a processing method thereof. Is.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials have been widely used because they can obtain images with high sensitivity and high resolution. For printing plate making, printed matter with good reproducibility of fine lines is required as a photographic material. Especially in the Japanese market, it is necessary to use Mincho typeface and Gothic typeface on the same paper surface so that both typefaces are reproduced at the same time. There is a strong demand for a printing and plate-making technique with excellent reproducibility. As an attempt to improve this, a method of increasing the absorption of extra incident light and reflected scattered light by increasing the concentration of the backing layer on the side opposite to the silver halide photographic photosensitive layer of the support has been put into practical use. This method can improve the image quality of the bright light reproducibility by improving the light absorption degree. However, since there is a strong demand for the reproducibility of higher density fine lines,
This method is not sufficient, and further improvement is desired.

In order to always obtain such an image with high reproducibility of fine lines of higher density, it is necessary to ensure the stability of development. For that purpose, a method of processing with a developing solution having a low pH can be mentioned. . If it can be processed at a low pH from the viewpoint of stability of development processing, it is possible to prevent the oxidation of the developing agent, but on the other hand, the development activity tends to decrease, and as a result, a high-contrast and high-density image cannot be obtained and reproduced. There is a problem that the property is likely to be deteriorated. Further, the treatment with a low pH developer also causes a problem that the dye is retained in the photosensitive layer because the decomposition of the dye is suppressed and color contamination is likely to occur.

It is difficult for a hydrazine compound to have a high contrast at a low pH, and when a hydrazine compound is processed with a developer having a high pH, the contrast is effectively advanced and the sharpness is improved, but at the same time, the developing agent is easily oxidized. In particular, for a low-sensitivity bright room silver halide photographic light-sensitive material used for reversing applications, a recipe is used in which silver halide grains are heavily doped with rhodium in order to provide low sensitivity and high contrast. However, such a technique of doping rhodium still does not satisfy the above-described reproducibility of high-density thin lines. Therefore, although it has been proposed to use hydrazine in combination to promote desensitization, it is difficult to exert its effect at low pH and satisfactory performance is not obtained.

[0005]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above-mentioned circumstances, and the object is to provide excellent printing reproducibility, excellent quality of blank characters, and less color contamination for printing plate making. The present invention provides a silver halide photographic light-sensitive material, which provides a hydrazine-containing bright-room light-sensitive material which can be processed at low pH and which has stability of processing.
It is an object of the present invention to provide an image having excellent light-mark reproducibility and blank character quality in a bright room light-sensitive material to be processed below and having little color contamination.

[0006]

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

(1). The silver halide grains are at least one selected from the platinum group and at least one selected from metal atoms of the fourth period of the periodic table, or at least one selected from the platinum group and at least one selected from rare earth elements. A silver halide photographic light-sensitive material characterized by containing one of the following.

(2). The silver halide grains are characterized in that the platinum group is selected from the following (a), the metal atom of the fourth period of the periodic table is selected from the following (b), and the rare earth element is the following (c): The silver halide photographic light-sensitive material as described in (1) above.

(A) Rhodium, osmium and ruthenium (b) Iron, cobalt, nickel and vanadium (c) Cerium (3). The silver halide photographic light-sensitive material according to (1) or (2), wherein the silver halide grains contain a non-metal oxidizing agent.

(4). The silver halide photographic light-sensitive material described in any one of (1) to (3), which contains at least one selected from a hydrazine compound, an amine compound, a redox compound and a tetrazolium compound.

(5). A method for developing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material described in (1) to (4) with a developer having a pH of 9 to 10.9.

(6). The silver halide photographic light-sensitive material described in (1) to (4) is used in a relative humidity of 20% or less and a temperature of 10 to 10.
A method for drying a silver halide photographic light-sensitive material, which comprises drying at 90 ° C.

(7). A method of storing a silver halide photographic light-sensitive material, which comprises storing the silver halide photographic light-sensitive material according to (1) to (4) at a relative humidity of 20% or more and 60% or less.

According to the present invention, a specific white metal and a specific metal atom of the 4th period of the periodic table, or a specific rare earth compound are used in combination to dope into a silver halide grain to obtain low sensitivity and high contrast. This has the effect of obtaining a clear image. Further, even if hydrazine is used together at a low pH, the accompanying effect that the desensitizing contrast is sufficiently satisfied is also exhibited.

The present invention will be described below.

The silver halide photographic light-sensitive material of the present invention comprises
Containing at least one selected from the platinum group and at least one selected from metal atoms of the fourth period of the periodic table, or at least one selected from the platinum group and at least one selected from rare earth elements It is characterized by that.

The platinum group means six elements of rhodium, ruthenium, palladium, osmium, iridium and platinum. In the present invention, silver halide grains contain at least one of these six elements. Of these six elements, rhodium, ruthenium and osmium are preferable from the viewpoint of achieving the object and effects of the present invention.

Further, examples of the metal atom in the 4th period of the periodic table include potassium to atomic number 19 to selenium 34. In the present invention, iron, cobalt, nickel and vanadium are preferable. Further, as the rare earth element, 17 elements such as scandium having an atomic number of 21, yttrium and lanthanoids having an atomic number of 57 to 71 can be mentioned, and cerium is preferable in the present invention.

Rhodium, ruthenium, osmium, iron, cerium, cobalt, nickel and vanadium which are preferably used in the present invention are preferably added in combination during the formation of silver halide grains. As the addition position, there are a method of uniformly distributing in the silver halide grains and a method of forming a core-shell structure and localizing to the core portion or the shell portion. It is often better to have more of them in the shell. In addition, instead of being localized in a discontinuous layer configuration, a method of increasing the abundance as the particles are continuously outside the particles may be used. The addition amount is 10 ^-9 to 1 per mol of silver halide.
The range of 0 ^-3 mol can be appropriately selected, and the range of 10 ^-5 to 10 ^-4 mol is particularly preferable.

Rhodium, ruthenium, osmium, iron,
Metal ions such as cerium, cobalt, nickel, and vanadium can have the ligands listed below in addition to the halogen atom as the ligand. As a specific example, ruthenium (Ru) will be described below as an example, but the present invention is not limited thereto.

[Ru (NO) Cl ₅ ] ^-2 , [Ru (NO) Br ₅ ] ^-2 [Ru (NO) I ₅ ] ^-2 , [Ru (NO) F ₅ ] ^-2 [Ru (CN) Cl ₅ ] ^-2 , [Ru (CN) Br ₅ ] ^-2 [Ru (CN) I ₅ ] ^-2 , [Ru (CN) F ₅ ] ^-2 [Ru (SCN) Cl ₅ ] ^-2 , [Ru (SCN) Br ₅ ] ^-2 [Ru (SCN) I ₅ ] ^-2 , [Ru (SCN) F ₅ ] ^-2 [Ru (SeCN) Cl ₅ ] ^-2 , [Ru (SeCN) Br ₅ ] ^-2 [Ru (SeCN) I ₅ ] ^-2 , [Ru (SeCN) F ₅ ] ^-2 [Ru (TeCN) Cl ₅ ] ^-2 , [Ru (TeCN) Br ₅ ] ^-2 [Ru (TeCN) I ₅ ]. ^-2, [Ru (TeCN) F _5] ^-2 [Ru (CO) Cl _5] ^-2, [Ru (CO) Br _5] ^-2 [Ru (CO) I _5] ^-2, [Ru (CO) F ₅ ] ^-2 [Ru (NH ₃ ) Cl ₅ ] ^-2 , [Ru (NH ₃ ) Br ₅ ] ^-2 [Ru (NH ₃ ) I ₅ ] ^-2 , [Ru (NH ₃ ) F ₅ ] ^-2 [RuCl ₆ ] ^-2 , [RuBr] ₆ ] ^-2 [RuI ₆ ] ^-2 , [RuF ₆ ] ^-2 [Ru (NO) Cl ₂ (H ₂ 0) ₂ ] ^-1 , [Ru (NO) Br ₂ (H ₂ 0) ₂ ] ^-1 [Ru (NO) F ₂ (H ₂ 0) ₂ ] ^-1 , [Ru (NO) I ₂ (H ₂ 0) ₂ ] ^-1 [Ru (NO) Cl ₄ (CN)] ^-2 , [Ru ( NO) Cl ₄ (SCN)] ^-2 [Ru (NO) Cl ₄ (SeCN)] ^-2 , [Ru (NO) Br ₄ (SeCN)] ^-2 , [Ru (NO) Cl ₃ (CN) ₂ ] ^-2, _{[Ru (NO) Br 3 (CN} ) 2 ] ^-2 [Ru (NO) Cl _5] ^-4, [Ru (NO) Br _5] ^-4 [Ru (NO) I _5] ^-4, [ Ru (NO) F ₅ ] ^-4 [Ru (CN) Cl ₅ ] ^-4 , [Ru (C N) Br _5] ^-4 [Ru (CN) _{I 5]} ^-4, [Ru (CN) F _5] ^-4 [Ru (SCN) Cl _5] ^-4, [Ru (SCN) Br _5] ^-4 [ Ru (SCN) I ₅ ] ^-4 , [Ru (SCN) F ₅ ] ^-4 [Ru (SeCN) Cl ₅ ] ^-4 , [Ru (SeCN) Br ₅ ] ^-4 [Ru (SeCN) I ₅ ] ^{- 4,} [Ru (SeCN) F _5] ^-4 [Ru (TeCN) Cl _5] ^-4, [Ru (TeCN) Br _5] ^-4 [Ru (TeCN) I _5] ^-4, [Ru (TeCN) F _5] ^-4 [Ru (CO) Cl _5] ^-4, [Ru (CO) Br _5] ^-4 [Ru (CO) I _5] ^-4, [Ru (CO) F _5] ^-4 [Ru (NH ₃ ) Cl ₅ ] ^-4 , [Ru (NH ₃ ) Br ₅ ] ^-4 [Ru (NH ₃ ) I ₅ ] ^-4 , [Ru (NH ₃ ) F ₅ ] ^-4 [RuCl ₆ ] ^-4 , [ RuBr _6] ^-4 [RuI _6] ^-4 [RuF _6] ^-4 _{[Ru (NO) Cl 4 (CN} ) ] ^-4 _{[Ru (NO) Cl 4 (SCN} ) ] ^-4 _{[Ru (NO) Cl 4 (SeCN} ) ] ^-4 [Ru (NO) Br ₄ (SeCN)] ^-4 [Ru (NO) Cl ₃ (CN) ₂ ] ^-4 , [Ru (NO) Br ₃ (CN) ₂ ] ^-4 , [Ru (NH ₃ ) ₆ ] Cl ₃ , [ For metals other than Ru (NH ₃ ) ₆ ] Br ₃ Ru such as rhodium, iron, cerium, osmium, cobalt, nickel and vanadium, R
Since it can be represented by replacing the u portion with Rh, Fe, Ce, Os, it is omitted, but the hexadentate ligand transition metal compound is disclosed in JP-A-2-2082 and JP-A-2-2085.
No. 3, No. 2-20854, and No. 2-20855 can be referred to.

As the alkali complex salt, general sodium salts and potassium salts can be selected, but in addition to this, primary, secondary and tertiary amine salts may be used. For example, K ₂ [R
uCl ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₄ [Ru ₂ Cl
₁₀ O] XH ₂ 0, K ₂ [RuCl ₅ (H ₂ O)] and the like.

The non-metal oxidizing agent refers to an inorganic or organic compound other than metal capable of oxidizing the latent image of silver halide grains. The latent image can be oxidized means that a film exposed to a 0.1 mol / l aqueous solution of these compounds (pH 2.0) is immersed at 25 ° C. for 2 minutes to destroy the latent image by 20% or more. It means that you can.

Non-metallic oxidants include hydrogen peroxide, chloramine T, bromosuccinimide, chlorosuccinimide, sodium hypochlorite (NaOCl), potassium hypochlorite, chlorine, bromine, iodine, and benzoyl peroxide. (BPO) or azobisisobutyronitrile (A
Examples thereof include organic peroxides such as IBN). These non-metal oxidizing agents can be diluted with water, alcohol, etc. before use. Alternatively, it may be added in the form of fine powder.

Silver halide grains containing the above metal atoms are dispersed in a hydrophilic colloid medium, for example, gelatin to prepare a silver halide emulsion, followed by polyethylene terephthalate, polyethylene naphthalate, polyethylene. The silver halide photographic light-sensitive material of the present invention can be obtained by coating it on tetrahydronaphthalate, syndiotactic polystyrene or triacetate cellulose support.

The silver halide may be any of octahedron, tetrahedron, amorphous plate and cubic crystal, but high-sensitivity tabular grains or high-hardness cubic grains are preferably used. AgBr, AgCl, AgClB as the silver halide composition
r, AgClBrI, AgBrI, AgClBrI, etc. can be optionally used, but Ag is used for high-sensitivity emulsions.
AgBrI rich in Br composition is preferable. For rapid processing, silver chloroiodobromide or silver chlorobromide emulsion having an AgCl content of 90 mol% or more and having a low iodine is preferable.

The grain size of silver halide for a printing photosensitive material is 0.
05-0.2 μm is often used.

When the above-mentioned element is applied for printing plate making, use of a hydrazine compound or a tetrazolium compound as a contrast-increasing agent, an amine compound as a contrast-increasing aid, or a redox compound releasing a development inhibitor by oxidation. You can As a hydrazine compound, -NHN
It is a compound having an H-group and can be represented by the following general formula as a typical one.

T-NHNH-CO-V, T-NHNH-COCO-V In the formula, T is an aryl group which may be substituted, V is a hydrogen atom, an aryl group which may be substituted, an alkyl group and an amino group. Represents a group. Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring. Preferred substituents are linear or branched alkyl groups (preferably having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl group, n-dodecyl group, etc.), alkoxy groups (preferably having 2 to 21 carbon atoms, such as methoxy). Group, ethoxy group, etc.), aliphatic acylamino group (preferably having 2 to 2 carbon atoms)
1 alkyl group such as acetylamino group heptylamino group), aromatic acylamino group and the like. In addition to these, for example, the above-mentioned substituted or unsubstituted aromatic ring is -CONH-,- _{O -, - SO 2 NH -} , -
NHCONH -, - including those attached with a linking group such as CH ₂ CHN-. The hydrazine compound can be synthesized with reference to the description in US Pat. No. 4,269,929. The hydrazine compound can be contained in the emulsion layer, in a hydrophilic colloid layer adjacent to the emulsion layer, or in another hydrophilic colloid layer. The hydrazine compound can be added after dissolving in alcohols such as methanol and ethanol, ethylene glycols, ethers, ketones and the like. The amount added is in the range of 10 ^-6 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol, per mol of silver halide.

Particularly preferred hydrazine compounds are listed below.

(1) 1-formyl-2-{[4- (3-
n-Butylureido) phenyl]} hydrazine (2) 1- (2,6-tetramethylpiperidinooxalylamide) -2- {4- [2- (2,4-di-tert)
Pentylphenoxy) butylamido] phenyl} hydrazine (3) 1- (2,6-tetramethylpiperidinooxalylamide) -2- {4- [2- (2,4-di-tert)
Pentylphenoxy) butylamido] phenylsulfonamidephenyl} hydrazine (4) 1- (2,6-tetramethylpiperidinooxalylamide) -2- {3- [1-phenyl-1'-p-chlorophenylmethanethioglycine Amidophenyl] sulfonamidophenyl} hydrazine (5) 1-formyl-2-{[4- (octyl-tetraethylene oxide-thio-glycinamide phenyl-
(Sulfonamido) phenyl]} hydrazine (6) 1-formyl-2- {4- [2- (2,4-di-
tert Pentylphenoxy) butylamido] phenyl} hydrazine Particularly preferred tetrazolium compounds are listed below.

(1) 2,3-di (p-methoxyphenyl) -5-phenyltetrazolium chloride (2) 2,3-di (p-methylphenyl) -5-phenyltetrazolium chloride (3) 2,3- Di (m-methylphenyl) -5-phenyltetrazolium chloride (4) 2,3,5-tri (p-methylphenyl) tetrazolium chloride (5) 2,3,5-tri (p-methoxyphenyl) tetrazolium chloride In addition to these, the tetrazolium compound described in JP-B-5-58175 can also be used.

The amine compound as a contrast enhancing agent can be represented by the following general formula containing at least one nitrogen atom.

RN (Z) -Q or RN (Z)-
L-N (W) -Q In the formula, R, Z, Q and W each represent an optionally substituted alkyl group having 2 to 30 carbon atoms.

Further, these alkyl group chains may be bonded with a hetero atom such as nitrogen, sulfur or oxygen. R and Z, or Q and W may combine with each other to form a 5- to 6-membered saturated and unsaturated ring. L represents a divalent linking group. Heteroatoms such as sulfur, oxygen and nitrogen may be contained in this linking group. The number of carbon atoms in the linking group of L is 1 to 200, the sulfur atom is 1 to 30, and the nitrogen atom is 1
Up to 20 and preferably up to 40 oxygen atoms, but are not particularly limited.

Specific examples of these amino compounds include:
Diethylaminoethanol, dimethylamino-1,2-propanediol, 5-amino-1-pentanol, diethylamine, methylamine, triethylamine, dipropylamine, 3-dimethylamino-1-propanol,
1-dimethylamino-2-propanol, bis (dimethylaminotetraethoxy) thioether, bis (diethylaminopentaethoxy) thioether, bis (piperidinotetraethoxy) thioether, bis (piperidinodiethoxy) thioether, bis (diethoxyethyl) Aminotetraethoxy) ether, 5-dibutylaminoethylcarbamoylbenzotriazole, 5-morpholinoethylcarbamoylbenzotriazole, 5- (2-methylimidazole-2-ethylene) carbamoylbenzotriazole, 5-dimethylaminoethylureylenebenzotriazole, 5 -Diethylaminoethylureylene benzotriazole, 1-diethylamino-2- (6
-Aminopurine) ethane, 1- (dimethylaminoethyl) -5-mercaptotetrazole, 1-piperidinoethyl-5-mercaptotetrazole, 1-dimethylamino-5-mercaptotetrazole, 2-mercapto-5
-Dimethylaminoethylthiothiadiazole, 1-mercapto-2-morpholinoethane and the like can be mentioned.

These amine compounds are described in JP-A-57-1.
20434, JP-A-57-129435, JP-A-5
7-129436, JP-A-60-129746, JP-A-56-94347, and JP-A-60-140340.
JP-A-60-218642 and JP-A-60-662.
48, US Pat. Nos. 417,498 and 3,02
No. 1,215, No. 3,046,134, No. 3,5
No. 23,787, No. 3,746,545, No. 4,
Those described in No. 013,471, No. 4,038,075, No. 4,072,523, No. 4,072,526 and the like can be appropriately selected and used.

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines and reductones as redox groups.

A preferred redox compound is a compound having a --NHNH-- group as a redox group, which can be represented by the following general formula.

(A) T-NHNH-CO-V-PUG, (b) T-NHNH-COCO-V-PUG In the formula, each T is an aryl group, an alkyl group, an amino group or a heterocycle which may be substituted. Represents a group. The aryl group represented by T and V contains a benzene ring or a naphthalene ring, and this ring may be substituted with various substituents. Preferred substituents include the general formula of the hydrazine compound described above, T and The groups mentioned under V are used. Examples of the photographically useful group represented by PUG in the general formula include 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-nitrobenztriazole, 4-nitrobenzo. Examples thereof include triazole, 5-nitroimidazole, 4-nitroimidazole and the like.

These photographically useful groups are T-NHNH-
It can be directly connected to the CO site of CO- via a hetero atom such as N or S, or via an alkylene, phenylene, aralkylene or aryl group and further via a hetero atom such as N or S. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2- (dodecylethylene oxide thiopropionamide) -5-
(5-nitroindazol-2-yl) hydroquinone, 2- (stearylamido) -5- (1-phenyltetrazol-5-thio) hydroquinone, 2- (2,4
-Di-t-amylphenoxypropionamide) -5
Examples thereof include-(5-nitrotriazol-2-yl) hydroquinone and 2-dodecylthio-5- (thiadiazole-2-thio) hydroquinone.

Redox compounds are described in US Pat.
The compound can be synthesized with reference to the description in JP-A-9,929. The redox compound can be contained in the silver halide photographic emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer. Redox compounds can be added to alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, esters such as ethyl acetate, acetone and methyl ethyl ketone. It can be added after being dissolved in the ketones.

Further, those which are hardly soluble in water or an organic solvent can be arbitrarily dispersed to have an average particle size of 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. For dispersion, a surfactant such as an anion or nonion, a thickener, a latex, or the like can be added and dispersed.

The amount added is in the range of 10 ^-6 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol, per mol of silver halide.

Particularly preferred redox compounds are listed below.

(A). 1- (4-nitroindazole-
2-yl-carbonyl) -2-{[4- (3-n-butylureido) phenyl]} hydrazine (b). 1- (5-nitroindazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert)
Pentylphenoxy) butylamido] phenyl} hydrazine (c). 1- (4-nitrotriazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert)
Pentylphenoxy) butylamido] phenyl} hydrazine (d). 1- (4-nitroimidazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert)
Pentylphenoxy) butylamide] phenylsulfonamidophenyl} hydrazine (e). 1- (1-sulfophenyltetrazole-4-
Methyloxazole) -2- {3- [1-phenyl-
1'-p-chlorophenylmethanethioglycinamide phenyl] sulfonamidophenyl} hydrazine (f). 1- (4-nitroindazol-2-yl-carbonyl) -2-{[4- (octyl-tetraethylene oxide-thio-glycinamide phenyl-sulfonamido) phenyl]} hydrazine oxidant of the developing agent in the highly exposed areas For example, since a large amount of semiquinone is produced, there are many reactions of hydrazine compounds. This reaction according to the exposure amount is called imagewise. Hydrazine that has reacted with the oxidized product of the developing agent has the further disadvantage that it deteriorates the image quality due to the image enlargement effect because it changes into a compound having a development activity and develops even the unexposed portion in the vicinity. The image quality can be improved by adopting a mechanism that suppresses the development of the highly exposed portion as the development reaction progresses. Redox compounds are used for this purpose.
However, since the redox compound reacts with the oxidant of the developing agent, it often requires a high pH, and thus the reaction is difficult to proceed at a low pH.

Therefore, a release mechanism that releases the development-inhibiting substance and the development-promoting substance as the development proceeds is preferable. One method is to disperse a development-inhibiting compound that is insoluble at pH 7 or less and soluble at pH 8 or more in the form of fine particles having an average particle size of 0.01 to 100 μm in the hydrophilic colloid layer, and at the time of development, Examples include solubilization to suppress development. The development-inhibiting substance in the form of solid fine particles can be present in the silver halide emulsion layer, in a layer adjacent to the emulsion layer, another layer via the adjacent layer, or the like. In order to exert the effect as the development progresses, a layer separated from the emulsion layer to be development-inhibited is preferable. Therefore, it is preferable that the emulsion layer is added to the layer through the adjacent layer, but depending on the case, the adjacent layer may be added. Since the development of the emulsion layer is delayed as it is closer to the support, the image quality is improved by dividing the emulsion layer into at least two layers so that the side closer to the support has higher sensitivity and the emulsion layer farther from the support has lower sensitivity. Although it can be improved, this is often not enough.

Therefore, development can be suppressed and the image quality can be improved by allowing the development inhibiting substance to diffuse and reach from the surface protective layer side toward the low-sensitivity emulsion layer far from the support while being solubilized during development. On the contrary, the image quality can be improved by releasing and diffusing the development promoting substance from the side close to the support to promote the development of the emulsion lower layer. Examples of development inhibitors for such purposes include 5-nitroindazole, 5-nitrobenzimidazole, 5-methylbenzotriazole, 4-nitroindazole, 1-phenyl-5-mercaprotetrazole, 1-p. -Carboxyphenyl-5-mercaptotetrazole and the like.
These can also be used as an antifoggant.
As the development accelerator, amines, thioether compounds,
Examples thereof include oxythioether compounds.

In the present invention, in addition to desensitization by metal doping, desensitization by using an organic desensitizer can be used together.

The organic desensitizers that can be used in the present invention are shown below.

(1) Phenosafranine (2) Pinacryptol Green (3) 2,3-Dimethyl-6-nitro-benzothiazolium paratoluene sulfonate (4) 2- (paranitrostyryl) quinoline paratoluene Sulfonate (5) 1,3-Diethyl-1'-methyl-2'-phenylimidazo [4,5-b] quinoxaline-3'-indolocarbocyanine iodide (6) Pinacryptol yellow (7) 1, 1,3,3'-hexamethyl-5,5'-dinitroindocarbocyanine paratoluene sulfonate (8) 5,5'-dichloro-3,3'-diethyl-6
6'-dinitrocarbocyanine iodide (9) 1,1'-dimethyl-2,2'diphenyl-3,
3'indolocarbocyanine bromide Hydrazine used in the present invention, a tetrazolium compound,
The addition amount of the organic desensitizer, the redox compound and the amine compound is 1 × 1 per mol of silver halide.
It is preferable to contain 0 ^{-6 to} 5 x 10 ^-2 mol, particularly 1 x
It is preferably 10 ^{−4 to} 2 × 10 ⁻² mol.

The following can be used for cross-linking gelatin, carboxylic acid, a polymer having a hydroxy group or an amino group.

For example, aldehydes such as glyoxal and mucochloric acid, cyanuric acid of sodium salt of 2,4-dichloro-6-hydroxy-s-triazinic acid, bis (aziridineacetamido) hexane and bis (aziridineacetamido) butane, etc. Aziridine or 1,2
Examples thereof include vinyl sulfone type hardeners such as bis (sulfonylacetamide) ethane, 1,3-bis (vinylsulfonyl) -2-propanolethane and bis (vinylsulfonyl) methyl ether. Particularly preferred hardeners are represented by the following general formula R ¹ -N (R ² ) -CO-pyridinium, where the pyridinium ring is R ³ and / or L-.
It is substituted with X-SO ₃ H. In the formula, R ¹ and R ² represent an alkyl group or an aryl group, and R ¹ and R ² may form a ring. R ³ represents a hydrogen atom or a substituent. L and X represent a single bond or a divalent group. X is a single bond or -O-,-
Represents N (R ⁴ ) —, and R ⁴ represents a hydrogen atom, an alkyl group or an aryl group.

More specifically, R ¹ and R ² are
A linear, branched or cyclic C1-C20 alkyl group (for example, a methyl group, an ethyl group, a butyl group, a cyclohexyl group, a 2-ethylhexyl group, a dodecyl group, etc.), a C6-C20 aryl group (for example, Phenyl group, naphthyl group and the like). R ¹ and R ² may have a substituent, and examples of the substituent include a halogen atom (for example, C
l, Br, I), an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group), an aryl group having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), an aryloxy group having 1 to 10 carbon atoms (eg, Phenoxy group) and the like.
Further, it is also preferable that ^two of R ¹ and R ² are bonded to each other to form a ring together with a nitrogen atom, and particularly preferable examples are cases where a morpholine ring, a pyrrolidine ring and a piperidine ring are formed, and the most preferable example is a pyrrolidine ring. If you have. R ³ represents a hydrogen atom or a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl group, benzyl group), an aryl group having 6 to 20 carbon atoms (eg, phenyl group), Halogen atoms (eg Cl, Br,
I), an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group), an aryloxy group having 6 to 20 carbon atoms (for example, a phenoxy group), and the like, and a hydrogen atom is particularly preferable.

L represents a single bond, an alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group), an arylene group having 6 to 20 carbon atoms (for example, a phenylene group) and those. combination resulting divalent group (e.g., _{-CH 2 -C 6 H 4 -CH 2} -
Group), an acylamino group (for example, —NHCOCH ₂ —)
Group), a sulfonamide group (for example, —NHSO ₂ CH ₂ —
Group) and the like, but preferably a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group.

X represents a single bond or -O-, -N (R ⁴ )-, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, benzyl group), carbon number. 1
To 20 alkoxy groups (for example, methoxy groups), with a hydrogen atom being particularly preferred.

Particularly preferred specific examples are shown below.

(1) Diethylcarbamoyl- (3-sulfo) pyridinium betaine (2) Diethylcarbamoyl- (3-sulfoester)
Pyridinium betaine (3) Pyrrolidinocarbamoyl- (4-sulfoethyl)
Pyridinium betaine (4) Morpholinocarbamoyl- (4-sulfoethyl)
Pyridinium betaine (5) Piperidinocarbamoyl- (4-sulfoethyl)
Pyridinium betaine (6) Morpholinocarbamoyl- (3-sulfomethylamide) pyridinium betaine (7) Pyrrolidinocarbamoyl- (4-sulfoethylamido) pyridinium tine These hardeners can be used according to a conventional method, It is preferable to use 0.01 to 1 mmol per 1 g of gelatin.

The matting agent is mainly composed of polymethylmethacrylate or silicon dioxide, and its surface may be changed in composition by an organic or inorganic surface modifier. The average particle size of the matting agent can be selected in the range of 0.1 to 30 μm. The particle size distribution may be monodisperse or polydisperse, but a method of mixing two or more types of monodisperse to obtain a desired degree of monodispersity is preferred. The monodispersity of the matting agent can be determined by applying the monodispersity of silver halide.

Anionic and nonionic surfactants are preferably used as the surfactant used in the dispersion of various additives used in the present invention, the coating aid or the antistatic agent.

The basic structure of the surfactant includes alkyl sulfosuccinic acid ester, alkyl benzene sulfonic acid, alkyl phenoxy alkylene oxide sulfonic acid ester, alkyl sulfonic acid ester and the like, and these alkyl groups have a carbon number of 2 to 30. Preferably, 4 to 16 are particularly preferably used. Specifically, dodecylbenzene sulfonic acid, nonylphenoxyethylene oxide sulfonic acid ester (n = 4), sulfosuccinic acid di (2-ethylhexyl ester sodium salt, dinonylphenoxyethylene oxide sulfonic acid ester (n = 12), undecylcarboxylic acid amide Polyethylene oxide (n = 5), triisopropyl naphthalene sulfonic acid sodium salt, 1-methyl-1,1-bis (3,5-tert-amyl-2-phenoxydecaethylene oxide (n = 10)) methane, perfluoro Sodium octyl sulfonate, sodium perfluorooctyl carboxylate, sodium polysulfonate (degree of polymerization 5
0,000), polystyrene maleic acid copolymer (degree of polymerization 20
10,000).

Dyes, sensitizing dyes, antifoggants, antioxidants such as hydroquinone, hydroquinone monosulfonate, resorcin, catechol, etc., spherical particles having an average particle size of 1 to 20 μm, amorphous silica, methyl methacrylate, etc. Matting agent, tin, titanium, vanadium, zinc, copper, lightly doped with indium and phosphorus,
Silver, antistatic agents such as metals and metal oxides such as palladium,
It can be appropriately selected according to the use and performance of using other compounds such as a thickener such as polystyrene sulfonic acid or styrene maleic acid having a molecular weight of about 50,000 to 1,000,000, a development modifier, and the like. Further, an alkali-soluble matting agent used when unnecessary after development can also be used. This is because the polymer contains a carboxyl group that is soluble in alkali, and homopolymers such as maleic acid and acrylic acid, styrene-maleic acid copolymers and methyl methacrylate-
There are derivatives such as methacrylic acid. In order to reduce the load of drying during rapid processing, a water-soluble polymer that is present during exposure and elutes during development can be contained. In this case, in order to prevent precipitation and precipitation in the developing solution, it is preferable not to have ionicity such as anions and cations, but precipitation and aggregation can be suppressed by combining other additives. Examples of the hydrophilic polymer preferably used include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan and the like. The molecular weight of the hydrophilic polymer can be appropriately selected from 600 to 1,000,000. The lower the molecular weight is, the better to elute into the processing solution quickly during the processing, but if it is too low, the film strength of the film is deteriorated. Since the abrasion resistance of the film is deteriorated when a hydrophilic polymer is used, it is preferable to add inorganic colloidal silica, colloidal tin, colloidal zinc, colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite and the like. Zeolites include analsite, erionite, mordenite, chabazite, gmelinite and levinite, and synthetic zeolites include zeolites A, X, Y and L.

Examples of the apatite include hydroxyapatite, fluoroapatite, chlorine apatite and the like. The preferable addition amount is 1 to 200% by weight with respect to the hydrophilic binder. By treating with a silane coupling agent, the above inorganic compound does not easily agglomerate even when added to the emulsion, and the coating solution can be stabilized. Further, cracking due to the inorganic compound can be prevented. As silane coupling agents, triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropyl methacrylate, trimethoxysilanopropylglycidyl, 1-mercapto-3-triethoxysilanopropane, 1-amino-3-triethoxysilanopropane, Triethoxysilanophenyl, triethoxymethylsilane and the like. The properties of the silane coupling agent can be improved by performing a high temperature treatment together with the above-mentioned inorganic compound, compared to the simple mixing. The mixing ratio is preferably selected in the range of 1: 100 to 100: 1.

The layer structure of the silver halide photographic light-sensitive material of the present invention has at least one light-sensitive emulsion layer on a support, and a protective layer can be provided on the light-sensitive emulsion layer.
The emulsion layer and the protective layer can be further divided into two or more layers.
It is also possible to install an intermediate layer between the protective layer and the emulsion layer to control the diffusion of additives and the transmission of light, and to suppress the chemical or physical influence of the adjacent layers. A filter dye can be fixed to the protective layer to block the safety light. For immobilization, fine particles can be used, an anion-cation ionic bond can be used, or a redox reaction that decomposes by oxidation or reduction can be used. Fixing the dye on the lower layer of the emulsion layer or on the side opposite to the support to prevent halation is good for improving the image quality. The antihalation layer is preferably provided below the emulsion layer. In the case of an X-ray silver halide photographic light-sensitive material having emulsions on both sides, a filter dye is fixed as a transverse light-blocking layer. When two or more emulsion layers are provided, the emulsion having high photosensitivity and development may be provided closer to the support side or may be provided farther. On the side closer to the support, less light will reach and the permeation of the developer will be delayed.Therefore, providing an emulsion layer with high sensitivity and high developability improves the image quality, so it is preferable to apply it to medical and printing sensitive materials. You can Since the difference in developability becomes large in the latter stage of development, a redox compound releasing a development inhibitor can be used for speed control. In order to enhance the effect of the development inhibitor released from the redox compound, it is preferable that the layer in which the redox compound is present is adjacent to the emulsion layer via the intermediate layer. The specific layer structure is in the order of support / adhesive layer / transverse light blocking layer or antihalation layer / emulsion layer / intermediate layer / redox-containing layer / protective layer. It can also be used in the order of support / adhesive layer / transverse light blocking layer or antihalation layer / redox-containing layer / intermediate layer / emulsion layer / protective layer. The gelatin used in these layers can be swelled with a known crosslinking agent, but in order to perform crosslinking in each layer, it is preferable to adjust the molecular weight or use a crosslinking accelerator. The amount of gelatin used in each layer is usually 0.1 to 2.0 g / m ² . The crosslinking agent is preferably used in an amount of 0.01 to 1 mmol per gram gelatin. In addition to gelatin, a hydrophilic polymer such as dextrin, starch, glucose or a hydrophobic latex can be introduced into each layer to control the degree of swelling. The degree of swelling is 1
The 20th to 200th place is common.

For the drying of each layer, the temperature and time are adjusted according to the evaporation rate of water. The temperature is 25 ° C to 200 ° C,
A time of 0.1 second to 200 seconds is generally applied. The degree of swelling can be measured under a microscope by immersion in water,
It can be determined with a swelling meter. As the degree of swelling, the ratio (Lw / Ld) of the dry film thickness = Ld (23 ° C., the film thickness after humidity conditioning at 50% relative humidity for 24 hours) to the swollen thickness Lw in water at 23 ° C. The value multiplied by 100 can be used as an index.

The film surface pH of the constituent layers of the silver halide photographic light-sensitive material of the present invention is the pH measured after coating and drying,
The measurement is carried out by dropping 1 ml of pure water per 1 cm ^{2 of the} measured portion and using a pH meter. To lower the pH, use citric acid,
Acids such as oxalic acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, carbonic acid,
Further, when raising the pH, an alkaline agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate or sodium acetate can be used. The same method can be applied when adjusting the pH when using a photographic additive.

A plurality of constituent layers of 3 to 10 layers of the silver halide photographic light-sensitive material of the present invention are 30 to 1000 m per minute.
US Patent No. 3,636,37 for simultaneous high speed coating
The known slide hopper method or curtain coating described in No. 4, No. 3,508,947 can be used. In order to reduce unevenness during coating, it is preferable to lower the surface tension of the coating solution or to use the above-mentioned hydrophilic polymer which can impart a thixotropic property in which the viscosity is reduced by a shearing force.

The silver halide photographic light-sensitive material of the present invention comprises
A protective layer (backing layer) can be provided. When providing a protective layer, an adhesive layer / antistatic layer /
It is common to provide a dye containing layer / protective layer. As the adhesive layer, a vinylidene chloride copolymer or a styrene-glycidyl acrylate copolymer is applied to a corona-discharged support in a thickness of 0.1 to 1 μm, and then an indium or phosphorus-doped average particle size of 0.01 is applied. ~ 1 μm tin oxide, 5
It can be obtained by coating with a gelatin layer containing fine particles of vanadium oxide. Further, the styrene sulfonic acid and maleic acid copolymer can be formed by forming a film with the aziridine or carboxyl active type crosslinking agent described above. A dye layer may be provided on these antistatic layers to form a backing layer. The backing layer may contain an inorganic filler such as colloidal silica for dimensional stability, silica for preventing adhesion, a methyl methacrylate matting agent, a silicone-based slipping agent or a release agent for controlling transportability, and the like. it can. As the backing dye, a benzylidene dye or an oxonol dye is used. These alkali-soluble or decomposable dyes can also be made into fine particles and fixed. The concentration for preventing halation is 0.1 at each photosensitive wavelength.
Preferably, the concentration is up to 2.0.

Examples of the developing agent used in the developing solution include hydroquinones such as hydroquinone, sodium hydroquinone sulfonate, and chlorohydroquinone, as well as 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-dimethyl-3. -Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, pyrazolidones such as 1-phenyl-4-methyl-3-pyrazolidone, and superadditive development of N-methylparaaminophenol sulfate and the like It can be used in combination with the main drug. Further, ascorbic acid or isoascorbic acid may be used together with the above-mentioned super-additive developing agent without using hydroquinone. Sodium sulfite or potassium sulfite as a preservative, sodium carbonate or potassium carbonate as a buffer, EDTA or EDTA.2 as a chelating agent
Na, EDTA.4Na, etc. 5-methylbenzotriazole as a fog inhibitor or silver sludge inhibitor, 2-
Mercaptobenzothiazole, 1-phenyl-5-mercaptotetrazole, 6-nitrobenzimidazole,
1- (4-carboxylic acid phenyl) -5-mercaptotetrazole, 1- (4-sulfonic acid phenyl) -5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercapto-5-sulfonic acid-benzimidazole, development acceleration As the agent, diethanolamine, triethanolamine, diethylaminopropanediol and the like can be included. An antifoggant can be added to a photographic light-sensitive material layer such as an emulsion layer or an emulsion protective layer to improve not only fog suppression but also sharpness and bright reproducibility.
The developer can be adjusted to a pH of 9 to 12 with an alkaline agent such as sodium hydroxide or potassium hydroxide. Adjustment of pH is generally good for storage.
Used in the range of 10.9, but p for rapid processing
It can also be used at H11 ± 0.5. The development process is
It can be carried out under processing conditions of 20 ° C. to 40 ° C. and 1 second to 90 seconds. Further, the replenishment amount of the developing solution or the fixing solution is 5 to 216 m per 1 m ² by using a development accelerator or a sensitizer.
It can be in the range of 1 or less. It is particularly effective to reduce the replenishing amount by using the emulsion sensitizing technique to reduce the amount of silver halide grains used, and can be achieved in combination with the above-mentioned development promoting technique.

The method for drying the silver halide photographic light-sensitive material of the present invention is as follows: relative humidity 20% or less, temperature 10-9.
The method of drying at 0 degreeC is mentioned.

The method is to first set a dry-bulb temperature,
It is carried out by leaving the silver halide photographic light-sensitive material (sample) to be dried in an atmosphere having a wet-bulb temperature lower than the dry-bulb temperature. The drying process consists of constant rate drying in which the surface temperature of the sample being dried is equal to the wet-bulb temperature, and constant rate drying in which the surface temperature of the sample gradually approaches the dry-bulb temperature, and finally, reduced-rate drying, in which the surface temperature of the sample becomes equal to the dry-bulb temperature. In the present invention, the two processes are divided into two processes, a relative humidity of 20% or less and a dry-bulb temperature of 2
It is characterized by being dried at 0 ° C. or higher. In particular, the rate-decreasing drying process greatly affects the photographic characteristics, so it is preferable to dry this process under the above conditions. The relative humidity can be determined from the dry-bulb temperature and the difference between the dry-bulb temperature and the wet-bulb temperature, and is preferably 20% or less, particularly preferably 10% or less. The dry temperature is calculated by adding this dry bulb temperature to 20
It is preferably not lower than 100 ° C., and if it is too high, the emulsion will be fogged or the contrast will be deteriorated and the photographic characteristics will be deteriorated. The drying rate can be set arbitrarily, but productivity is improved if the rate is high, so drying within 10 minutes, or within 5 minutes is often adopted. As a method of increasing the drying speed, it is desirable to set the applied water content of the first sample, the so-called carried-in water content, to a small value, but if a certain amount of water is required for uniform application, the dry bulb temperature and the wet Increasing the difference in sphere temperature (decreasing the relative humidity) and increasing the heat transfer coefficient (increasing the air volume) are preferably applied.

The silver halide photographic light-sensitive material of the present invention may be stored at a relative humidity of 20% or more and 60% or less.

The silver halide photographic light-sensitive material is preferably packaged and stored in a packaging material which can be kept in a certain atmosphere in order to prevent deterioration of photographic performance and physical properties.
As an atmospheric condition, it is preferable that the atmosphere is not exposed to an oxidizing substance or a reducing substance and is stored in a state of appropriate humidity and temperature. When the humidity is low, the photographic additives crystallize and precipitate, the binder cracks, or fog increases.

Further, when the humidity is high, the front side of the silver halide photographic light-sensitive material and the adjacent back side thereof stick to each other to cause uneven exposure and uneven development. Also at this time, the fog is increased, the contrast is changed, and the photographic performance is often deteriorated. In order to prevent this, it is necessary to adjust the temperature and humidity and store it at the most preferable temperature. The silver halide photographic light-sensitive material of the present invention has a relative humidity of 20% or more and 60 or less.
It is preferable to store the content at not more than%. A packaging material is preferably used for storage, but it is preferable that the packaging material keeps confidentiality. Materials used for this purpose include high-density polyethylene, low-density polyethylene, polypropylene, polyvinylidene chloride, polyacrylonitrile and the like. It is preferable to store these airtight materials in an airtight manner. The thickness of the wrapping material has an influence on the moisture permeability, so that it is necessary to select it preferably. Generally, a thickness of 1 μm to 1 mm is adopted, and especially 5 μm to 1 mm.
A thickness of 00 μm is preferred. The material thus packaged can be further packaged in double or triple layers.

[0075]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 << Bright room photosensitive material for printing plate making >> A bright room photosensitive material for printing plate making was prepared as follows.

<Preparation of Silver Halide Emulsion for Bright Room> As shown in Table 1, metal ions were doped to give an average grain size of 0.
A silver halide having a thickness of 13 μm, AgCl of 98 mol% and Br of 2 mol% was prepared.

<Preparation of bright room light-sensitive material for printing plate making> A bright room silver halide emulsion was prepared using the prepared silver halide, and a polyethyl acrylate-butyl acrylate copolymer latex was prepared on a polyethylene terephthalate support. The silver halide emulsion layers were coated so that the coating amount was 0.5 g / m ² and the silver coating amount was 1.5 g / m ² , to prepare samples 1 to 15. Incidentally, during coating, the silver halide emulsion was divided into two and the chemical sensitization method was changed to provide a difference in sensitivity of 60% to provide an upper layer (low sensitivity) and a lower layer (high sensitivity). The compositions of the prepared silver halide emulsion and emulsion protective layer are shown below.

(Emulsion Layer Upper Layer Low Sensitivity) Hardening Agent 1-Formyl-2- {4- [2- (2,4-di-tert-pentylphenoxy) butylamido] phenyl} hydrazine (with an average particle diameter of 0.12 μm Solid dispersion) 0.02 g / silver 1 mol. Hardening aid bis (1-piperidyltriethylene oxaside) thioether, nonylphenoxide docosaethylene oxide sulfonate sodium salt 0.2 g / silver 1 mol Antifoggant hydroquinone mono Sulfonate, hydroquinone aldoxime, 1- (p-carboxyphenyl) -5-mercaptotetrazole, benzotriazole, 1-butanesulfonic acid-2,3, -dithiacyclohexane, adenine, butyl gallate 12 mg each / silver 1 mol・ Thickener Polystyrene sulfonic acid (molecule 500,000), styrene - maleic acid copolymer, respectively polyvinylpyrrolidone 0.1 g / m ² · redox compound 1- (5-nitroindazole-1-yl) -2- {4- [2- (2,4 Di-tert-pentylphenoxy) butylamido] phenyl} hydrazine (solid dispersion having an average particle size of 0.12 μm) 0.02 g / silver 1 mol (emulsion layer lower layer high sensitivity) -hardening agent 1-formyl-2- {4- [2- (2,4-di-tert-pentylphenoxy) butylamido] phenyl} hydrazine (solid dispersion having an average particle size of 0.12 μm) 0.02 g / silver 1 mol. Hardening aid bis (1-piperidyltriethyleneoxa). Side) thioether, nonylphenoxide coxaethylene oxide sulfonate-sodium salt 0.2 g / silver 1 mol-antifoggant High Doloquinone monosulfonate, hydroquinone aldoxime, 1- (p-carboxyphenyl) -5-mercaptotetrazole, benzotriazole, 1-butanesulfonic acid-2,3, -dithiacyclohexane, adenine, butyl gallate 12 mg / each Silver 1 mol-Thickener Polystyrene sulfonic acid (molecular weight 500,000), styrene-maleic acid copolymer polyvinylpyrrolidone 0.1 g / m ² (emulsion protective layer) with gelatin 0.5 g / m ² latex Coating amount 0.2 g / m ² Matting agent of silicon dioxide (average particle size 4 μm) 0.03 g / m ² The gelatin of each layer was crosslinked to 0.2 mmol / g gelatin with the hardener of the specific example (4). .

<Processing Step> The obtained Samples 1 to 15 were returned using a bright room printer based on the line drawing originals prepared in advance, and processed in the following steps using an automatic developing machine.

[0081] The composition of the treatment liquid is as follows.

(Composition of developer) 1-phenyl-3-pyrazolidone 1.5 g erythorbic acid 30 g 5-nitroindazole 0.250 g 5-methylbenzotriazole 0.06 g potassium bromide 3.0 g sodium sulfite 50 g potassium hydroxide 30 g Boric acid 10 g Water was added to make 1 L, and pH was adjusted to 10.20.

(Composition of fixing solution) Ammonium thiosulfate (72.5% W / V) aqueous solution 240 ml Sodium phosphite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Acetic acid (90% W / V aqueous solution) 13.6 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g Water was added. The volume was adjusted to 11 and the pH was adjusted to 5.0.

<Evaluation> With respect to the sample after the treatment, the quality of blank characters, storability and color contamination were evaluated.

(Outlined Characters) The extracted characters were evaluated by visually observing the reproducibility of Mincho and Gothic characters each having a size of 7 points with a 10-fold loupe. In each evaluation, a visual sensory relative evaluation of 7 steps was performed. Rank 7 is the best, Rank 1 is the worst, and practically 3 is the useful limit.

(Storability) Storability was 23 ° C. and relative humidity was 5
After controlling the humidity at 0% for 24 hours, the light reproducibility after standing at 55 ° C. for 72 hours was evaluated. In each evaluation, a visual sensory relative evaluation of 7 steps was performed. Rank 7 is the best, Rank 1 is the worst, and practically 3 is the useful limit.

(Color Contamination) Color contamination was evaluated by stacking five pieces of film on a sample of white paper. In each evaluation, a visual sensory relative evaluation of 7 steps was performed. Rank 7 is the best, Rank 1 is the worst, and practically 3 is the useful limit.

Table 1 shows the results.

[0089]

[Table 1]

The metal ion dope is shown by the amount used (molar amount) per mol of silver. Rhodium is trivalent with a hexacoordinate chlorine atom, Ru and Os are nitrosyl coordinating,
[Ru (NO) Cl ₅ ] ^-2 and [Os (NO) Cl ₅ ] ^-2
Was used. Chlorides were used as the other metals. CLO: sodium hypochlorite, BPO:
Benzoyl peroxide, AIBN: azobisisobutyronitrile.

As is clear from Table 1, when doping with Rh, Ru and Os, when a metal doping selected from iron, nickel, cobalt, vanadium and cerium is used together,
It can be seen that the extracted character quality and residual color are excellent. Further, it can be seen that the performance is further improved by using a non-metal oxidizing agent such as hydrogen peroxide or chloric acid.

Example 2 An experiment was carried out in the same manner as in Example 1, except that the quality of blank characters and the deterioration of color contamination of the sample with respect to the change in pH of the developer used were examined. First, adjust the pH of the developer to 11.
As a result of the evaluations listed in 5, all color contamination deteriorated. or,
When the pH is set to 10.0 or less, specifically 9.0 and 8.5, the quality of the extracted characters is severely deteriorated only by the doping of Rh, Ru and Os, and it is selected from iron, nickel, cobalt, vanadium and cerium. When the metal dope was used together, the deterioration of the extracted character quality was reduced, and when the non-metal oxidizing agent was used, the deterioration was almost eliminated.

Example 3 Samples 7 and 8 produced in Example 1 were selected, the drying conditions were changed as shown in Table 2 below, and the quality of blank characters and the deterioration of color contamination were examined.

Table 2 shows the results.

[0095]

[Table 2]

As is clear from Table 2, when the drying conditions are a relative humidity of 20% or less and a temperature of 10 ° C. or more and 90 or less, the quality of the extracted characters and the color contamination are excellent.

Example 4 After the sample 5 produced in Example 1 was selected and dried, the storage conditions were changed as shown in Table 3 below, and the performance was evaluated after the sample was left at a temperature of 55 ° C. for 72 hours. . Upon storage, the sample was completely sealed with aluminum foil and packaged.

The results are shown in Table 3.

[0099]

[Table 3]

As is apparent from Table 3, the deterioration of the above performance is the smallest when the relative humidity of the packaging material is 20 to 60%.

Example 5 A sample 9 was made to contain a tetrazolium compound (T compound) or a hydrazine compound (H compound) as shown in Table 4 below, and development processing was carried out in the same manner as in Example 1 to obtain the quality and color of blank characters. The effect of pollution was investigated.

The results are shown in Table 4.

[0103]

[Table 4]

As can be seen from Table 4, the light-sensitive material containing the tetrazolium compound and the hydrazine compound gives high blank character quality even though the pH is not high.

[0105]

According to the present invention, silver halide grains are doped with a combination of a transition metal of Rh, Ru and Os and a heavy metal selected from iron, nickel, cobalt, vanadium and cerium or a rare earth compound. Thus, a remarkably excellent effect that a low-sensitivity and high-contrast image is obtained can be obtained. Further, even when hydrazine is used together at a low pH, the accompanying effect that the desensitizing contrast is sufficiently satisfied is also exhibited.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 11/16 G03C 11/16

Claims (7)

[Claims] 1. A silver halide grain comprising at least one selected from the platinum group and at least one selected from metal atoms of the fourth period of the periodic table, or at least one selected from the platinum group and a rare earth element. A silver halide photographic light-sensitive material comprising at least one selected from the group consisting of: 2. The platinum group is selected from the following (a), the metal atom of the fourth period of the periodic table is selected from the following (b), and the rare earth element is the following (c): The silver halide photographic light-sensitive material according to claim 1. (A) Rhodium, osmium and ruthenium (b) Iron, cobalt, nickel and vanadium (c) Cerium 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains contain a non-metal oxidizing agent. 4. The silver halide photographic light-sensitive material according to claim 1, containing at least one selected from a hydrazine compound, an amine compound, a redox compound and a tetrazolium compound. 5. A method for developing and processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 1 with a developer having a pH of 9 to 10.9. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the relative humidity is 20% or less and the temperature is 10 to 90 ° C.
A method for drying a silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material is dried. 7. A method of storing a silver halide photographic light-sensitive material, which comprises storing the silver halide photographic light-sensitive material according to claim 1 at a relative humidity of 20% or more and 60% or less.