JPS6289951A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a stable sensitive material having very high contrast and undergoing no deterioration in the performance even after storage at high temp. and humidity by incorporating specified compounds into hydrophilic colloidal layers including a silver halide emulsion layer. CONSTITUTION:When hydrophilic colloidal layers including at least one silver halide emulsion layer are formed on a support by coating, a compound represented by formula 1 and at least one kind of compound represented by formula 2, 3 or 4 are incorporated into the hydrophilic colloidal layers. In the formula 1, each of R1-R3 is H or a group showing a negative value as Hammett's sigma-value (sigmap) and X<-> is an anion. In formula 2, each of R4-R6 is 1-12C alkyl, alkenyl or the like, a salt thereof or H. In formula 3, each of R7-R9 is H, halogen or optionally substituted amino, the substituent may be hydroxy, R16 is optionally substituted 1-8C alkyl and the substituent may be phosphoric acid. In formula 4, each of R11 and R12 is H or optionally substituted amino, the substituent may be hydroxy, R13 is optionally substituted 1-8C alkyl and the substituent may be phosphoric acid. It is necessary that the triphenyltetrazolium compound represented by formula 1 has electron donative groups as the substituents R1-R3 of the phenyl groups.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material for forming a novel photographic image, and more specifically, for forming a high-contrast halftone image. This invention relates to a novel silver halide photographic material that has high utility value in the printing and plate making field.

[Conventional technology]

It is conventionally known that photographic images with extremely high film resistance can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is about 0.
Halogenated silver chlorobromide or silver chloroiodide emulsion with fine grains of 5 μ or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 moles or more. A method is known for producing high-contrast halftone dot images or line images by processing silver photosensitive materials with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions. The light-sensitive material is known as a lithium-type silver halide photographic light-sensitive material, and normally during the photolithography process, the continuous tone density changes of the original are converted into a set of halftone dots with areas proportional to the density. are doing. Such conversion uses a lithium-type silver halide photographic light-sensitive material, photographs the original through a cross-line screen or a contact screen, and then converts it into a photosensitive material that has a very low sulfite ion concentration and contains only a hydroquinone-type imaging agent. A halftone image is formed by developing with a so-called Lith type developer. This lithium-type silver halide photographic light-sensitive material itself does not have sufficient high contrast; for example, even when processed with a commercially available developer for photographic paper, the gamma is only 5 to 6; Since fringing, which must be avoided most often, occurs frequently, it is said that combination with the above-mentioned lithium type developer is essential for halftone negative/positive applications.

This Lith-type developer is described in J.N.C. Neil's Journal of the Franklin Institute (J, A, C, Yule: J, Fr.
Anklin In5trute), Volume 239,
It is described in detail on page 221 (1945), and is a developing solution containing essentially only hydroquinone as a developing agent and having a low concentration of bad sulfate ions that serve as an antioxidant for the developing agent.

Such developers have poor shelf life and are susceptible to auto-oxidation, so in order for plate makers to consistently obtain high-quality halftone negative or halftone positive images, they must reduce the activity of the developer, which decreases over time. Although it is necessary to manage the developer to maintain a constant value, it is unavoidable that the operation becomes complicated.

The benefits of improving the retention of Lith-type developers are extremely large, and great efforts have been made to do so.
This is completely inadequate when compared with a continuous tone developer such as a methol-hydroquinone developer or a developer which exhibits a preservability comparable to that of a phenidone-hydroquinone developer.

Therefore, several attempts have been made to form a high-contrast image comparable to lithographic development using a phenidone-hydroquinone developer having a high sulfite ion concentration. For example, Japanese Patent Application Laid-Open No. 56-106244 states that high-contrast images can be obtained by using a hydrazine compound and by containing a development-promoting amount of an amine compound in the developer. Also, Special Publication No. 59-17825, No. 59-17818, No. 59-17819, No. 59
-17820, 59-17821, 59-17
Patent publications such as No. 826 and No. 59-17822 disclose silver rhodanide photographic materials containing a tetrazolium compound.

[Problem that the invention seeks to solve]

In the former technique using a hydrazine compound, the pH of the developer
It is necessary to make the value very high, around 12, and there is a problem with the stability of the liquid. In addition, black spots called black spots occur in non-image areas, which is a drawback that has a negative impact on commercial value.

Further, although the tetrazolium compound disclosed in the latter does not have the drawbacks of the former, it cannot be said to be fully satisfactory in terms of contrast and halftone dot quality. It is true that in recent years, the performance has not been sufficiently commensurate with the remarkable movement towards quality improvement in the printing and plate making field, and it is true that high-contrast image forming methods using useful tetrazolium compounds have been developed. Improvements were awaited.

Furthermore, when stored under high temperature and high humidity conditions, the performance deteriorates and it becomes impossible to obtain images with sufficiently high contrast, so improvements have been desired.

Is the present invention a tetrazolium compound? The purpose of this invention is to solve the above-mentioned problems with the silver halide emulsion used, and to provide a stable silver halide photosensitive material that has extremely high contrast and does not deteriorate in performance even when stored at high temperature and high humidity. be.

[Means to solve the problem]

As a result of intensive research, the present inventors have discovered that the present inventors have a support and a hydrophilic colloid layer coated on the support, including at least one silver halide emulsion layer, and that the hydrophilic colloid layer is A compound represented by formula [1] and the following general formula [2]
It has been found that the above-mentioned problems can be solved by using a silver halide photographic material containing at least one of the compounds shown in [3], [3], or [4], and that a high-contrast and stable light-sensitive material can be obtained.

General formula CI) CR1, R2, R3 are each a hydrogen atom or /%
Represents a group with a negative met sigma value (σp), and ρ
.

X" represents an anion.) In the formula, R4, R5 and R8 are an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an amine group, an aryl group, a hydroxyl group, a mercapto group, and a carboxyl group. represents a group or a salt thereof, or a hydrogen atom.The above alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, and aryl group may all have a substituent.

During the ceremony, R? , Rs and R8 represent a hydrogen atom, a halogen atom, a hydroxy group, or an amino group optionally substituted with a hydroxy group, and R86 represents the number of carbon atoms optionally substituted with a phosphoric acid group or a hydroxy group, etc. 1-8
Represents an alkyl group (e.g. methyl, ethyl, hydroxyethyl, etc.).

General formula [4] In the formula, R1+ and R12 are hydrogen atoms, hydroxy groups,
R13 represents an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl , hydroxyethyl, etc.).

In the present invention, substituents R+, R of the phenyl group of the triphenyltetrazolium compound represented by the general formula [1]
2. Rs needs to be a hydrogen atom or an electron-donating group with a negative Hammett's sigma value (σp), that is, an electron-donating group.

The Hammett sigma value for phenyl substitution has been reported in many publications, such as the Journal of Medical Chemistry.
Medical Chemistry) Vol.
Page 304, '1977, written by C. Hansch (C.H.
Ansch), etc., and examples of groups with negative sigma values include, for example, the methyl group (σ1)=-
0,17, below all σp values), ethyl group (-0,1
5), cyclopropyl group (-0,21), n-propyl group (-0,13), 1so-propyl group (-0,15)
, cyclobutyl group (-0,15), n-butyl group (-0
,16), 1so-butyl group (-0,20), n-pentyl group (-0,15''l, cyclohexyl group (-0,2
2), amine 7 group (-0,66), acetylamino group (-
0,15), hydroxyl group (-0,37), methoxy group (-0,27), ethoxy group (-0,24), propoxy group (-0,25), butoxy group (-0,32'
), pentoxy group (-0,34), etc., and all of these are useful as substituents for the compound of general formula [1] of the present invention.

Specific examples of the compound represented by the general formula [1] used in the present invention are listed below, but the compound of the present invention is not limited thereto.

(Exemplary Compounds) The tetrazolium compounds used in the present invention are described in, for example, Chemical Revi.
ews), Vol. 55, pp. 335-483.

The tetrazolium compound of the present invention is used in an amount of about 1 mg to about 10 g, preferably about 10 m9 to 1 about 2 g per mole of silver halide contained in the silver halide photographic material of the present invention. Preferably, the remainder is white, -2.' Typical specific examples represented by the general formula [2] include the following.

Typical specific examples represented by general formula [3] or [4] include the following.

(3-1) 6-amituprine riboside (3-2) 6-
Chloro-purine riboside (3-3) 6-oxy-purine riboside (3-4) 6-methylamino-purine riboside (3-5) 2-amino-6-oxy-purine riboside (3-6) 5'-phosphoric acid-6 -Amino-purine riboside (3-7) 5'-phosphoric acid-6-chloro-purine riboside (3-8) 5'-phosphoric acid-6-oxy-purine riboside (3-9) 5'-phosphoric acid-6-methylamine /-purine riboside (3-10) 5'-hydroxymethyl-6-amitupuriboside (3-11) 5'-methyl-6-amitupuriboside General formula C2] [3] and [4] The compound shown is H o 'f > eHt motv corresponding I XIO ~ 1 × 1
It is preferable to use the addition amount in the range of 0 mol, particularly preferably in the range of 1×10 to 1×10 mol. This compound can be added by any conventional method for adding additives to photographic emulsions. For example, water-soluble compounds are
The general formula [l] ~ can be used by making an aqueous solution with an appropriate concentration, and by dissolving a compound that is insoluble or poorly soluble in water in a suitable organic solvent that is miscible with water, and adding it to an emulsion as a solution.
The addition position of the compound represented by [4] in the emulsion 1 manufacturing process can be arbitrarily selected.

The silver halide photographic material of the present invention comprises a support and at least one hydrophilic colloid layer containing a silver halide emulsion coated on the support, and this silver halide emulsion is coated directly onto the support. Alternatively, it may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid may be further coated as a protective layer on the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. In this case, the silver halide emulsion layer may be provided with an intermediate layer of a hydrophilic colloid layer, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. Good too. General formulas [1] to [4] of the present invention
] The layer containing the compound represented by is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid layer.
Or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The most preferred embodiment of the present invention is the general formula [1
This is a silver halide photographic light-sensitive material in which the compounds represented by [4] are contained in a silver halide emulsion layer, and the hydrophilic colloid is gelatin or a gelatin derivative.

In order to incorporate the tetrazolium compound of the present invention into the hydrophilic colo-rd layer, the tetrazolium compound may be dissolved in appropriate water and/or an organic solvent and then added, or the solution dissolved in an organic solvent may be added to gelatin or a gelatin derivative. etc.) Examples include a method in which the colloid is added after being dispersed in IJ wax, or a method in which it is added after being dispersed in latex. The present invention may use any of these methods.

The tetrazolium compound used in the present invention can be used alone to obtain preferable image characteristics 3. Further, even if two or more of these tetrazolium compounds are used in combination in an appropriate ratio, the image characteristics will not be adversely affected. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound other than the present invention may be used in an appropriate ratio.

In one preferred embodiment of the present invention, the tetrazolium compound according to the present invention is added to the silver halide emulsion layer. In another preferred embodiment of the present invention, it is added to a hydrophilic colloid layer directly adjacent to a hydrophilic floid layer containing a silver halide emulsion layer, or to a hydrophilic floyd layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound according to the invention may be dissolved in a suitable organic solvent such as water, methanol, ethyl alcohol,
/ - Dissolved in alcohols, ethers, esters, etc. and coated directly on the outermost layer of the silver halide emulsion layer of a silver halide photographic light-sensitive material. It may also be incorporated into a silver halide photographic light-sensitive material.

In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound of the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, and anionic activators, specifically lower groups such as p-1-luenesulfonic acid anions. Alkylbenzenesulfonic acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalenesulfonic acid anions, lauryl sulfate anions, tetraphenylborons, G2
Examples include dialkyl sulfosuccinate anions such as -ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl boriethe/xysulfate anions, stearate anions, and polyacrylic acid anions.

Such anions may be added to the hydrophilic colloid layer after being premixed with the tetrazolium compound of the present invention, or may be added alone to the silver 10-genide emulsion layer (containing or not containing the tetrazolium of the present invention) or It can be added to the hydrophilic colloid layer.

There are no particular limitations on the amount of silver halide ε used in the silver halide photographic material of the present invention, but silver chloride or silver chlorobromide is preferred. The composition ratio of silver chlorobromide is AgCl//Br
=10010~2A8 Noizu Retemoyoi. The average grain size of the silver halide grains is preferably 0.10 μ to 0.40 μ, and is expressed as (standard deviation of grain size)/(average grain size) xto.

It is more preferable to have a narrow particle size distribution with a variation coefficient of 15% or less.

Further, in the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, etc. may be present.

The silver halide used in the present invention can be sensitized with various chemical sensitizers. As a sensitizer,
For example, activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers ( (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooleite, potassium cumolithiocyanate, potassium chlorooleate, 2-oresulfobenzothiazole methyl chloride, ammonium chlorovaldate, potassium chlorooleate, sodium chlorooleate, etc. Various noble metal sensitizers represented by baradite and the like can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

Further, the silver halide emulsion used in the present invention may be optically sensitized for one second or using two or more types of sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Although any conventional sensitizing dye can be used, optical sensitizing dyes that can be advantageously used in the present invention include:
Examples include cyanines, merocyanine m, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols and hemioxonols, and the optical properties of these Preferably, the sensitizing dye contains a basic group such as thiazoline, thiazole, etc. or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbylic acid, pyrazolone, etc. as a nitrogen-containing heterocyclic nucleus in a part of its structure. Such a nucleus can be substituted with alkyl, hydroxyalkyl, halogen, phenyl, cyano, or alkoxy, and these optically sensitizing dyes may be fused with a carbocyclic or heterocyclic ring.

Note that when the above optical sensitizing dyes, particularly merocyanine sensitizing dyes, are used, not only optical sensitization but also the effect of widening the development latitude 3 can be obtained.

□ Silver halide emulsions used in the present invention are disclosed in, for example, US Pat. No. 2.444.607 and US Pat. No. 2.716.
No. 062, No. 3.512.982, West German Application Publication No. 1.189°380, No. 2.058.626,
No. 2.118.411, Special Publication No. 43-4133,
U.S. Patent No. 3,342,596, Japanese Patent Publication No. 47-441
No. 7, West German Application Publication No. 2.149,789, Japanese Patent Publication No. 39-2825, Japanese Patent Publication No. 13566-1977, preferably compounds such as 5,6-drimethylene-7-hydroxy-S-triazolo (1,5-a)
Pyrimidine, 5,6-titramethylene-7-hydroxy-S-)riazolo(1,5-a) Pyrimidine, 5-methyl-7-hydroxy-8-triazolo(1,5-a
) Pyrimidine, 7-hydroxy-5-triazolo (
1,5-a) pyrimidine, 5-methyl-6-promorph-hydroxy-S-)riazolo (1,5-a) pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, gallic acid) propyl, sodium gallate), mercaptan! (1-
7enyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benztriazoles (5-buambenttriazole, 5-mercaptobenztriazole), benzimidazole ffi, (6-nitro-kunzimidazole), etc. It can be stabilized using

The silver halide and tetrazolium compounds according to the present invention are added to the hydrophilic colloid layer, and the hydrophilic colloid particularly advantageously used in the present invention is gelatin. Albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives,
For example, U.S. Patent No. 2.614.928, U.S. Pat.
phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in each specification of U.S. Pat. No. 5,753, or each of U.S. Pat. Ethylene group in styrene acrylate, acrylic ester, methacrylic acid, methacrylic ester, etc. as described in the specification? These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc. .

Examples of the support used in the present invention include baryta paper, polyethylene corrugated paper, polypropylene synthetic paper, glass board,
Cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropyl non-films,
Typical examples include polycarbonate film and polystyrene film. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

As described above, the photosensitive material of the present invention has at least one hydrophilic colloid layer containing the silver halide of the present invention on the support, and the hydrophilic colloid layer on the side of the layer containing the layer. The tetrazolium compound of the present invention is contained in at least one layer of the protective layer having an appropriate thickness, that is, preferably 0.1 to 101t, particularly preferably 0.8 to 2μ. Preferably, a gelatin protective layer is applied.

The hydrophilic colloid used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners,
Surfactant, image stabilizer, ultraviolet absorber, antistain agent, pH adjuster, antioxidant, antistatic agent, thickener,
Granularity improvers, dyes, mordants, brighteners, development speed regulators, matte eggs, etc. can be used within the range that does not impair the effects of the present invention.

Among the above-mentioned various additives, those that can be particularly preferably used in the present invention include those described in U.S. Pat.
Publication No. 939, West German Application Publication No. 1.904゜604 Specification, JP-A-48-63715, JP-A-45-15
No. 462, Belgian Patent No. 762.833, U.S. Patent No. 3.767,410, Belgian Patent No. 55
8.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active no.a)f Examples of hardening agents and ultraviolet absorbers such as vinyl sulfone, incyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl, as well as ultraviolet absorbers, include those described in US Patent No. 3. ．． 25'3.921, British Patent No. 1.309.
' Compounds described in the specifications of No. 349, especially 2-(2'-hydroxy-5-tertiary butylphenyl)
benzotriacy)v, 2-(2'-hydroxy-3/
, s/-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3'-tert-butyl-5'
-butylphenyl)-5-chlorobenzotriazole,
Examples of dyes include 2-(2'-hydroxy-31,S/-di-tert-butylphenyl)-5-chlorobenzotriazole, and dyes described in U.S. Patent No. 2.072
．． No. 908, German Patent No. 107.990, U.S. Patent No. 3.048.487, U.S. Patent No. 515.988, etc. It may be contained in a protective layer, emulsion layer, intermediate layer, etc.

British Patent No. 548.532 describes coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control the physical properties of photosensitive materials. , same No. 1゜216, 389
No. 3,026.202, U.S. Patent No. 3,514
, specifications of No. 293, Japanese Patent Publications No. 44-26580, No. 43-17922, No. 43-17926, No. 43-
13166, French Patent No. 48-20785, French Patent No. 202.588, Belgian Patent No. 7'l'3.
Anionic, cationic, nonionic, or amphoteric compounds described in the specifications of No. 459, JP-A-48-101118, etc. can be used, but among these, especially those having a sulfone group Anionic surfactants such as succinic ester sulfonates, alkylnaphthalene sulfonates TL, alkylbenzenesulfonates, and the like are preferred.

In addition, as an antistatic agent, Tokuko Sho 4fi・-24159
No., Japanese Patent Application Publication No. 48-89979, U.S. Patent No.
Specifications of 2.882゜157, 2.972.535, JP-A-48-20785, JP-A-48-4313
No. 0, No. 48-90391, Special Publication No. 46-24159
There are compounds described in the following publications: No. 46-39312, No. 48-43809, and JP-A No. 47-33627, and examples of matting agents include, for example, British Patent No. L 221.980. , U.S. Patent No. 2.992.10
1, French Patent No. 2.956.884, French Patent No. 1.39
Compounds described in the specifications of No. 5゜544, Japanese Patent Publication No. 48-43125, etc., especially silica gel with a particle size of 0.5 to 20 μm, and polymethyl methacrylate with a particle size of 0.5 to 20 μm. Examples include merging.

The tin halide photographic material fF containing the tetrazolium compound of the present invention in a hydrophilic colloid layer including a silver halide emulsion layer is developed in the presence of a compound represented by the following general formula [5]. It is preferable.

[In the formula, R21 is a 5- or 6-position nitro group, R2
□ represents a hydrogen atom or a C4-C5 lower alkyl group; M represents a cation such as an aqueous atom, an alkali fully bent atom, alkaline earth gold, a flea atom, or an ammonium ion; ] Specific compounds represented by the general formula [5] include 5-nitroindazole, 6-nitroindazole, etc., but the present invention is not limited thereto in any way.

The compound represented by the general formula [5] is an organic solvent such as diethylene glycol, triethylene glycol, ethanol, jetanolamine, and triethanolamine;
It may be added to the developer after being dissolved in an alkali such as sodium hydroxide, an acid such as acetic acid, or it may be added as is.

The compound represented by the general formula [5] is about 1 per 11 developer solution.
R9 to 1.000 R9 is preferred, and more preferably a concentration range of about 50m9 to 300m9 is included.

Examples of the developing agent for the black and white silver halide photographic light-sensitive material of the present invention include the following. This developing agent can be used together with the compound represented by the above-mentioned general formula [5].

Representative examples of HO(CH=CH)-0I-T type developing agents include hydroquinone, as well as catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone, promono\hydroquinone, isopropylhydroquinone, toluhydroquinone, Methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-diethylhydroquinone% 2.5-
Shipp 7enethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-7enylcatechol, 4-phenyl-
Catechol, 3-methoxytefur, 4-acetyl-pyrogallol, 4-(2'-hydroxybenzoyl)
Examples include pyrogallol and sodium ascorbic acid.

In addition, typical examples of HO-(CH=CH)-NH2 type developers include ortho- and rose-amino/phenolmataha aminopyrazolones, and 4-aminophe/-/L
7.2-amino-6-phenylphenol, 2-amino/
-4-chloro-6-phenylphenol, 4-amino-
2-phenylphenol, 3゜4-diaminophenol, 3-methyl-4,6-diaminophenol, 2.4-
Cyamylsorcinol, 2. ．． 4.6-triaminophenol, N-methyl-p-aminophenol, N-β-
Examples include hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, and 2-amine naphthol.

Further, HiN (CH=CH+open) type developers include, for example, 4-amino-2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-diethylaniline, and
-(4-amino-3-methylphenyl)-morpholine,
p-phenylenediamine, 4-amino-N, N-dimethyl-3-hydroxyaniline, N, N, N, N'
-tetramethylbaraphenylenediamine, 4-amino-
N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino/-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-(β- methoxyethyl)-3-methyl-aniline, 4
-amino-3-methyl-N=ethyl-N-(β-methylsulfonamidoethyl)-aniline, 4-ami2N
-Butyl-N-γ-sulfobutylaniline, 1-(4-
Examples include aminophenyl)-pyrrolidine, 6-amino-1-ethyl-1,2,3,4-tetrahydroquinone, and 9-aminoylolidine.

Examples of the heterogeneous developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethy/l/-3-
3-pyrazolidones such as hyrazolidone, ■-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5
-Pyrazolone, 1-(p-aminophenyl)-3-amino-2-pyrazoline, 1-7enyl-3-methyl-4-
Examples include amino-5-pyrazolone, 5-aminouracil, 5-ami/-2,4,6-)lihydroxyphyrimidene, and the like.

Other books include The Theory of the Photographic Process, Volume 4, by T.I. James. i+Ji(Th
e'l'heory of the photogra
phic process, FourthEdit
ion) pp. 291-334 and Journal of
The American Chemical Society (Journ)
al of the American Chemistry
al 3ociety) Volume 73, No. 3.100 (
1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Furthermore, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the present invention, the effects of the invention will not be diminished. can be mentioned. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjustment of I)H using caustic alkali, alkali carbonate, or amine used in general black-and-white developing solutions and providing a buffer function, as well as thermal development suppression and benzene)
Organic development inhibitors such as IJ azole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol,
Development accelerators such as benzyl alcohol and polykylene oxide, alkylaryl sulfonic acids, surfactants such as IJ, natural saponins, sugars or alkyl esters of the above compounds, glutaraldehyde, formalin, succinic aldehyde, etc. It is optional to add a hardening agent, an ionic strength adjusting agent such as sodium sulfate, etc.

The developer used in the present invention may contain an organic solvent such as alkanolamines or glyfurs. Examples of the alkalamines mentioned above include monoethanolamine, jetanolamine, and triethanolamine, and triethanolamine is preferably used. The preferred amount of these alkanolamines used is 5 to 500 g per 11 of the developer, more preferably 20 g.
-200g.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, I+4-butanediol, 1.5
-bentanediol and the like, but diethylene glycol is preferably used. And - The preferred amount of these glycols used is 5 to 500 g, more preferably 20 to 2,009 g per developer. These organic solvents can be used alone or in combination.

By developing the silver halide photographic material of the present invention using a developer containing the above-mentioned development inhibitor, a photographic material having extremely excellent storage stability can be obtained.

The J)H value of the developer having the above composition is usually 9~
12, but from the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or less, particularly preferably around 30°C,
Further, the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes often brings about good results. Processing steps other than development, such as washing, stopping,
It is optional to adopt steps such as stabilization, fixation, and if necessary, preduration and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples.

(Example 1) Silver chlorobromide emulsions EM-1 to EN and i-8 were prepared using the following solutions A, B, and C.

[Solution A]

r Compounds represented by general formulas [2], [3] and [4] □ (Compounds and poisons are shown in Table 1) 1 Ossein gelatin 17.9j Polyisopropylene-polyethyleneoxy ■ Schiffuccinic acid ester Sodium salt 5 ml 110% ethanol solution) Distilled water 1280 cc
[Solution B] i Nitric acid
1
70. 9F Distilled water 410ml [Solution C] (Distilled water 407ml17
:, Solution A was kept at 40°C, stirred using the mixer described in JP-A-57-92523 and JP-A-57-92524, and then mixed with solution B and solution CJd by the dub-recipit method.
The second surface of the emulsion was formed. During the first 5 minutes of mixing, the EAg of the emulsion was
Maintain the voltage at 0 mV, and 5 minutes after the start of mixing, add 3 mol/7 (D
Adjusted to 120 mV using sodium chloride aqueous solution,
Thereafter, this value was maintained using the aqueous sodium chloride solution.

After adding Solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, then desalted and washed with water in a conventional manner.
After dispersion by stirring at 55° C. for 30 minutes, the volume was adjusted to 750 cc.

For the measurement of the EAg value, a metal silver electrode and a double junction type saturated Ag/AgC1 reference electrode were used (the double junction electrode configuration disclosed in JP-A-57-197534 was used).

A variable flow rate roller tube metering pump was used to add solutions B and C.

During the addition, the emulsion was sampled and observed using an electron microscope to ensure that no new particles were generated within the system, and it was confirmed that the amount added did not exceed the critical growth rate within the system.

During the addition, the p T-1 value in the system was controlled to be kept constant at 3.0 using a 3% aqueous nitric acid solution.

When the side length average particle size of the thus obtained E M -1 to EM -8 was determined using an electron microscope, all the samples had a diameter of 0.
The particles were cubic grains of 25±0.01 μm and exhibited very good monodispersity.

Each of these emulsions was gold-sulfur sensitized (6-methyl-4-hydroxy-1,3°33 as a stabilizer).
．． 7-chitrazaindene was added and 1-(
β-hydroxyethyl)-3-phenyl-5-((3-
γ-sulfopropyl-α-pensooxazolinidene)
-ethylidene]thiohydantoin was added at 150 m9 per 1 mole of Ag to optically sensitize.

Then 2,3-di-p-tolyl-5 per mole of Ag
-Phenyltetrazolium chloride (exemplary compound (1)
-2) to 700 m, I+9, 400 m9 of p-dodecylbenzenesulfonic acid sodium, 3.5 g of subonin, and styrene-maleic acid copolymer 21, an amount of Ag of 40 g/m, and an amount of gelatin of 2. It was coated on Nijesu to give a coating weight of 0.01 m/m. At that time, 1-decyl-2-(3-i,
I pentyl) succinate-2-sulfonic acid sodium 3
0m 7m2, formalin 25mq/ as a hardening agent
Samples 1 to 8 were obtained by applying a protective layer containing m'' in multiple layers.

Each of the obtained samples was divided into two halves, and the other half was incubated at 5°C1 relative humidity 80°C to evaluate the stability of performance.
%, then sealed and packaged with a moisture-proof material and heat-treated at 50° C. for 72 hours. Both samples were exposed to light using a tungsten light source using an optical I2 camera, and the test samples were processed in an automatic processor with a developing tank capacity of 401 using a developer having the following formulation and a commercially available fixer.

[Development processing conditions]

(Process) (Wet Pupil) (Time) Development
A'C 30 seconds fixing RO'0 20 seconds water washing
Room temperature Nodding seconds [Developer composition] (Composition A) (Composition) When using the developer, add the above composition A,
They were dissolved in the order of their composition and finished to 11 for use.

A photographic characteristic curve was drawn for the developed sample, and the sensitivity and the sharpness of the legs of the characteristic curve were measured. Sensitivity is calculated from the reciprocal of the exposure amount required to form an optical density of 2.5EM
The relative sensitivity is shown with the sample prepared using -2 set as 100. Also, the breakage of the legs is 0.5 from the optical density OI.
It is shown in 1 light range (logE value) at The smaller this value is, the more desirable the leg portion is.

The results are summarized in Table 3.

As shown in Table 3, it can be seen that the emulsions of the present invention have extremely high contrast and exhibit little performance deterioration at high temperatures.

(Example 2) Using E M -1 used in Example 1, coating liquid E+! '
Coated samples 9 to 14 were prepared in the same manner as in Example 1 except that the compounds represented by the general formulas C', : ], [3] and [4] were added as shown in Table 4. Obtained.

The obtained sample was subjected to heat treatment, exposure, and development treatment in the same manner as in Example 1. The photographic characteristic curve, sensitivity, and characteristic curve break were measured for the developed sample.

Sensitivity is the optical density, which is calculated from the reciprocal of the exposure amount required to form EM.
Relative sensitivity is shown as 0.

In addition, the breakage of the legs was indicated by the exposure range (logE value) from 0.1 to 0.5 optical degrees. This value is small (・l
This indicates that the legs have a good sharpness, which is a desirable characteristic.

The results are summarized in Table 5. As shown in Table 4 and Table 3 of Table 5 below, the emulsion of the present invention has extremely high contrast, and even if it is added at the time of preparing the coating solution, it will not deteriorate its performance under high temperatures as well as when it is added at the time of preparation. It can be seen that there is a small amount of emulsion.

(Example 3) Using EM-2 used in Example 1, coated samples 15 to 21 were obtained in the same manner as in Example 1. However, as the tetrazolium salts used in preparing the coating solution, those shown in Table 6 were used. This sample was subjected to stepwise exposure to xenon light using a contact screen G N Type R (150L'') manufactured by Dainippon Screen Mfg. Co., Ltd. and an optical wedge.Then, a development process was carried out according to Example 1, and each sample was The sensitivity and quality of the lock points (dot quality) were evaluated.

Table 6 Triphenyltetrazolium Compounds The Hammett vp values of the substituents of the above compounds are -CT(3(
-0,17) -0CH3(-0,27)-CF,
(0,54,) -NO3(0,78) -COC
H3(0,50), sample 15.16.17.1
The tetrazolium compounds used in 8 are the above-mentioned exemplary compounds (1-2χ(1-1), (1-7), (1
-6).

For so-called 50% dots, where the area of the halftone dot and the clear area are equal, the dot quality was visually judged by the condition of the fringe (blur) that occurs around the halftone dot.The dot quality was evaluated on a 5-point scale with 5 being the smallest fringe. . That is, a score of 5'' is excellent, and a score of 1 Pa is extremely poor. 5
0% dot quality is 3゛.

If it is less than , it is generally not acceptable.

Furthermore, the sensitivity was calculated from the exposure amount required to form a halftone dot density of 95%, and expressed as a relative sensitivity with Sample 1 set as 100.

These results are shown in Table 7.

Table 7 Samples 15-18 obtained according to the present invention as shown in Table 7
It can be seen that these samples have superior dot quality compared to samples Nos. 19 to 21, and exhibit very little performance deterioration under high temperature and high humidity conditions.

〔Effect of the invention〕

As is clear from the examples above, the photosensitive material according to the present invention has extremely high contrast, and the shaded areas indicate excellent dot quality during exposure.

Furthermore, the quality stability over time of storage is also extremely good.

Claims (1)

[Scope of Claims] A support having a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer, and the hydrophilic colloid layer having the following general formula [1] A silver halide photographic material containing at least one compound represented by the formula [2], [3] or [4] below. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, and R_3 each represent a hydrogen atom or a group with a negative Hammett sigma value (σp), and X^■ Represents an anion group. ] General formula [2] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_4, R_5 and R_6 have 1 to 12 carbon atoms.
substituted or unsubstituted alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, substituted or unsubstituted amino group, aryl group, hydroxyl group, mercapto group,
Represents a carboxyl group or a salt thereof, or a hydrogen atom. ] General formula [3] ▲ Contains mathematical formulas, chemical formulas, tables, etc. group, or an optionally substituted alkyl group having 1 to 8 carbon atoms. ] General formula [4] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ [In the formula, R_1_1 and R_1_2 represent a hydrogen atom, a hydroxy group, a methyl group, or an optionally substituted amino group, and R_1_3 represents a phosphoric acid group, or represents an optionally substituted alkyl group having 1 to 8 carbon atoms. ]