JPS61149946A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high contrast dot image by using silver halide (AgX) particles produced in the presence of a water soluble Rh salt having a specified concn. in an AgX emulsion layer formed on a support and by incorporating a specified compound into a hydrophilic colloidal layer. CONSTITUTION:When hydrophilic colloidal layers including at least one AgX emulsion layer are formed on a support to obtain a photosensitive AgX material, AgX particles produced in the presence of a water soluble Rh salt by 1X10<-7>-5X10<-7>mol per 1mol AgX are used in the AgX emulsion layer, and a tetrazolium compound represented by the formula (where each of R1-R3 is H or a group whose sigmaP is negative, but all of R1-R3 are not H, and X<-> is an anion) is incorporated into at least one of the hydrophilic colloidal layers. A photographic image having the high contrast and the superior dot quality in net exposure can be obtd. by using the resulting photosensitive material. The photosensitive material has stable quality during storage and is suitable for a photomechanical process.

Description

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

[Conventional technology]

2. Description of the Related Art Conventionally, it has been known that a photo me with extremely high contrast can be formed using a silver halide photosensitive material. If kept, the average grain size of silver halide grains will be approximately 0.
Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion, which has fine grains of 5p or less, has a narrow particle size distribution, has a uniform grain shape, and has a high silver chloride content, for example, more than the parent mole. Light-sensitive materials are treated with subsulfurized ions! A method is known in which a halftone dot image or line image with higher contrast is obtained by processing with an alkaline developer containing only hydroquinone as a developing agent and having a low pH.

This type of silver halide light-sensitive material is known as a Lith-type halogen oven photographic light-sensitive material, and it has an area of a size proportional to the continuous tone density change of the original during the photolithography process. It is converted into a set of halftone dots. 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 processes a so-called lithium-ion silver halide photographic material, which has a very low concentration of sulfite ions and contains only a hydroquinone developing agent. A halftone image is formed by developing with a mold developer. This lithium-type silver halide photographic material is
The contrast itself is not sufficient; for example, even when processed with a commercially available photographic paper developer, the gamma is only 5 or 6, and there are many fringes that must be avoided when forming halftone dots. Therefore, for halftone dot negative/l-digital printing, it is said that combination with the above-mentioned Lith type developer is indispensable. Regarding this squirrel type developer, please refer to J.N.C.
Neil's Journal of the Fraftalin Institute (J, A, C, Yule: J, F
ranklin In5trute), No. 239@
, p. 221 (1945), and substantially contains only hydroquinone as a developing agent;
This is a developer solution with a low concentration of sulfite ions, which act 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-hydride tetraquinone 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 type developer having a high sulfite ion concentration. For example, Japanese Patent Application Laid-Open No. 56-106244 states that a high-contrast image can be obtained by using a hydrazine compound and by containing a development-promoting amount of an amino compound in the developer. Also, Special Publication No. 59-17825, No. 59
-17818, 59-17819, 59-17
No. 820, No. 59-17821, No. 59-17826
No. 59-17822 and the like disclose silver halide 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 bef bars occur in non-image areas, which is a drawback that has a negative impact on commercial value.

Although the latter disclosed tetrazolium compound 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 this is due to the fact that the performance cannot be said to be sufficiently commensurate with the remarkable movement towards quality improvement in the printing plate making field in recent years.
Improvements in high-contrast image forming methods using useful tetrazolium compounds have been 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, which has been desired to be improved.

The present invention uses a tetrazolium compound to solve the above-mentioned problems in silver saponide emulsions, and produces stable silver halide emulsions that have extremely high antibacterial properties and do not deteriorate in performance even when stored at high temperatures and high humidity. It provides photosensitive materials.

[Means for Solving the Problem] As a result of intensive research, the present inventors have found that in a silver halide photographic light-sensitive material having at least one layer of hydrophilic co-tetraide waste containing 1 mole of silver halide on a support. , the silver halide grains contained in the silver halide emulsion layer are silver halide 1
It is formed in the presence of a water-soluble rhodium salt of t x to-7 to 5 x 10-7 moles per mole, and at least one of the hydrophilic colloid layers has the following general formula (
It has been found that the above-mentioned problems can be solved by a silver halide photographic material containing at least one compound represented by jJ, and a high-contrast and stable photographic material can be obtained.

CR1* Rt p Rs each represent a hydrogen atom or a group having a negative Hammett's sigma value, and xe represents a3o. However, u, t R2t R
.

are never hydrogen atoms at the same time. ] Examples of water-soluble rhodium salts used in the present invention include cesium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc. Preferably, trivalent rhodium norogen complex compounds, such as hexaxerorhodium ( These are phantom acids or their salts and rhodium trichloride trihydrate.

In the present invention, the amount of the water-soluble rhodium salt added is 1.5 mm per mole of silver halide. Ox 10-7~5. Ox to-
'Seven. If the water-soluble rhodium salt is less than 1,0XIO-mol, stability under high temperature and high humidity conditions, which is one of the objectives of the present invention, will not be sufficient.

On the other hand, if the amount exceeds 5.0XlO-mol, as is well known to those skilled in the art, the desensitizing effect of the water-soluble rhodium salt on silver halide increases, making it difficult to obtain the desired sensitivity. Become.

In the present invention, the water-soluble rhodium salt is present during the formation of silver halide grains, which refers to the formation time and the emulsification and physical ripening process of silver halide, and can be present at any time in this process by any method. You can add it with However, the preferred time to add is during emulsification, and the more preferred method is to add a water-soluble rhodium salt to the halide solution. The distribution of rhodium ion in the silver halide emulsion is preferably uniform for each silver halide grain, and there are no particular restrictions on the distribution in one grain.
The distribution on the particle surface and inside the particle may be uniform, or the distribution may lean towards the surface side or the inside side.

In the present invention, substituents R1r R of the phenyl group of the triphenyltetrazolium compound represented by the general formula (11)
1+ R1 needs to be a hydrogen atom or one with a negative Hammett's sigma value (σ,) indicating the ability to attract electrons, that is, an electron-donating group.

Hammett's sigma value for phenyl substitution is reported in many publications1, for example, Journal of Medica.
l Chemistry) Volume K, page 304, 1
977, written by C. Hansch.
Examples of groups with negative sigma values include methyl group ('p''=-0,17, hereinafter referred to as σ), ethyl group (-0,15), etc. Cyclopropyl group (-0,21), n-propyl group (-0,1
3), 1so-propyl group (-0,15'), cyclobutyl group (-0,15), n-butyl group (-0,16)
, 1so-butyl group (-0,20), n-benzi/' group (-0,15), cyclohexyl group (-0,22),
7 amine groups (-0,66'), 7 acetylamino groups (-0
,15'), hydroxyl group (-0,37), methoxy group (-0,27'), ethoxy group (-0,24), propoxy group (-0,25), butoxy group (-0,32) ,
Examples include pentoxy group (-0,34), and all of these are useful as a fit group for the compound of general formula [I] 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.

The tetrazolium compound used in the present invention is described, for example, in Chemical Revie.
ws) Volume 3, pp. 335-483.

The tetrazolium compound of the present invention is preferably used in an amount of #J1η to about 1 Op, preferably about tOIIP to about 211 per mole of silver halide contained in the silver halide photographic material of the present invention.

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, the silver halide emulsion layer may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer 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 between the layers, or may be interlayered with the silver halide emulsion layer. I
An intermediate layer may be provided between the two. The layer containing the tetrazolium compound of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The most preferred embodiment of the present invention! ? ! The silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material in which the tetrazolium compound of the present invention is 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 colloid layer, the tetrazolium compound can be dissolved in appropriate water and/or an organic solvent and then added, or the solution dissolved in an organic solvent can be added to a hydrophilic colloid layer such as gelatin or a gelatin derivative. Examples include a method in which the compound is added after being dispersed in a sex colloid matrix, or a method in which the compound 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. Further, even if two or more of these tetrazolium compounds are used in combination in an appropriate ratio, 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.

One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention to a 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 colloid layer containing a silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer.

In addition, as another type 3III, the tetrazolium compound according to the present invention is dissolved in a suitable organic solvent, such as water, alcohols such as methanol and ethanol, ethers, esters, etc., and halogenated by an overcoating method or the like. It may be incorporated into the silver halide photographic material by directly coating the outermost layer on the side of the silver halide emulsion layer of the silver photographic 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 the higher anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower alkylbenzenes such as p-)luenesulfonic acid anions. sulfone anion,
Dialkylsulf7-osuccinate anions such as p-dodecylbenzenesulfonate anions, alkylnaphthalenesulfonate anions, laurylsulfate anions, tetraphenylborons, di-2-ethylhexylsulfosuccinate anions, cetyl Examples include polyether alcohol sulfate anions such as riethenoxysulfate anions, stearate anions, and polyacrylate anions.

This higher anion 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 halide emulsion layer containing or not containing the tetrazolium of the present invention or to the hydrophilic colloid layer. Can be added to the colloid layer.

There are no particular limitations on the silver halide 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 ArcI! /Br=
Either Zoolo-2/9B may be used.

Preferably AlCl/Br = 90/10 to 501
The composition ratio is 50%. The average grain size of the silver halide grains is preferably 0.15 μ to 0.40 tt, and the grain size distribution has a coefficient of variation expressed by (standard deviation of grain size)/(average grain size) x Zoo of 15% or less. Narrow ones are more preferable.

Used in the present invention. Silver halide can be sensitized by various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate,
allylthiocarbamide, t-thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, stannic chloride, etc.), e.g. Various noble metal sensitizers represented by potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-oresulfobenzothiazole methyl coumatide, ammonium chloroparadate, potassium chloroputinate, sodium chlorovaradite, etc. These 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 using one or more sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Various sensitizing dyes can be used, but optical sensitizing dyes that can be advantageously used in the present invention include:
Examples include cyanines, merocyanines, 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, thiobarbyl, pyrazolone, etc. as a nitrogen-containing heterocyclic nucleus in 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.

In addition, when the above-mentioned optical sensitizing dyes, especially merocyanine-based sensitizing dyes, are used, not only optical sensitization but also the effect of widening the development latitude can be obtained.

Further, the silver halide emulsion used in the present invention is disclosed in, for example, US Pat. No. 2,444. f107, same number 2,716゜0
No. 62, No. 3,512,982, West German Application Publication No. 1,189,380, No. 2,058,626, No. 2,118,411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,596, Special Publication No. 47-4417
No., West German Application Publication No. 2,149,789, Special Publication No. 3
No. 9-2825, and compounds listed in Japanese Patent Publication No. 13566/1983, preferably, for example, 5,6-)rimethylene-7-hydroxy-&-)riazolo(1,5-a)pyrimidine, 5,6- Chitramethylene-7-hydroxy-
8-triazolo(1,5-8)pyrimidine, 5-methyl-7-hydroxy-8-triazolo(1,5-a)pyrimidine, 7-hydroxy-8-)riazoloi, 5-a)
Pyrimidine, 5-methyl-6-promorph-hydroxy-8-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptan Ii (1 -yUni-5-mercaptotetrazole, 2-mercaptobenzthiazole), benztriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-
Nidrobenzimidazole) etc. can be used for stabilization.

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. Pat. No. 2,614,928, U.S. Pat.
Phenylcarbamyl gelatin, acylated gelatin, heptalated gelatin as described in each specification of US Patent No. 5,753, or each specification of US Patent No. 2,548,520 and US Patent No. 2,831,767 Examples include gelatin graft polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in The wood colloid has a layer that does not contain silver halide, such as a haleyshiron prevention layer, a protective layer,
It can also be applied to the middle class.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Typical examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. 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. containing the tetrazolium compound of the present invention in at least one of the scraps, and a protective layer having an appropriate pancreatic thickness on the layer side, that is, preferably 0.1 to 10 μm, particularly preferably 0.8 to 2 μm. Preferably, a protective layer of gelatin 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, anti-stain agent, p)i adjuster, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development speed adjustment A matting agent, a matting agent, etc. can be used within a 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. 39, West German Departing Reactor Publication No. 1.904,604, JP-A-48-63715, JP-A-45-154
Publication No. 62, Belgian Patent No. 762.833, U.S. Patent No. 3,767.410, Belgian Patent No. 551
Substances described in the specifications of No. 3,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, polyoxygen-based, ethylene glycol-based, and active halide hardeners. Examples of hardeners and ultraviolet absorbers such as Tagen-based, vinyl sulfone-based, isocyanate-based, sulfone ester-based, carbodiimide-based, mucochlor-based, and acyloyl-based agents include those described in U.S. Pat.
, 253,921, British Patent No. 1, 309.

Compound rings described in each specification etc. of No. 349, especially 2
- (2'-hydroxy-5-tertiary butyl 7-ethyl)benzotriazole, 2-(2'-hydroxy-31,5
1-di-tertiary butylphenyl)benzotriazole, 2
-(2-hydroxy-31-tertiary butyl-5-butylphenyl)-5-chlorobenzotriazole, 2-(
Examples of dyes include 2〆-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, and dyes described in U.S. Pat. No. 2,072,90
No. 8, Sec. Patent No. 107.990, U.S. Patent No. 3,0
Compounds described in each specification such as No. 48,487 and US Pat. No. 515,988 can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer, or the like. Further, as coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548,532, No. 1,216,3
89, U.S. Patent No. 3, 026°202, U.S. Patent No. 3,
Specifications of No. 514,293, Japanese Patent Publication No. 44-26580
No. 43-17922, No. 43-17926, No. 43-13166, No. 48-20785,
French Painting Patent No. 202,588, Belgian Patent *773
Anionic, cationic, nonionic, or amphoteric compounds described in the specifications of , No. 459, Patent Publication No. RW 34s-101118, etc. can be used, but among these, especially those having a sulfone group Anionic surfactants such as succinic acid ester sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, and the like are preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
Publications of JP-A-48-89979, U.S. patent ff1
Specifications of Nos. 2,882,157 and 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 Japanese Patent Publications No. 46-39312, No. 48-43809, JP-A-47-'536.27@I), etc., and as matting agents, for example, British Patent No. 1 , 221,980, U.S. Patent No. 2,992
, No. 101, No. 2,956,884, Inter-French Patent No. 1
, 395.

Compounds described in the specifications of No. 544, Japanese Patent Publication No. 48-43125, etc., especially silica gels having a particle size of 0.5 to 20 μm, and silica gels having a particle size of 0.5 to 20 μm.

Examples include polymers of trimethyl methacrylate.

A silver halide photographic material containing the tetrazolium compound of the present invention in the silver halide emulsion layer and/or its adjacent layer can be developed in the presence of a compound represented by the following general formula (IIJ).

General Formula [1[) [In the formula, R8 represents a 5- or 6-position nitro group, and R1 represents a hydrogen atom or a C3 to C5 lower alkyl group.

M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion.

] As a specific compound represented by general formula (II), 5-
Examples include nitroindazole and 6-nitreindazole, but the present invention is not limited thereto.

The compound represented by the general formula (II) can be dissolved in organic solvents such as diethylene glycol, triethylene glycol, ethanol, jetanolamine and triethanolamine, alkalis such as sodium hydroxide, acids such as acetic acid, etc. and added to existing bone fluid. It may be added or may be added as is.

The compound represented by general formula (1) is about 1 per 1e of developer.
"9 to t, oooη is preferred, more preferably about 5
It is included in the concentration range from cape 0 to 300η.

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 (IJ).

HO-(-C)] = C)I-q O) (Representative examples of type developing agents include hydroquinone, and others include catechol, birogalyl and its derivatives, ascorbic acid, tabrohydroquinone, and bromohydroquinone. Hydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2゜3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2
．． 3-dibromohydroquinone, 2. s-dihydroxyacetophenone, 2゜5-diethylhydroquinone,
2,5-di-p-7enethylhydroquinone, 2,5-
Dibenzoylaminohydroquinone, catechol, 4-
Examples include chlorocatechol, 3-phenylcatechol, 4-7enylcatechol, 3-methoxy-catechol, 4-acetylubitetragallol, 4-(2'-hydroxybenzoyl)pyrogallol, and sodium ascorbate.

In addition, HO-(-C)I = C)1-)-N)l, typical type developers are ortho and para aminophenol or aminovirazone, 4-aminophenol, 2-aminophenol, 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-hydroxyethyl-p-aminophenol,
Examples include p-hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Furthermore, )l, N-+-Q NakaOH+-N)1. Examples of mold developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, p -phenylenediamine, 4-amino-N,
N-dimethyl-3-hydroxyaniline, N, N, N'
, N'-tetramethylparaphenylenediamine, 4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-N-(
β- and do-4xyethyl)-aniline, 4-amino-N-
Ethyl-(β-methoxyethyl)-3-methyl-aniline, 4-amino-3-methyl-N-ethyl-N-(β-
Methylsulfonamidoethyl)-aniline, 4-amino-N-butyl-Nr-sulfobutylaniline, 1-
(4-aminophenyl)-virolidine, 6-ami/-1
-ethyl, 1,2゜3.4-tetrahydroquinone, 9
- Ami/illoridein, etc.

Petrocyclic type developers include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-hyrazolidone, 1-phenyl-4-methy/i/-4-hydroxymethyl-3- Pyrazolidone, 3-pyrazolidones such as 1-7enyl-4-methyl-4-hydroxythi/I/-3-pyrazolidone, 1-7enyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)- 3-
Amino-2-hylazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5-aminouracil,
Examples include 5-amino-2,4,6-)lyhydroxyphyrimidene.

Others include The Theory of the Photographic Process, 4th edition, by T. H. James.
theory of the Photographic
Process.

Fourth Edition) No. 291-33
4 pages and Journal of the American Chemical Society.
Developers such as those described in E. Erican Chemical Society, Volume N, p. 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. Further, even if a sulfite salt such as sodium sulfite, potassium sulfite, or ammonium sulfite is used as a preservative in the developing solution of the present invention, the effects of the present invention will not be impaired, which is one of the features of the present invention. It can be mentioned as follows. Hydroxyanine and hydrazide compounds may also be used as preservatives. In addition, it is necessary to adjust the pH with caustic alkali, alkali carbonate, or amines used in general black-and-white developers, and provide a buffer function, as well as inorganic development inhibitors such as brompotali, organic development inhibitors such as penztriazole, and ethylenediaminetetraacetic acid. metal ion t
l scavenger, development accelerator such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, surfactant such as sodium alkylaryl sulfonate, natural saponin, saccharide or alkyl ester of the above compound,
It is optional to add hardening agents such as glutaraldehyde, formalin, and glyoxal, and ionic strength adjusting agents such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent. Examples of the above-mentioned alkanolamine include monoethanolamine, jetanolamine, and triethanolamine, and triethanolamine is preferably used. The preferred amount of these alkanolamines is Developer II! 5 to 500g per serving, preferably 20g
~2009.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, tetrapyrene glycol, triethylene glycol, 1,4-butanediol, 1,5
-bentanediol and the like, but diethylene glycol is preferably used. The preferred amount of these Glyfurs used is 11! The amount is 5 to 5,009 grams per serving, preferably 20 to 200 grams. 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 pH value of the developer having the above composition is 9 to 12,
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 (
The temperature is preferably below ℃, especially around 30"C,
Further, the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes often brings about good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, pre-hardening and neutralizing steps, 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〕

The present invention will be specifically explained below with reference to Examples, but embodiments such as emulsion composition, preparation process, type of tetrazolium compound, etc. are not limited by these Examples.

(Example 1) A silver chlorobromide emulsion was prepared using the following solutions A, B, and C.

[Solution A]

[Solution B] [Solution C] Solution A was kept warm at 40°C, and solutions B and C were mixed by the double jet method while stirring using the mixer described in JP-A-57-92523 and JP-A-57-92524. was added.

Table 1 The addition flow rate of each solution B and C was varied incrementally over the addition period as shown in Table 1 to form silver halide grains. The EA# of the emulsion was maintained at 160 mV for the first 5 minutes of mixing, and adjusted to 120 mV using a 3 mol/l aqueous sodium chloride solution 5 minutes after the start of mixing, and thereafter maintained at this value using the aqueous sodium chloride solution.

After adding Solutions B and C, the emulsion was subjected to Ostwald ripening for 0 minutes, then desalted and washed with water by the usual method, and then an aqueous solution of ossein gelatin 6001 (containing 30 g of ossein gelatin) was added. After dispersing by stirring at 5°C, the volume was adjusted to 750 cc.

A metallic silver electrode and a double junction type saturated Ag/Ag C1' reference electrode were used to measure the EAg value (
The structure of the electrode used was a double junction disclosed in Japanese Patent Application Laid-open No. 19753/4. ).

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 pH value in the system was controlled to be kept constant at 3.0 using a 3% aqueous solution of nitrogen.

Seven emulsions EM-1 to EM-7 were prepared according to the conditions described above by changing the rhodium trichloride trihydrate dish of solution C as shown in Table 2.

Table 2 When the side length average grain size of EM-1 to EM-7 obtained in this way was determined using an electron microscope, all the samples had a diameter of 0.25±0.0.
The particles were cubic crystal grains of 1 ts and exhibited very good monodispersity.

These emulsions were subjected to total sulfur sensitization, and 6
-Methyl-4-hydroxy-1,3,3a.

7-chitrazaindene was added and 1-(β
-hydroxyethyl)-3-phenyl-5-((3-γ
-Sulfopropyl-α-penzoxazolinidene)-
15 per mole of Ag (ethylidene) thiohydantoin
0'9 was added for optical sensitization.

Then 2,3-p-)zyl-5 per mole of AJ
-Eltetrazolium chloride (Exemplary compound (2)
)) was added to 700'P, sodium p-dodecylbenzenesulfonate 400%, saponin 3.59%, styrene-maleic acid copolymer polymer 2.9%, AJ amount 4.09.
/♂, gelatin amount z, and 09/rrl were applied onto the base. At that time Zera 41. zp/n? 1-decyl-2-(3-isopentyl) as a spreading agent so that
A protective layer containing 30 η/i of sodium succinate-2-sulfonate and 5 η/m of formalin as a hardening agent was coated in multiple layers.

Each of the obtained samples was divided into two halves, and the other half was kept at 5℃ and relative humidity 80℃ to evaluate the stability of performance.
After controlling the humidity, the specimens were sealed and packaged with anti-dispersion material and heat treated at 50"C for 72 hours. Both samples were exposed to light using an optical wedge with a tungsten light source.

The above test sample was processed using a developing solution with the following formulation and a commercially available fixer in an automatic developing machine with a small developing tank capacity.

[Development processing conditions]

(Process) (Temperature) (Time) Development
public °C (capital) seconds fixation yu °C
Washing with water for a second at room temperature [Developer composition] (Composition person) (Composition) When using the developer, add the above set of $4A in pure water 5001.

Melt in order of composition, 11! It was finished and used.

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 2.5.EM-
Relative sensitivity is shown with the sample prepared using 4 as 100. In addition, the breakage of the legs was indicated by the exposure range (I!op E value) from optical density 0.1 to 0.5. The smaller this value is, the more desirable the leg portion is.

The results are summarized in Table 3.

Table 3 As shown in Table 3, it can be seen that the emulsion of the present invention has extremely high contrast and exhibits little deterioration in performance under high temperature and high humidity conditions. Further, EM-6 and EM-7 containing a large amount of water-soluble magnesium salt have low sensitivity, and it is quite difficult to obtain a sensitivity suitable for practical use.

[Example 2] Using EM-4 used in Example 1, a coated sample was obtained in the same manner as in Example 1. However, the tetrazolium salts used in preparing the coating solution were those shown in Table 4. This sample was subjected to stepwise exposure to xenon light using a contact screen G N Type R (150L) manufactured by Dainippon Screen Manufacturing Co., Ltd. and an optical wedge. The samples were developed in accordance with Example 1, and the sensitivity and halftone dot quality (dot quality) of each sample were evaluated.

Table 4 Triphenyltetrazolium compounds The Hammett's Vp values of the substituents of the above compounds are -CH, (-
0,17) -0CH, (-0,27)-CF',
(0,54) -No! (0,78) -〇OCR
, (0,50), and the tetrazolium compounds used in Samples 1, 2, and 3.4 are the exemplified compounds (
2).

Corresponds to (1), (7), and (6).

For so-called 50% dots, where the area of the halftone dot and the clear area are equal, the dot quality is evaluated on a 5-point scale, where the condition of the fringe (bore) that occurs around the halftone dot is visually determined, with the smallest fringe being rated at 5. did. In other words, 15'' is excellent and @III is extremely bad.5
0% dot quality below 13' is generally unacceptable.

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 5.

Table 5 As shown in Table 5, Samples 1 to 4 obtained in the present invention were:
It can be seen that these samples have superior dot quality compared to Samples Nos. 5 to 8, 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] In a silver halide photographic light-sensitive material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, silver halide grains contained in the silver halide emulsion layer; is formed in the presence of a water-soluble rhodium salt of 1×10^-^7 to 5×10^-^7 mole per mole of silver halide, and at least one of the hydrophilic colloid layers A silver halide photographic material, characterized in that it contains at least one compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R_1, R_2, R_3 each represent a hydrogen atom or a group whose Hammett's sigma value (σ_p) is a negative value, and X^■ represents an anion. . However, R_1, R_2,
R_3 is never a hydrogen atom at the same time. ]