JPS62139546A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance contrast and to improve storage stability by incorporating a specified triphenyltetrazolium compound and a specified pyrazolidine type compound in a hydropophilic colloidal layer including a photosensitive silver halide emulsion layer. CONSTITUTION:The triphenyltetrazolium compound is represented by formula I in which each of R<1>-R<3> is H or a group having a negative Hammett's sigmavalue (sigmarho), such as methyl or methoxy; and X<-> is an anion. The pyrazolidine type compound is represented by formula II in which X is H or acetyl; R is aryl; and each of R11-R14 is H, alkyl, or aryl. As a result, both of said compounds are incorporated in the hydrophilic colloidal layer, a high-contrast image can be obtained even with a stable developing solution high in sulfite ion concentration, and storage stability can be enhanced under high humidity.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material that is used for forming novel photographic images, and more particularly, it relates to a silver halide photographic material that is capable of forming a high-contrast halftone image. This article relates to a novel silver halide photographic material that has high utility value in the printing plate-making field.

[Background of the invention]

It is conventionally known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is approximately 0.
．． Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of 5μ or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 moles or more. Photosensitive (O-material, low sulfite ion concentration,
A method of obtaining a high-contrast halftone dot image or line image by processing with an alkaline developer containing only hydroquinone as a developing agent is known.

This type of silver halide light-sensitive material is known as a lithium-type silver halide photographic light-sensitive material, and has an area of a size proportional to the continuous tone density change of the original during the photolithography process. It is used to convert to a set of halftone dots. Such conversion involves using a lithium-type silver halide photographic light-sensitive material, photographing the original through a cross-line screen or contact screen, and then using a so-called lithium-ion silver halide photographic material, which has a very low sulfite ion concentration and contains only hydroquinone developing agent. This is done by forming a halftone image by developing with a Lith type developer. This lithium-type silver halide photographic light-sensitive material has two
The tonality is not sufficient; for example, even when processed with a commercially available photographic paper developer, the gamma is only 5 or 6, and fringes, which must be avoided in halftone dot formation, occur frequently, so halftone negatives/ For positive use, it is said that combination with the above-mentioned Lith type developer is indispensable. Regarding this Lith-type developer, please refer to J.N.C. Neil's Journal of the Franklin Institute (J.
A, CYule: J, Franklin In5trt
ute), Vol. 239, p. 221 (1945), contains essentially only hydroquinone as a developing agent, and has a low concentration of sulfite ions, which act as an antioxidant for the developing agent. It is a developer.

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. It is necessary to manage the developer in order to maintain a constant value, but this operation inevitably becomes complicated.

The benefits of improving the stability of Lith-type developers are extremely large, and a great deal of effort has been made to do so. For example, Sakura Doll Type 611, Sakura Doll Type 621. Compared to the same type 431 (Sakura Doll is a registered trademark) developer which exhibits a preservability comparable to that of the same type 431, it is completely inadequate.

Therefore, a phenidone-hydroquinone type developer with a high sulfite ion concentration was used to develop l1il!, which is comparable to Lith development. Several attempts have been made to form accurate images. For example, JP-A-56-106244 states that a high-contrast image can be obtained by using a hydrazine compound and by containing an amount of an amino compound in a developing solution to promote development.

Also, Special Publications No. 59-17825, No. 59-17818, No. 59-17819, No. 59-17820, No. 5
No. 9-17821, No. 59-17826, No. 59-1
Each publication such as No. 7822 discloses a silver halide photographic light-sensitive material 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 significant drawback in terms of commercial value.

Further, although the tetrazolium compound disclosed in the latter does not have the drawbacks of Moeha, it cannot be said to be fully satisfactory in terms of contrast and halftone dot quality. It is true that this performance cannot be said to be fully commensurate with the remarkable movement towards quality improvement in the printing and plate making field in recent years, 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, which has been desired to be improved.

The present invention solves the above-mentioned problems in silver halide emulsions using tetrazolium compounds, and provides a stable silver halide photosensitive material that has extremely high contrast and does not deteriorate in performance even when stored under high temperature and high humidity conditions. This is what we offer.

[Means for solving problems]

As a result of intensive research, the present inventors have found that the present inventors have a hydrophilic colloid layer including a support and at least one photosensitive silver halide emulsion layer coated on the support, and the hydrophilic colloid layer is as follows. A silver halide photographic material containing a compound represented by the general formula (1) and a compound represented by the following general formula (II) solves the above problems and provides a high contrast and stable photographic material. I found out what I can get.

General Formula (I) In the formula, n l , n t , and R3 represent a hydrogen atom or a group having a negative Hammett's sigma value (σp), and xo represents an anion.

General formula [I1] ■ t In the formula, X does not represent a hydrogen atom or an acedel group.

R represents an aryl group. n II, n +t+R13
and 114 represent a hydrogen atom, an alkyl group, or an aryl group, and may be the same or different.

The acedel group represented by X in general formula (U) may be substituted. For example, alkyl groups (methyl, ethyl, etc.)
Although it may be an acetyl group substituted with, etc., it is preferable that X is a hydrogen atom.

Examples of the aryl group represented by R in formula [I1] include phenyl, naphthyl, tolyl, and xyl, with phenyl being particularly preferred. These groups may be substituted. For example, halogen atoms (chlorine, bromine, etc.), alkyl groups (methyl, ethyl, propyl, etc.), alkoxy groups (methoxy, ethoxy, etc.), sulfonyl groups, amide groups (methylamide, ethylamide, etc.) It may also be an aryl group substituted with, etc.

Rt+, l 1tAl 13 and R of general formula (II)
The alkyl group represented by 14 has a carbon number of I to IO.
Alkyl groups (eg, methyl, ethyl, propyl, butyl, etc.) are preferred, and these alkyl groups may be substituted with hydroxyl, amino, acyloxy, etc. In addition, as an aryl group,
Phenyl group, naphthyl J&, xylyl group, tolyl group, etc. can be used, but phenyl group is particularly preferred. , propyl group, etc.), alkoxy group (hydroxy group, methoxy group,
ethoxy group, etc.).

In the present invention, substituents 1t', R of the phenyl group of the triphenyltetrazolium compound represented by the general formula [I]
", It" needs to be a hydrogen atom with a negative Hammett's sigma value (σp) indicating an electron-donating group, that is, an electron-donating group.

Hammett's sigma value for phenyl substitution has been reported in many publications, e.g. Journal of Medical Chemistry Uou
rnul of Medical Chemistry
) Vol. 20, p. 304, 1977, C. IIansch et al.
σp = -0,17 (hereinafter all σp values), ethyl group (-0,15), 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), cyclohexyl group (
-0,22), amino group (-0,66), acedelamino group (-0,15), hydroxyl group (-0,37),
Methoxy group (-0,27), ethoxy group (-0,24)
, propoxy group (-0,25), butoxy group (-0,3
2), pentoxy group (-0,:(4), etc.), and these are useful as substituents for the compound of the general formula [■] 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 Review (Chemical Review).
s) It can be easily synthesized according to the method described in Section 55, Sections 335 to 483.

The tetrazolium compound of the present invention is a halogenated silver compound contained in the silver halide photographic light-sensitive material of the present invention.
From about 1 mg to 10 g per mole, preferably about 10
Preferably, the amount is in the range of 1 mg or more up to about 2 g.

Further, specific examples of the compound represented by the general formula [■] are shown below, but the present invention is not limited to these compounds.

し+13 しν
LJL, +13n-27U-28 ■-31n-32 II-35II-36 The compound represented by the general formula (n) of the present invention can be synthesized, for example, according to the description in JP-A No. 58-50535. .

General formula contained in the silver halide photographic material of the present invention [
The amount of the compound ((ii)) is 5 x 10 per mole of silver halide contained in the silver halide photographic light-sensitive material of the invention.
- @ or up to 5 x 10-'molJ, preferably 5 x 1G-' or l x 10-'+110
The range is preferably 72.

The silver halide photographic material of the present invention comprises a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support. It may be coated directly or via a hydrophilic colloid layer that does not contain a 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 have an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer between the silver halide emulsion layer and the protective layer. Good too. The layer containing the tetrazolium compound of the present invention and the compound of general formula (If) is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. be.

In the most preferred embodiment of the present invention, in order to contain the tetrazoliu compound of the present invention and the compound of general formula (II) in the silver halide emulsion layer, the hydrophilic colloid is composed of gelatin or a gelatin derivative. It is a photosensitive material.

In order to incorporate the tetrazolium compound of the present invention and the compound of general formula (II) into the hydrophilic colloid layer, the tetrazolium compound is dissolved in appropriate water and/or an organic solvent and added, or a solution dissolved in an organic solvent is added. Examples include a method in which the compound is added after being dispersed in a hydrophilic colloid matrix of gelatin or a gelatin derivative, 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 types of tetrazolium compounds are used in combination in an appropriate ratio, image characteristics will not be adversely affected. Furthermore, a tetrazolium compound of the present invention and a tetrazolium compound other than the present invention may be used in an appropriate ratio.

In a preferred embodiment of the present invention, the general formula (i
) and general formula (II
) may be 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 colloid layer containing a silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound represented by the general formula [I] and the compound represented by the general formula [ll] are dissolved in a suitable organic solvent, such as water, alcohols such as methanol and ethanol, ethers, esters, etc. Then, by overcoating method etc., silver
It may also be incorporated into the silver halide photographic light-sensitive material by directly coating the outermost layer on the side of the silver halide emulsion layer.

It is not effective when it is contained in the backing layer. For example, when 1-phenyl-3-pyrazolidone was contained in the backing layer of the example described later, the effect was significantly inferior to that of the present invention, and the result was 0, which is not suitable for practical use. I couldn't get it.

In the present invention, when an anion is combined with the tetrazolium compound of the present invention represented by general formula (1) and reduces the hydrophilicity of the tetrazolium compound of the present invention,
Particularly favorable L) results are obtained. Examples of such anions include acid groups of inorganic acids such as perchloric acid, sulfonic acids,
Acid radicals of organic acids such as carboxylic acids, anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalenesulfonic acid anions, lauryl Sulfate anions, tetraphenyl borons, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, stearic acid anions, etc. , polyacrylic acid anions, and the like.

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 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 decagenide used in the silver halide photographic material of the present invention, but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide is AgC (2/B
r=100/O~2/98, but preferably AgCN/Br=too/10~5
The composition ratio is 0/50. The average grain size of the silver halide grains is preferably 0.10μ to 0.40μ, and has a narrow grain size distribution with a variation coefficient of 15% or less expressed by (standard deviation of grain size)/(average grain size) x too. is more preferable.

When preparing the silver halide emulsion of the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing the emulsion coating solution.

The rhodium salt used in the present invention may be a simple salt or a filtrate salt. Typically, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are used.

The amount of rhodium salt added can be freely changed depending on the required sensitivity and gradation, but it ranges from 10-9 mol to 1 mol of silver.
A range of o-4 moles is useful.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used for the purpose of imparting high-intensity properties, and can preferably be used in the range of 10-9 to 10-4 moles per mole of silver.

The silver halide used in the present invention can be sensitized with various chemical sensitizers.

Examples of sensitizers include 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 chlorooolite, potassium aurithiocyanate,
Various noble metal sensitizers represented by potassium chloroaurate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroaurate, sodium chlorovaladite, etc., each alone or in combination of two or more. □Can be used. 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 cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear merocyanines, and trinuclear or tetranuclear merocyanines. Cyanines, styryls,
Examples include holopolar cyanines, hemicyanines, oxonols, hemioxonols, etc.
These optical sensitizing dyes contain a basic group such as thiazoline, thiazole, etc. or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbital acid, pyrazolone, etc. at -11 (in their structure) as a nitrogen-containing heterocyclic nucleus. Preferably, 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, for example, U.S. Patent No. 2.444,
No. 607, No. 2,716,062, No. 3,512
, No. 982, Seisotu Application Publication No. 1,189,380,
Same No. 2.058,626, Same No. 2,118,411,
Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,59
No. 6, Special Publication No. 47-4417, Western Sozu Application Publication No. 2,
No. 149,789, Special Publication No. 39-2825, Special Publication No. 4
9-13566, preferably for example 5.6-)limethylene-7-hydroxy-S
-triazolo(1,5-a)pyrimidine, 5,6-titramedylene-7-hydroxy-S-triazolo(1,5
-a) Pyrimidine, 5-methyl-7-hydroquine-3-
Triazolo(1,5-a)pyrimidine, 7-hydroxy-8-triazolo(1,5-a)pyrimidine, 5-methyl-6-promorph-hydroxy-S-triazolo(1
, 5-a) Pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodenyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazole (5-bromobenzotriazole, 5-methylbenzotriazole),
It can be stabilized using benzimidazoles (6-nitropenzimidazole) and the like.

The silver halide and the tetrazolium compound represented by the general formula (() and the compound of the general formula (11) 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. However, examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, and gelatin derivatives. ,
For example, U.S. Pat. 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 U.S. Pat. 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 Colloids are layers that do not contain silver halide, such as antihalation layers, protective layers,
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 11, and borisdyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

As described above, the photographic material according to the present invention has at least one hydrophilic colloid layer containing silver halide on the support, and at least one hydrophilic colloid layer on the side of the layer containing the layer. The layer contains a tetrazolium compound represented by general formula [I] and a compound represented by general formula C11), and a protective layer having an appropriate thickness on the layer side, that is, preferably 0.1 to 10μ, Particularly preferably 0.8 to 2μ
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, undestining agent, pTn conditioner, 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 as thickeners or plasticizers include those described in U.S. Pat.
Publication No. 939, Seisou Zu Application Publication No. 1,904,604, Japanese Patent Application Publication No. 1973-63715, Japanese Patent Publication No. 1973-15
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 halogen-based, vinyl sulfate, etc. 1: Various hardeners and ultraviolet absorbers such as those based on carbon, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl include, for example, U.S. Patent No. 3,253,921 and British Patent No. 1. ,309,34
Compounds described in each specification etc. of No. 9, especially 2-(
2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2°hydroxy-3°.

5'-di-tertiary butylphenyl)benzotriazole,
2-(2-hydroxy-3′-tertiary butyl-5°-butylphenyl)-5-chlorobenzotriazole, 2-(
Examples of dyes include 2°-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, and examples of dyes include U.S. Pat.
No. 8, Sozu Patent No. 107,990, U.S. Patent No. 3,0
48.487, US Pat. No. 515,988, etc. can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer, or the like. British Patent No. 548.532 describes coating aids, emulsifiers, permeability improvers, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials in processing solutions. , same No. 1,216,3
No. 89, U.S. Patent No. 3,026,202, U.S. Patent No. 3.5
Specifications of No. 14.293, Japanese Patent Publications No. 44-26580, No. 43-13166, No. 4g-20785, French Patent No. 202.588, Belgian Patent No. 7
Specifications of No. 73,459, JP-A-48-1 [1111
Anionic, cationic,
Nonionic or amphoteric compounds may be used, but among these, anionic surfactants having a sulfone group, such as succinate sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, and the like are particularly preferred.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
Japanese Patent Application Laid-open No. 48-89979, U.S. Patent Nos. 2 and 8
Specifications of No. 82,157 and No. 2,972,535, Japanese Unexamined Patent Publication No. 48-20785, No. 4g-43130,
4B-90391, JP 46-24159, JP 46-39312, JP 48743809, JP 4
There are compounds described in various publications such as No. 7-331327, and as matting agents, for example, compounds described in British Patent No. 1.
No. 221.980, U.S. Patent No. 2,992,101;
Same No. 2.956.884, Buddhist Temple Patent No. 1,395,5
Compounds described in the specifications of No. 44, Japanese Patent Publication No. 43125, etc., especially silica gel with a particle size of 0.5 to 20μ, polymethyl methacrylate with a particle size of 0.5 to 20μ Examples include merging.

The silver halide photographic material containing the tetrazolium compound represented by the general formula [I] and the compound represented by the general formula (II) of the present invention is developed in the presence of the compound represented by the following general formula [■]. is preferred.

[In the formula, RI is a 5- or 6-position nitro group, It
, represents a hydrogen atom or a C3 to C1 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-nitroindazole, but the present invention is not limited thereto.

The compound represented by the general formula (III) can be dissolved in an organic solvent such as diethylene glycol, triethylene glycol, ethanol, jetanolamine and triethanolamine, an alkali such as sodium hydroxide, an acid such as acetic acid, etc. to form a developer. It may be added or may be added as is.

The compound represented by the general formula (ffi) is contained in a concentration range of about 1 mg to 1, preferably QQOs+g, and more preferably about 50 mg to 3011 mg, per 112 of the developer.

The following developing agents can be used for developing the silver halide photographic material of the present invention.

This developing agent can be used together with the compound represented by the above-mentioned general formula (In).

00 CH=[II Typical examples of OH-type developing agents include hydroquinone, as well as catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone,
Isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2゜3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.3-dibromohydroquinone, 2.5-dihydroxyacetophenone, 2.5-diethylhydroquinone, 2.5-dichlorohydroquinone -p
-Phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4-(2°-human) xybenzoyl) pyrogallol, sodium ascorbic acid, etc.

In addition, as tlo (-[II= C8 sho Ni1l type developer), ortho and para aminophenol or aminopyrazolone are typical, and 4-aminophenol, 2-amino-6-phenylphenol, 2-aminophenol, etc. -4-chloro-6-phenylphenol, 4-amiku-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6,-diaminophenol, 2.
4-cyamylsorcinol, 2,4.6-triaminophenol, N-methyl-p-aminofuconol, N-β
-Hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like.

Further, examples of the NH, type developer include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline,
-(4-amino-3-methylphenyl)-morpholine,
p-phenylenediamine, 4-amino-N, N-dimethyl-3-hydroxyaniline, N,N, No, No-tetramethylparaphenylenediamine, 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-amino-N-butyl-N-γ-sulfopsin , 6-amino-1-ethyl,
Examples include 1,2,3,4-tetra, hydroquinone, and 9-aminoyllolidine.

Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone! -Phenyl-4.4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
Examples include -pyrazoline, -phenyl-3-methyl-4-amino-5-pyrazolone, and 5-aminouracil.

Others: The Theory of James, T. Il.
The Photographic Process 4th Edition
ory or the Photographic P
rocess, Fourth Edition) No. 29
1-334 and Journal of the American Chemical Society.
American Chemical 5ociety
) Volume 73, No. 2, which can be effectively used in the present invention.

These developers may be used alone or in combination with 2Fi or more, 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 developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired, and one of the effects of the invention will be improved. Can you list it as a feature? Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. l) by caustic alkali, carbonate alkali or amine, etc. used in general black and white developers.
H adjustment and buffer function, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, and development with methanol, ethanol, benzyl alcohol, polyalkylene oxide, etc. Accelerators, surfactants such as sodium alkylaryl sulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, ionic strength regulators such as Natwau sulfate 11, etc. Additions are optional.

The developer used for developing the photosensitive material of the present invention includes (1
Alkanolamines and glycols may be contained as organic solvents. ] Examples of the alkanolamines include monoethanolamine, jetanolamine,
Among them, triethanolamine is preferably used. The preferred amount of these alkanolamines used is 5 to 500 g, more preferably 20 to 200 g, per developer IQ.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, ■, 4-butanediol, 1.5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g, more preferably 20 to 200 g, per 112 g of the 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 p14 value of the developer having the above composition is 9 to 12, but from the viewpoint of storage stability and photographic properties, the pH value is 10 to 11.
A range of is preferred.

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 lower, especially around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably, within 2 minutes often brings about good results. Processing steps other than development, such as washing, stopping, stabilizing,
It is optional to adopt steps such as fixation, and if necessary, dura mater and neutralization, and these steps can be omitted as appropriate. Furthermore, these processes may be so-called manual development processes such as plate development and frame development, or mechanical processes such as roller development and hanger development.

EXAMPLE A silver chlorobromide emulsion was prepared using the following solutions of A liquid, r(liquid), and C liquid.

[Solution Δ]

[Ossein gelatin 17gL
/A distilled water 128hQ [solution B] [-silver nitrate 170g (
- Distilled water 410m12
[Solution C] - Sodium chloride 3LOg1 Ossein gelatin I1g1 - Distilled water 40" The ltnQ solution was kept at 40°C, and
Solution B and solution C were added by the double jet method while stirring using the mixer described in No. 92524.

Table 1 The addition flow rate of each solution B and C was changed incrementally over 80 minutes to form silver halide grains. During the first 5 minutes of mixing, the EAg of the emulsion was 160mV
After 5 minutes from the start of mixing, the voltage was adjusted to 120 mV using a 3moC/12 aqueous sodium chloride solution, and thereafter this value was maintained using the aqueous sodium chloride solution. Furthermore, during the mixing, plf was maintained at 3.0 with an IN nitric acid aqueous solution.

After adding Solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, followed by desalting and washing with water in the usual manner, and then an aqueous solution of ossein gelatin 600a+12 (containing 30 g of ossein gelatin) was added to give 55 After dispersion by stirring at ℃ for 30 minutes, the temperature was adjusted to 750o+12.

The obtained particles had an average particle diameter of 1a of 0.20 μm and a monodispersity of IO.

To measure the EAg value, a metal silver electrode and a double junction type saturated g/Ag (4 reference electrode) were used.

(The double jump cushion disclosed in JP-A No. 57-197534 was used as the electrode structure.) 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 grains were generated, thereby confirming that the amount added did not exceed the critical growth rate in the system.

This emulsion was subjected to total sulfur sensitization, and as a stabilizer,
6-Methyl-4-hydroxy-1,3,3a,7-titrazaindene was added, and ■-(β-hydroxyethyl)-3-phenyl-5-((3-γ-sulfopropyl-α) was added as a sensitizing dye. -penzoxazolinyden)-edylidene] thiohydantoin was added in an amount of 150 mg per mole of silver halide contained in the emulsion for optical sensitization.

Next, per mole of silver halide, 700 mg of the compound of general formula (1) shown in Table 2, 150 mg of the compound of general formula [■] shown in Table 2, 400 mg of sodium p-dodecylbenzenesulfonate, and styrene. 2 g of maleic acid copolymer 1 styrene-butyl acrylate acrylic acid copolymer latex (average diameter approx. 0.25
μ) Add 15g to obtain Agff13.58/m2, gelatin fi2.00/, m'
It was coated on a subbed polyethylene terephthalate film base as described in Example (1) of Publication No. 9941.

At that time, 30% of ■-decyl-2-(3-isopendel)succinate-2-sulfonic acid sodium was added as a spreading agent so that the gelatin was 7 m2.
A protective layer containing 25 mg/m' of formalin and 25 mg/m' of formalin as a hardening agent was simultaneously coated.

Table 2 Triphenyltetrazolium compounds (compounds of general formula CI) The Hammett's σρ values of the substituents of the compound of general formula (1) are -CI+3-0.17) -0[II3(-0,
27) CFs (0,54) N02 (0°7g)
-COCH3(0,50), sample 1.2.3
．． The tetrazolium compounds used in Example 4 correspond to the above-mentioned exemplary compounds 1-2.1-1.1-7.1-18, respectively.

Each of the obtained samples was divided into two parts, and the other half was kept at 23°C and relative humidity of 48°C to evaluate the stability of performance.
%, then sealed and packaged with a moisture-proof material and heat-treated at 55° C. for one week. Both samples were exposed to light using a tungsten light source using an optical wedge.

The above test sample was processed using an automatic developing machine GR-27 (Roku Konishi Photography) using a developing solution and a fixing solution according to the following formulation.
(manufactured by).

[Development processing conditions]

(Process) (Temperature) (Time) Development
28℃ 30 seconds fixation
Wash with water at 28℃ for about 20 seconds at room temperature
Approximately 20 seconds [Developer composition] (Composition A) Pure water (ion exchange water) 150 m
QL Potassium Bromide 4.5g
(Composition) Pure water (ion exchange water) 3ml
2LH-phenyl-3-pyrazolidone 50
When using 0m9 developer, add the above composition A in 500mf2 of water.
, melted in order of composition, finished to ρ and used.

[Fixer prescription]

(Composition A) rAmmonium thiosulfate (72.5% W/V aqueous solution) 2
40m121 Sodium sulfite
179L acetic acid (90% w/w aqueous solution)
13.6m12 (composition) Pure water (ion exchange water) 17m
12' (aqueous solution with ALO1 equivalent content of 8.1% w/v)
When using the 26.59 fixer, the above composition A and composition r3 were dissolved in 500 ml of water in that order, and finished to IQ.

The ptT of this fixer was about 4.3.

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 for sample N.
Relative sensitivity is shown with o, 1 as 100. The legs are cut in the exposure range from optical density 0.1 to 0.5 (RogE
value). 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 samples of the present invention have high contrast and little performance deterioration during storage at high temperatures. On the other hand, samples 5 to 5 lacking the compound of general formula [11]
Sample No. 8 became difficult to cut after heat treatment, and samples No. 9 to No. 11, which used triphenyltetrazolium compounds having substituents with high Hammett values, exhibited this tendency even more strongly and were found to have significantly poor heat resistance. .

〔Effect of the invention〕

The present invention provides a silver halide photographic light-sensitive material with excellent stability, which allows images with extremely high contrast to be obtained even with a stable developing solution with a high concentration of sulfite ions, and which exhibits extremely little performance deterioration even when stored under high humidity conditions. Manufacture has become possible.

Applicant: Roku Konishi Photo Industry Co., Ltd. Procedural Amendment March 13, 1985 1. Description of the case 1985 Patent Application No. 281756 2. Name of the invention Silver halide photographic light-sensitive material 3. Person making the amendment Case and Relationship Patent applicant address: Konishiroku Photo Industry Co., Ltd., 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-1 Sakuracho, Hino-shi, Tokyo 191 (tel: 0425-83-152)
1) 5. "Detailed Description of the Invention" column of the specification to be amended.

6. Contents of amendment The Detailed Description of the Invention column should be amended as follows.

(2) Compound 1-7 on page 12 is corrected as follows.

(3) Compound 1-13 of the 13th TX is corrected as follows.

(4) Compounds 11-18 on page 17 are corrected as follows.

Claims (1)

[Scope of Claims] The hydrophilic colloid layer has a support and a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer coated on the support, and the hydrophilic colloid layer has the following general formula [ A silver halide photographic material containing a compound represented by the following general formula [II] and a compound represented by the following general formula [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents, X^
■ represents an anion. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X represents a hydrogen atom or an acetyl group. R represents an aryl group. R_1_1, R_1_2, R
_1_3 and R_1_4 represent a hydrogen atom, an alkyl group, or an aryl group, and may be the same or different, respectively. ]