JPS62134641A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a stable silver halide photographic sensitive material having high contrast and undergoing no deterioration in the performance even after storage at high temp. and humidity by using a silver halide emulsion having a prescribed average particle size and a prescribed degree of single dispersion and contg. a prescribed amount of Rh, gold sensitized silver halide having a prescribed composition and a tetrazolium compound. CONSTITUTION:Hydrophilic colloidal layer including at least one silver halide emulsion layer are formed on a support to obtain a silver halide photographic sensitive material. At this time, the silver halide in the emulsion layer has 0.05-0.5mum average particle size and 5-25 deg. of single dispersion and contains 10<-7>-10<-2>mol% Rh basing on the amount of the silver halide, gold sensitized silver chlorobromide or silver chloroiodobromide contg. >=50mol% silver chloride, at least one kind of compound represented by formula I (where each of R<1>-R<3> is H or a group having negative sigmap but R<1>-R<3> are not simultaneously H atoms) and at least one kind of compound represented by formula II (where R is H, ammonium, 1-32C alkyl or a metallic atom).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material for forming a novel photographic image, and more specifically, to a silver halide photographic material for forming a halftone image with high rice trust. This invention relates to a novel silver halide photographic material that has high utility value in the field of printing plate making.

[Background of the invention]

It is conventionally known that photographic images with extremely high contrast can be formed using silver halide photographic materials. For example, silver halide grains are fine particles with an average particle size of about 0.5μ or less, have a narrow particle size distribution, have a uniform grain shape, and have a high salt odor, such as a silver chloride content of 50 moles or more. There is a method for obtaining high-contrast halftone dot images or line images by processing a silver halide photosensitive material made of silver oxide or silver chloroiodide emulsion with an alkaline developer containing only hydroquinone as a developing agent with a low concentration of sulfite ions. Are known.

This type of silver halide light-sensitive material is known as a lithium-type silver halide 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 used to convert to 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 develops the original with very low 111 mosulfate ion concentration and hydroquinone development 1:
This is done by forming a halftone image by developing with a so-called Lith type developer containing only a drug.

This lithium-type silver halide photographic material itself does not have sufficient high contrast; for example, when processed with a commercially available photographic paper developer, the gamma is only 5 to 6, and halftone dots are formed. 1. Since fringing, which must be avoided most frequently, occurs frequently, it is said that combination with the lithium type developer described in -11 is essential for halftone negative/positive printing. This squirrel-type phenomenon liquid is described in J.N. C. Neal's Journal of the Franklin Institute (J-A-C-Yulc: J.
Franklin 1nsLiLuLa), 23rd
9, page 221 (+945), and is substantially described in detail on page 221 (+945) of Hyde [J quinone (development=hz), which is a sulfite ion 0 degree that serves as an antioxidant for the developing agent. It is a developer with a low

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 type developer having a high sulfite ion concentration. For example, JP-A-56-106244 states that a high-contrast image can be obtained by using a hydrazine compound and by including a development-promoting amount of an amino compound in the developer.

Also, Special Publication No. 59-17825, No. 59-178111
No. 1, No. 59-17819, No. 59-17820,
No. 59-17821, No. 59-■7826, No. 59
A silver halide photographic light-sensitive material containing a tetrazolium compound is disclosed in various publications such as No.-17822.

[Problem that the invention seeks to solve]

In the former technique using a hydrazine compound, p) of the phenomenon liquid
(need to be very high, around 12), and there is a problem with the stability of the liquid.Also, black spots called black pellicles occur in non-image areas, which is a significant drawback in terms of commercial value.

Moreover, the tetrazolium compounds disclosed in the latter do not have the same drawbacks as the former, or 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. Improvement was in order.

Furthermore, when stored at high temperatures and in a birdhouse, the performance deteriorates and it becomes impossible to obtain images with sufficiently high contrast, so improvements have been desired.

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. It provides:

[Means for solving problems]

As a result of intensive research, the present inventors have discovered that in a silver halide photographic light-sensitive material in which a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer is provided on a support, at least one photosensitive silver halide emulsion layer is provided. The silver halide contained in the tiger layer has an average grain size of 0.05 to 05 μm and a monodispersity of 5 to 2.
silver chlorobromide or silver chlorobromoiodide containing at least 50 mol % of silver chloride, which is gold sensitized and contains 10-9 to 10-4 mol of rhodium per mol of silver halide in the formula 5; and at least one type of compound selected from the compounds represented by the following general formula (1) in at least one layer of the hydrophilic colloid layer, and at least one type of general formula [2]
It has been found that the above-mentioned problems can be solved by using a silver halide photographic light-sensitive material containing the compound represented by the following, and a high-contrast and stable light-sensitive material can be obtained.

General formula (1) In the formula, rt' and R''R3 represent a hydrogen atom or a group having a negative Hammett's sigma value (σp), and X represents an anion.However, RI, R1, and R3 are hydrogen atoms at the same time. It is never.

General formula (II) In the formula, R represents a hydrogen atom, an ammonium salt, an alkyl group having 1 to 32 carbon atoms, or a metal atom.

In the present invention, substituents 1' and R' of the phenyl group of the triphenyltetrazolium compound represented by general formula (1)
, II3 needs to be a hydrogen atom or one with a negative Hammett's sigma value (σp) indicating the ability to attract electrons, that is, an electron-donating group.

Hammett's sigma values for phenyl substitution have been reported in many publications, such as the Journal of Medical Chemistry (Jo
Urnul of Medical Chemistry
y) Vol. 20, p. 304, 1977, in the paper by C. IIansch et al., and examples of groups with negative sigma values include, for example, methyl 5
(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 (-0,2
[+), n-pentyl group (-0,15), cyclobutyl group (-0,22), amino group (-0,66), acetylamino group (-0, I5), hydroxyl group (-0,37
), methoxy group (-0,27), ethoxy group (-0,2
4), propoxy group (-0,25), butoxy group (-0
, 32), pentoxy group (-0,34), etc.
All of these are useful as substituents in the compounds of general formula CI) of the present invention.

Specific examples of compounds represented by the general formula CI) used in the present invention will be listed below, but the compounds of the present invention are not limited thereto.

(Exemplary Compounds) The tetrazolium compounds used in the present invention are described, for example, in Chemical Reviews.
) It can be easily synthesized according to the method described in No. 55a1, pages 335-483.

The tetrazolium compound of the present invention may be used in an amount of about IB or more, preferably about 10 mg or more, per mole of silver halide contained in the silver halide photographic material of the present invention.
It is preferable to use a range up to g.

Specific examples of the compound represented by general formula (II) are shown below, but the present invention is not limited to these compounds.

(Exemplary compounds) 11-1 Gallic acid rho 2 Potassium gallate n-3 Sodium gallate! 1-4 Ammonium gallate II -5 Strontium gallate 11-6 Gallic acid methoxy ester I-7 Gallic acid brobooxy ester 11-8 Gallic acid butquin ester [I-9 Gallic acid isoamyl ester IT-10 Gallic acid octyl ester ■-11 Dodecyl gallic acid ester n-+2 Sodium gallic acid ■-13 Isoamyl gallic acid fluoride ll-14 Dodecyl gallic acid fluoride ■-15 Nonyl gallic acid Silver halide photographic material of the present invention General formula C included in
The bond of the compound II) is 5X per mole of silver halide contained in the silver halide photographic photosensitive material of the invention.
10-' or 5 x 10-'no (!, preferably s x 1o-6 or I x 10-'mo
It is preferable to set it in the evening range.

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, and the silver halide emulsion is coated on the support. Coated directly or via a hydrophilic colloid layer containing no silver halide emulsion,
A hydrophilic colloid layer may be further coated on the silver halide emulsion layer as a protective layer. Also, one layer of silver halide emulsion may be divided into silver halide emulsion layers of different sensitivities, for example high sensitivity and low sensitivity. In this case, an intermediate layer of a hydrophilic colloid layer may be provided between the silver halide emulsion layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. It may be provided. General formula C of the present invention
The layer containing the compound of I) and the compound of general formula (II) is a hydrophilic colloid layer, preferably a hydrophilic colloid layer with silver halide pores i'141 ='Δ and/or a hydrophilic colloid layer adjacent to the silver halide emulsion layer. It is a sexual colloid layer.

The most preferred embodiment of the present invention is the general formula [I
] and a compound of the general formula (In) are contained in the silver halide emulsion layer, and the hydrophilic colloid is gelatin or a gelatin derivative, or is a silver halide photographic light-sensitive material.

In order to incorporate the compound of general formula (1) and the compound of general formula (II) of the present invention into the hydrophilic colloid layer, the compound may be added after being dissolved in appropriate water and/or an organic solvent, or dissolved in an organic solvent. Examples include a method in which a solution is dispersed in a hydrophilic colloid matrix such as gelatin or a gelatin derivative, and then added, or a method in which the solution is added after being dispersed in latex. The present invention may use any of these methods.

The compound of general formula (1) used in the present invention can be used alone to obtain preferable image characteristics. Further, even if two or more of these compounds are used in combination in an appropriate ratio, the image characteristics will not be adversely affected.

One preferred embodiment of the present invention is to add the compound of general formula (1) and the compound of general formula [II] of the present invention to a silver halide emulsion layer. In another preferred embodiment of the present invention, it is added to an existing aqueous colloid layer directly adjacent to a hydrophilic colloid layer containing a silver halide emulsion layer, or to a shallow aqueous colloid layer adjacent via an intermediate layer.

In another embodiment, the compounds of general formula (1) and general formula (II) of the present invention are dissolved in a suitable organic solvent, such as water, alcohols such as methanol and ethanol, ethers, esters, etc. The silver halide photographic material may be impregnated by directly coating the outermost layer on the side of the silver halide emulsion layer of the silver halide photographic material using an overcoating method or the like.

In the present invention, particularly favorable results may be obtained when an anion is used in combination with the compound of the general formula CI) of the present invention and lowers the water resistance of the compound of the general formula (II) of the present invention.

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, anionic activators, and specifically, low-handling alkylbenzenes such as p-toluenesulfonic acid anions. Sulfonate anions, p-dobnolbenzenesulfonate anions, alkylnaphthalenesulfonate anions, lauryl sulfate anions, tetraphenylporones, No.2-
Dialkyl sulfozacnonate anions such as edylheginol sulfozacnonate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoquine sulfate anions, stearic acid anions, etc.
Can you name polyacrylic acid anions?

Such anions may be added to the hydrophilic colloid layer after being mixed in advance with the compound of general formula (1) of the present invention, or may be added alone to the silver halide containing or not containing the tetrazolium of the present invention. It can be added to the emulsion layer or the hydrophilic colloid layer.

As the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention, actual silver iodide, such as silver chlorobromide, containing at least 50 mol % of silver chloride is used.

The average particle diameter of the silver halide particles may be in the range of 0.05 to 0.5 μm, more preferably 0.10 to 0.40 μm.

The monodispersity of the silver halide grains according to the present invention is expressed by the following formula (
Defined in 1). Its value is 5-25, preferably 8-2
It is important to adjust it so that it is 0.

The grain size of the silver halide grains according to the present invention is conveniently expressed by the ridge length of a single-layer grain, and the 1/111 degree is the value obtained by dividing the standard deviation of the grain size by the 3F average diameter. Expressed as a double value.

Further, as the silver halide that can be used in the present invention, a type having a multilayer laminated structure of at least two layers can be used. For example, silver chlorobromide particles may have silver chloride in the core and silver bromide in the shell, or conversely silver bromide in the core and silver chloride in the shell. At this time, iodine can be contained in any layer within 5 mol%.

In order to increase the gradation of the silver halide emulsion according to the present invention, an appropriate amount of rhodium salt is added at the time of preparation. 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 4.

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

The amount of rhodium salt added varies depending on the type of gradation rhodium J2 salt required, the time of addition, etc., but is in the range of 10-8 mol to lo-4 mol per mol of silver, particularly preferably 10- ' to 10-6 are 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 high-intensity properties and can be preferably used in amounts ranging from 10@-8 to 10@-8 moles per mole of silver.

In the present invention, a gold-sensitized silver halide emulsion is used. Examples of total sensitizers include potassium chloride [10 oleite, potassium aurithionanate, potassium chloride J4]
Various known gold compounds such as chloroaurate and 2-ourosulfobenzothiazole medyl chloride can be used, and thiocyanides such as [J Danammon] can also be used as an auxiliary agent.

Further, the above silver halide emulsion can be sensitized using a gold sensitizer and various other chemical sensitizers.

Examples of these sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), and selenium sensitizers (N
, N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, stannic chloride, etc.), various noble metals such as ammonium chloroparadate, potassium chloroplatinate, sodium chlorovaradite, etc. Sensitizers and the like can be used alone or in combination of two or more. 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, melonoaenes, trinuclear or tetranuclear melonanines, trinuclear or tetranuclear melonanines, styryls, holoboraenes, heminoenes, oxonols, etc. These optically sensitizing dyes have a nitrogen-containing heterocyclic nucleus and a basic group such as deazoline or thiazole, or rhodanine, thiohydantoin, or oxazolin as a nitrogen-containing heterocyclic nucleus. non-geon,
Those containing a nucleus such as barbylic acid, thiobarbital acid, pyrazolone, etc. are preferable.Such a nucleus can be substituted with argyl, hydrogynealkyl, halogen, phenyl, cyano, or alkoxy, and these optical sensitizing dyes can be substituted with carbocyclic or It may be fused with a heterocycle. In addition, when the above-mentioned optical sensitizing dyes, particularly melonanine-based sensitizing dyes, are used, not only optical sensitization but also the effect of widening the phenomenon latitude can be obtained. Further, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat.
No. 2,716,062, No. 3,512,98
No. 2, West German Application Publication No. 1゜189.380, No. 2
, 058,626, 2,118,411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3.342.596,
Special Publication No. 47-4417, West German Application Publication No. 2.149
．． No. 789, Special Publication No. 39-2825, Special Publication No. 49-1
3566, preferably for example 5,6-drimedylene-7-hydroquine-S-triazolo(1,5-a)pyrimidine, 5,6-titramethylene-7-hydroquine-S-triazolo(1,5-a) ) pyrimidine, 5-methyl-7-hydroquine-5-)riazolo(1,5-a)pyrimidine, 7-hydrokyl s -
triazolo(1,5-a)pyrimidine, 5-methyl-6
-BromorphophytroxyS -triazolo(1,5
-a) Pyrimidine, mercaptan M (1-phenyl-5
- Stabilization using mercaptotetrazole, 2-mercaptobenzdeazole), benzotriazoles (5-prombenozotriazole, 5-methylbenzotriazole), henraimidazoles (6-nitrobenzimiguzole), etc. Be able to do it.

Although the faceted silver halide and the compound of general formula (1) and the compound of general formula (II) according to the present invention are added to the hydrophilic colloid layer, 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, gelatin derivatives, For example, U.S. Patent No. 2,61
Phenylcarbamyl gelatin, anlylated gelatin, phthalated gelatin as described in U.S. Pat. No. 4,928 and U.S. Pat. No. 2,525,753, or U.S. Pat. Polymerizable monomers having an edylene group, such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester, as described in the specifications of , No. 831, 767, are graft-polymerized onto gelatin. These hydrophilic colloids can be used in layers that do not contain silver halide, such as halide prevention layers, protective layers, intermediate layers, etc.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass temporary paper,
Cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide 1, films, polypropylene films,
Typical examples include polycarbonate film, polystyrene film, and the like. 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 the compound of the general formula [I] and the compound of the general formula C [I) of the present invention, and a protective layer having an appropriate thickness on the layer side, that is, preferably 0.1 to
Preferably, a gelatin protective layer of 10 .mu.m, particularly preferably 0.8 to 2 .mu.m, is applied.

The hydrophilic colloid used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners,
Surfactant, image stabilizer, ultraviolet spring absorber, antistain agent, pH, J1 regulator, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development speed Conditioners, matting agents, etc. can be used within the range that does not impair the effects of the present invention.

Among the above-mentioned various additives, those which can be particularly preferably used in the present invention are those described in US Pat. No. 2.960.404, Japanese Patent Publication No. 43-4
Publication No. 939, West German Application Publication No. 1,904,604, Japanese Unexamined Patent Publication No. 48-63715, Japanese Patent Publication No. 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, evoquino-based, edylenimine-based, active halogen-based, Various hardeners and ultraviolet absorbers such as vinyl sulfone type, isonoanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc., include, for example, U.S. Pat.
, 253,921 and British Patent No. 1.309,349, particularly 2-(2°
-hydroxy-5-tertiary butylphenyl)benzo) lyazole, 2-(2°hydroxy-3°.

5'-di-tertiary butylphenyl) benzotriazole,
2-(2-Hydroquine-3°-tertiary butyl-5′-butylphenyl)-5-chlorobenzotriazole, 2-(
Examples of dyes include 2°-hydroxy-3°, 5°-di-tertiary butylphenyl) = 5-chlorobenzotriazole, and dyes described in U.S. Pat. No. 2,072゜90
No. 8, German Patent No. 107.99Q, U.S. Patent No. 3,0
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 liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548.532, 1,216th,
No. 389, U.S. Patent No. 3.026,202, U.S. Pat.
Specifications of No. 514,293, Japanese Patent Publication No. 44-26580
No. 43-13166, No. 4g-20785, specifications of French Patent No. 202.588, Belgian Patent No. 773,459, Japanese Patent Application Laid-open No. 1973-10111
Anionic, cationic, etc. described in Publication No. 8, etc.
Nonionic or amphoteric compounds can be used, and among these, anionic surfactants having a sulfone group, such as succinic acid ester 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. 4111-89979, U.S. Patent No. 2
, 882,157 and 2,972,535, JP-A-48-20785, and JP-A-4B-43120.
There are compounds described in Japanese Patent Publication No. 4B-90391, Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 46-39312, Japanese Patent Publication No. 48-43809, and Japanese Patent Application Laid-open No. 47-33627. For example, British patent no.
．． No. 221,980, U.S. Patent No. 2,992.1■,
No. 2.956.884, French Patent No. 1,395,5
Compounds described in the specifications of No. 44, Japanese Patent Publication No. 48-43125, 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 compound of general formula (1) and the compound of general formula [11] of the present invention is preferably developed in the presence of a compound represented by the following general formula (III).

[In the formula, 1, , is a nitro group at the 5- or 6-position, n
+z represents a hydrogen atom or a C9-C1 lower alkyl group. M represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or an ammonium ion. ] As a specific compound represented by the general formula [I■], 5-
Examples include nitroindazole and 6-nitroindazole, but the present invention is not limited thereto.

Compounds represented by the general formula CIII] include a
It may be added to the developer after being dissolved in a solvent, an alkali such as sodium hydroxide 11, an acid such as acetic acid, or it may be added as is.

The compound represented by the general formula [: In ) is a developer IQ
It is preferably included in a concentration range of about 1 mg to 1.000 mg, more preferably about 50 B to 30 OB.

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 Cm.

[0ICl1=CI) Typical examples of 011 type developing agents include hydroquinone, as well as catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2゜3-nochlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxoacetophenone, 2.5-diethylhydride [lquinone, 2.
5-di-p-phenethylhide "l quinone, 2.5-
Dibenzoylaminohydroquinone, catechol, 1
-chlorocatechol, 3-phenylcatechol, 4-phenylcatechol, 3-methoxycatechol, 4-
Examples include acetyl-pyrogallol, 4-(2°-hydroginebenzoyl)pyrogallol, and ascorbic acid sorta.

Also, 110 children Cl1=CI1 square Ni1. Typical type agents include ortho and para aminophenols or aminopyrazolones, such as 4-aminophenol, 2-amino-6-phenylphenol, 2-7mi/-
4-chloro-6-phenylphenol, 4-amiku2
-phenylphenol, 3,4-noaminophenol,
3-Methyl-4,6,-aminofgonol, 2.4-
Diamylsolnonol, 2.4.6-triaminophenol, Hamedyl p-aminephenol, N-β-hydroquinethyl-p-aminophenol, p-hydroquinophenylaminotoacid, 2-amino There are naphthol etc.

Further, as the tlzN + C= C sho NIL type developer, for example, 4-amino-2-medyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-(4-amino-3 -methylphenyl)-morpholine, p-phenylenediamine, 4-amino-N,N-
trimethyl-3-hydroquinaniline, 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=edyru(β-methoxyethyl)-3-methyl-aniline, 4-amino-3-methyl-N-ethyl-N=(β-methylsulfonamidoethyl) -aniline, 4-amino-
N-butyl-N-γ-sulbodelaniline, 1-(4
-aminophenyl)-pyrrolidine, 6-amino-1-ethyl, 1,2.3.4-tetrahydroquinone, 9-aminoyurolidine, and the like.

Examples of the hetero-armor type developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-tumedel-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymedyl-3-pyrazolidone, 1 -phenyl-4-methyl-
3- such as 4-hydroquinemethyl-3-pyrazolidone
Pyrazolidones, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 5-aminouracil and the like.

Others, T, 11. The theory by James
The Photographic Process 1st Edition (TheTh
theory of the Photographic
Process, Fourth Edition) 2nd
pp. 91-334 and Journal of the American Chemical Society.
American Chemical 5ociet
y) The agents described in Vol. 73, No. 3, p. 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.

In addition, if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the photosensitive solution of the present invention (4-material phenomenon), the effect of the present invention will not be impaired or destroyed. One of the features of the invention is that > i etc. to control A'I of pt-t and have a buffer function, as well as inorganic phenomenon suppressors such as bromopotassium, organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, etc. , development accelerators such as Hensyl alcohol and polyalkylene ochind, sodium alkylarylsulfonate,
It is optional to add surfactants such as natural saponins, saccharides or alkyl esters of the above compounds, hard agents such as glutaraldehyde, polymerin, glyoxal, ionic strength regulators such as sodium sulfate, and the like.

The developing solution used for developing the photosensitive material of the present invention includes Rh
It may contain alkanolamines or glycols as a solvent. Examples of the above-mentioned alkanolamine include monoethanolamine, noethanolamine, and triethanolamine, and triethanolamine is preferably used. The preferred amount of these alkanolamines to be used is 5 to 500 g, more preferably 20 to 200 g, per 1 liquid.

In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1.・1-Butanediol, 1.
Although 5-bentanediol and the like are available, diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g, more preferably 20 to 200 g, per developer IQ.

These organic solvents can be used alone or in combination.

The silver halide photographic material of the present invention can be processed with a developing solution containing the above-mentioned development inhibitor to obtain a photosensitive material with excellent storage stability.

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 is 5
The temperature is preferably 0°C or lower, particularly preferably around 30'C,
Further, the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which often yields good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, prehardening 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 illicit development processes such as roller development and bunker development.

Example A silver chlorobromide emulsion was clarified using the following solutions A, B and C.

[Solution A]

1 Ossein geladin 17g1-
Tar solution 50.2' 7A
'Kl Water 12Hm12 [Solution B] Silver nitrate 170gL Distilled water =llOmC [Solution C] Sodium chloride 38.0gL
Distilled water 401m'Q Keep solution A at 40°C, and add solution B and solution C by double jet method while stirring using the mixer described in JP-A-57-92523 and JP-A-57-92524. did.

Below - City 1.・・・ノ゛＼Lノ' Table 1 The addition flow rates of each of the solutions B and C were varied incrementally over a period of 80 minutes as shown in Table 1 to form silver halide grains. During the first 5 minutes of mixing, the EAg of the emulsion was kept at 160 mV.
After 5 minutes from the start of mixing, the voltage was adjusted to 120 mV using a 3 moQ/Q aqueous sodium chloride solution, and this value was maintained thereafter using the aqueous sodium chloride solution. Further, during mixing, r) [-1 to 3.0
was held at

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 600 mρ of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) was added. After dispersing by stirring at 55° C. for 30 minutes, the temperature was adjusted to 750 mC.

The average particle size of the obtained particles was 0.20 μm, and half the particle diameter was 10.

A metal silver electrode and a double junction saturated Ag/AgC12 reference electrode were used to measure the EAg value.

(The double jump cushion disclosed in JP-A No. 57-197534 was used as the electrode structure.) A variable flow rate roller duplex constant m pump was used to add solutions B and C.

During the addition, the emulsion was sampled to confirm that no new grains were generated using an electron microscope (Rm), and it was confirmed that the amount added did not exceed the critical growth rate change in the system.

This emulsion was divided into two parts, one half was subjected to total sulfur sensitization by adding 10 mg of sodium thiosulfate pentahydrate and 10 mg of trichloroauric acid per mole of silver, and the other half was subjected to total sulfur sensitization. Sulfur sensitization was performed by adding only sodium sulfate. As a stabilizer for each sensitized emulsion, 6-methyl-4-hydroquine-1,3,3a, ? -Tetrazaindene was added, and 1-(β-hydroquinoedyl)-3-phenyl to 5-C(3-γ-sulfopropyl-α-penzooxazolinidene)-ethylidene]diohydantoin was added as a sensitizing dye. 150 mg per mole of silver halide contained in the emulsion
was added for optical sensitization.

Next, 700 mg of the compound of general formula [I] shown in Table 2 per mole of silver halide, 1.5 g of the compound of general formula CII) shown in Table 2, and sodium p-dodenlebenzenesulfonate. 400 mg, 2 g of styrene-maleic acid copolymer, styrene-butyl acrylate acrylic acid copolymer latex (lower average particle size approximately 0.25μ)
) Add 15g of gelatin and add 3.5g/m' of gelatin. Apply it on the base so that it becomes QO/m2. At that time, gelatin 11. l-denol-2-(3-isopendel)succinate-? ~21 Shiju'no drunkenness 2' Nokehon ffnmσ/m"
A protective layer containing 25 mg/m' of formalin as a hardening agent was simultaneously coated.

Each of the obtained samples was divided into two halves, and the other half was kept at 23°C1 relative humidity 4 to evaluate the stability of performance.
After controlling the humidity to 8%, it was 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 phenomenon liquid and a fixing liquid according to the following formulation.
(manufactured by).

The test sample contents and test results are shown in Table 2.

[Development processing conditions]

(Process) (Temperature) (Time) Development
Fix at 28°C for 30 seconds 288
C 20 seconds water washing Room temperature 20 seconds [Developer composition] (Composition A) Pure water (ion exchange water) 150 m
Q-ethylene glycol 509 ■ 1 Potassium sulfite (55% w/v aqueous solution) 1
00m (! Potassium acid 5
0g Hydroquinone 15g
5-methylbenzotriazole 200m9
1-phenyl-5-mercaptotetrazole 30mg
Potassium hydroxide Adjust the pH of the solution to 10.4 mL Potassium bromide 4.59 (composition) Pure water (ion exchange water) 3 m
Qf Noedylene Glycol 50gt
Endyenediaminetetraacetic acid disodium salt 25B1 acetic acid (90% aqueous solution) 0.3 m (1
5-Nitroindazole 110mg
11-phenyl-3-pyrazolidone 500
When using developer B, add 500 m0 of water. In "2nd composition A,
They were melted in the order of their phase formation, finished into IQ, and used.

[Fixer prescription]

(Composition A) “Ammonium diosulfate (72.5% w/v aqueous solution) 2
40m (sodium citrate dihydrate
29L acetic acid (90% w/w aqueous solution)
13.8mQ (composition) Pure water (ion exchange water) 17m
Q□ Shikuhe Q203 equivalent content is 8.1%W/guest aqueous solution)
When using the 26.59 fixer, it was dissolved in 500 mf2 of water in the order of composition A and composition, and finished to IQ.

The l) r-1 of this fixer was about 43.

As shown in Table 2 below, it can be seen that the samples of the present invention have extremely high contrast and sensitivity, and exhibit little performance deterioration when stored under high humidity. On the other hand, in the sample lacking the compound of general formula II, the leg j13 was difficult to cut after heat treatment, and furthermore, it was revealed that the sensitivity was low when sensitized quickly, and the heat resistance was poor.

〔Effect of the invention〕

According to the present invention, it is possible to produce a silver halide photographic material with high sensitivity and excellent stability with extremely little deterioration in performance even when stored under high humidity conditions, with zero manufacturing steps.

Applicant: Konishiroku Photography Co., Ltd. You lost your hand, IJ Sei τ! P March 60, 1988

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on a support, wherein a halogen contained in at least one of the silver halide emulsion layers is provided. Silver oxide has an average particle size of 0.05 to 0.
5 μm, monodispersity of 5 to 25, containing 10^-^3 to 10^-^4 moles of rhodium per mole of silver halide, and gold sensitized, containing at least 50 mole % silver chloride. Silver chlorobromide or silver chlorobromo iodide, and at least one layer of the hydrophilic colloid layer has the following general formula [I]
1. A silver halide photographic light-sensitive material characterized by containing at least one compound selected from the compounds represented by the formula [II] and at least one compound represented by the general formula [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, R^3 represent a hydrogen atom or a group whose Hammett's sigma value (σp) is a negative value, X^
■ represents an anion. However, R^1, R^2, and R^3 are never hydrogen atoms at the same time. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a hydrogen atom, an ammonium group, and a carbon number of 1 to 32
represents an alkyl group or a metal atom. ]