JPH0668613B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention is used in the field of photoengraving, and is capable of rapidly forming a super-high contrast image with a highly stable processing solution. Especially negative type).

(Prior Art) It is known that a photographic image having an extremely high contrast can be formed by using a certain type of silver halide, and such a photographic image forming method is used in the field of photolithography.

For example, silver chlorobromide (at least 50% silver chloride content
In the lithographic silver halide light-sensitive material consisting of the above, the effective concentration of sulfite ion was made extremely low (usually 0.1 mol / mol).
Below) by treating with a hydroquinone developer,
There is known a method of obtaining a line drawing or a halftone dot image having a high contrast and a high blackening density in which an image portion and a non-image portion are clearly distinguished. However, in this method, since the concentration of sulfurous acid in the developer is low, the development is extremely unstable against air oxidation, and various efforts and ingenuities are being used to keep the solution activity stable. It was.

Therefore, the developing method as described above (lith development system)
To eliminate the instability of image formation due to, developing with a processing solution having good storage stability, there is a demand for an image forming system capable of obtaining ultrahigh contrast photographic characteristics, U.S. Pat.No. 4,166,742,
4,168,977, 4,221,857, 4,224,401, 4,2
No. 43,739, No. 4,272,606, No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material added with a specific acylhydrazine compound was added at 0.15 mol / sulfite preservative at pH 11.0 to 12.3. A system has been proposed which includes the above and is processed with a developer having good storage stability to form a super-high contrast negative image having a γ of more than 10. This new image forming system can only use silver chlorobromide with a high silver chloride content in conventional ultra-high contrast image formation, whereas
The feature is that silver iodobromide or silver chloroiodobromide can also be used.

Generally, in a silver halide photographic light-sensitive material, the image blackening density obtained per unit amount of developed silver increases as the size of silver halide grains decreases, but the sensitivity of silver halide generally increases with the size of silver halide grains. The higher it gets. Therefore, in order to obtain a light-sensitive material which gives high sensitivity and high blackening density, it is necessary to add more silver halide emulsion having a larger grain size per unit area. However, a light-sensitive material containing a large amount of silver halide emulsion takes a long time for fixing, washing with water and drying at the stage of development processing, resulting in impaired rapid processability.
Further, silver is expensive, and the production amount and the reserve amount are limited. Therefore, it is required to produce a light-sensitive material using as little silver as possible.

For this reason, research on a silver halide light-sensitive material having high image density and high sensitivity by using less silver has been conducted for many years.

On the other hand, this new high-contrast negative image forming system achieves a significantly higher high-sensitivity high-sensitivity image at the same time as black spots due to contagious development.
per), which is an undesired phenomenon, which is a problem in the photomechanical process.

A black spot is a black spot made of minute developed silver that is generated in a portion that is originally unexposed and should become a non-image.
Black spots frequently occur due to a decrease in sulfite ion, which is generally used in a developer as a preservative, and an increase in pH value, and the commercial value as a photosensitizing material is significantly reduced. Therefore, great efforts have been made to improve this black spot, but the improvement of the black spot is often accompanied by a decrease in sensitivity and gamma (γ). It was strongly desired.

On the other hand, in this field, in order to satisfy the delicate tone reproduction and artistic expression of the image, a reduction process is applied to reduce the halftone dot area, or the line width of the line drawing is enlarged or reduced. Often partial or total modifications are made. Therefore, it is one of the extremely important performances whether or not it has a reduction processing property especially in the light-sensitive material for plate making. In this respect also, the silver halide photographic light-sensitive material which improves the black spot and gives a high maximum density. Material was desired.

As one of such methods, Japanese Patent Application No. 60-64199 discloses a silver halide photographic light-sensitive material having a grain size of 0.5 μm or less and containing two kinds of monodisperse emulsions and a hydrazine derivative. However, even with this method, it was still insufficient in terms of obtaining a high blackening density with a small amount of silver.

(Problems to be Solved by the Present Invention) A first object of the present invention is to provide a silver halide photograph capable of obtaining a high blackening density with few black spots, high sensitivity and high contrast (for example, γ is 10 or more). A photosensitive material and an image forming method are provided.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having improved processability for reduction processing.

(Means for Solving the Problems) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and to contain the hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. In the above silver halide photographic light-sensitive material, the emulsion layer contains two types of monodisperse silver halide grains having different average grain sizes, and each of the two types of monodisperse silver halide grains has an average grain size of 0.1.
It can be achieved by a silver halide photographic light-sensitive material characterized in that monodisperse silver halide grains having a size of .about.0.4 .mu.m and small size are chemically sensitized.

The above object could be achieved to some extent by the method disclosed in Japanese Patent Application No. 60-64199, in which two kinds of silver halide grains having different grain sizes are mixed and used, but less silver is used. However, it is not always sufficient in terms of obtaining high sensitivity and high Dmax. On the other hand, the present invention can achieve the above-mentioned object more effectively by chemically sensitizing small-sized silver halide grains.

The large size monodisperse particles used in the present invention preferably have higher sensitivity than the small size monodisperse particles, but have a drawback that the blackening concentration per a certain amount of silver is low because of the large particle size. Combined with a chemically sensitized small size monodisperse emulsion, preferably with a small size emulsion having a lower sensitivity than a large size emulsion, to use a single chemically sensitized silver halide grain alone. High sensitivity, high Dmax and excellent reduction performance can be obtained at the same black spot level as compared with the case where it is not.

In other words, the phenomenon that a remarkable effect can be seen by using the chemically sensitized small-sized particles together is that, as a result of earnest research, the infectious development active species generated by the development of large-sized particles is exposed to light. It is considered that this is because the sub-latent image of the small-sized particles thus formed can be efficiently developed, and further, the infectious development to the unexposed particles is accelerated. Therefore, it is possible to easily perform development even in rapid processing with a total processing time of 90 seconds to 120 seconds from the time when it is put into the automatic developing machine until it comes out. This chemically sensitized emulsion composed of small-sized silver halide grains has a high infectious development activity, while the sub-latent image portion contributes effectively to the image density, which results in the unexposed portion. It is possible to obtain high sensitivity and Dmax before black spots occur in the. Therefore, it is remarkably advantageous in terms of sensitivity and Dmax as compared with an unchemically sensitized emulsion in which a sub-latent image is difficult to form. Here, the sub-latent image is well known to those skilled in the art, an image is not formed when the development is carried out under the condition that the hydrazine derivative does not exist, and as described later, for example, gold When it is developed after being assisted, a substantial image can be formed.

In the present invention, the sensitivity of the small or large size silver halide emulsion can be evaluated in more detail as follows.

That is, a small- or large-sized silver halide emulsion-containing layer containing a hydrazine derivative and a protective layer are coated on a support and subjected to development processing as described in Example 1 to obtain sensitivity. . Here, the amount of coated silver can be evaluated, for example, by applying 3 g / m ² .

Here, the difference in sensitivity between the large size monodisperse emulsion and the small size monodisperse emulsion preferably used in the present invention is not particularly limited, but is preferably 0.1 to 1.0 as ΔlogE, and more preferably ΔlogE.
0.2 to 0.7.

As a method of chemically sensitizing the small size monodisperse emulsion, known methods such as sulfur sensitization, reduction sensitization and gold sensitization can be used, and they can be used alone or in combination. The preferred chemical sensitization method is sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as tithisulfate, thioureas, thiazoles, and rhodanines can be used. Specific examples are U.S. Patents 1,574,944 and 2,278,947.
No. 2, No. 2,410,689, No. 2,728,668, No. 3,501,313,
No. 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg during chemical sensitization is preferably 8.3 or less, more preferably
It is in the range of 7.3 to 8.0. Furthermore, Moisar, Klein Gelatine.
Proc.Symp.2nd, 301 to 309 (1970) and the like, the method of using polyvinylpyrrolidone in combination with thiosulfate also gives good results.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061. In the present invention, a silver halide emulsion such as rhodan potassium or thioether may be used together with chemical sensitization, or surface conversion by KI may be used together. Furthermore, a sensitizing dye or
Chemical sensitization may be carried out in the presence of a stabilizer such as tetrazaindene. Large-sized particles generally tend to cause black spots, and therefore it is preferable not to carry out chemical sensitization or to provide a means such that black spots do not occur even when chemically sensitized. For example, if chemical sensitization is applied shallowly,
Alternatively, there is a method of preventing the generation of black spots by using rhodium. Here, “shallow” means that the time for chemical sensitization is shorter than that for chemical sensitization of small-sized grains, or the amount of chemical sensitizer added is suppressed. When rhodium is used, it is preferably added during grain formation, and the preferable rhodium is rhodium ammonium chloride, and the preferable addition amount is 1 × 10 ⁻⁸ to 8
It is in the range of ^{x10 -6} mol.

In the present invention, the degree of chemical sensitization that serves the purpose can be evaluated based on the presence or absence of a sublatent image or its degree. The presence of Asen image can be THJames, J.Colloid.Sci 3 447 to make sure I go-between in gold intensification methods, such as those by connexion reported in (1948). For example, the above-mentioned film evaluated for sensitivity is exposed through a step wedge having a density difference of 0.1, immersed in a gold intensifying solution having the following formulation A at 20 ° C. for 10 minutes, and then washed with running water for 10 minutes. After that, it can be evaluated by developing with a developing solution having the following formulation B at 38 ° C. for 20 seconds. Chemically sensitized emulsions that easily form sub-latent images have higher sensitivity (ΔlogE) than unchemically sensitized emulsions.
Is extremely large. Here, the increase in sensitivity is expressed by ΔlogE = [sensitivity (logarithm of exposure dose giving density 1.5) at 38 ° C. for 20 seconds after pretreatment with gold intensification solution A] − [development solution 38
Sensitivity at 20 ° C. for 20 seconds].

The increase in sensitivity of large-sized particles by the gold intensification method is ΔlogE
Is preferably less than 0.4, more preferably 0.1 to 0.3, and the increase in sensitivity for small size is preferably 0.4 or more, more preferably 0.5 to 0.7.

There is no particular limitation on the halogen composition of the silver halide emulsion used in the present invention, and any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide can be used. It may be one. The halogen composition of the two kinds of emulsions may be the same or different.

The silver halide emulsion used in the present invention can be prepared by various methods known in the field of silver halide photographic light-sensitive materials. For example, P.Glafkides's "Chimie e.
t Physique Photographique) ”(Paul Montell (P
aul Montel) 1967), GFDuffin, "Photographic Emulsion Chemistry"
(1966 published by The Focal Press)
Year), VLZelikmanet a
l) "Making and Coating Photo (Making and Coating Photo)
graphic Emulstion ”(The Focal Press (The
Focal Press) 1964) and the like.

The average grain size of the small-sized silver halide grains used in the present invention is preferably 90% or less, more preferably 80% of the average grain size of the large-sized silver halide grains.
% Or less.

The average grain size of the silver halide emulsion grains is preferably 0.02 μm to 0.5 μm, particularly preferably 0.1 μm to 0.
It is preferable that the average particle size of large size and small size monodisperse particles is included in this range at 4 μm. JP-A-57
Average particle size 0.7 μm as disclosed in −58137
The above particles are not preferable because black spots are rapidly deteriorated.

In the present invention, the coated silver amount of the small size monodisperse emulsion is preferably 40 to 90 wt%, and more preferably 50 to 80 wt% with respect to the total coated silver amount.

In the present invention, the monodisperse emulsions having different grain sizes are preferably introduced into the same emulsion.

Note The total amount of coated ^{silver, 1g / m 2 ~8g / m} 2 is preferred.

As a method of reacting the water-soluble silver salt (aqueous silver nitrate solution) with the water-soluble halogen salt, any one-side mixing method, simultaneous mixing method, or a combination thereof may be used. As one type of double jet method, pAg in the liquid phase where silver halide is formed
Can also be used, that is, the control double jet method can be used. Grains can also be formed by using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea.

With the control double jet method and the grain forming method using a silver halide solvent, it is easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. This is an effective means.

The monodisperse emulsion preferably has a regular crystal form such as a cube, an octahedron and a tetradecahedron, and a cube and an tetradecahedron are particularly preferable.

The monodisperse emulsion in the present invention is the number of the whole
An emulsion having a distribution in which the size of grains accounting for 90% is within ± 40% of the average grain size, preferably within ± 20%.

The silver halide grains may have a uniform inner layer and surface layer, or may have different layers.

Even if a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof are allowed to coexist in the silver halide emulsion used in the present invention in the process of formation or physical ripening of silver halide grains. Good.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is 10 mol / mol of silver.
^A silver halide which is produced in the presence of ^-8 to 10 ^-5 mol of iridium salt or its complex salt and is 70 mol% or more, particularly 90 mol% or more of silver bromide is preferred. The silver iodide content is preferably 10 mol% or less, more preferably 0.1 to 5 mol%, and the silver iodide content on the grain surface is larger than the average silver iodide content of the grains. Is preferred. By using an emulsion containing such a silver haloiodide, photographic characteristics with higher sensitivity and high gamma can be obtained.

When using silver chlorobromide, 50 mol% or more, especially 70 mol%
The above is preferably a silver halide containing silver bromide.

In the above, it is desirable to add the above amount of iridium salt before the physical ripening in the production process of the silver halide emulsion, especially at the time of grain formation.

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, for example, iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), potassium hexachloroiridium (IV), hexachloroiridium, ammonium (III) acid. And so on.

Preferred examples of the hydrazine derivative used in the present invention include aryl hydrazides having a sulfinic acid residue bonded to a hydrazo moiety described in U.S. Pat. No. 4,478,928, and compounds represented by the following general formula (I). Is mentioned.

In formula (I) R ₁ -NHNH-G-R ₂ , R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Represents a group, a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an N substituted or unsubstituted iminomethylene group.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly 1 to 3 carbon atoms.
20 straight, branched or cyclic alkyl groups. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group or the like.

The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrrolazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. .

Particularly preferred as R ₁ is an aryl group. R ₁
The aryl group or unsaturated heterocyclic group of may be substituted, and typical examples of the substituent include a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20) and an aralkyl group (preferably Has 1 to 3 carbon atoms in the alkyl moiety
Monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably Are those having 2 to 30 carbon atoms), sulfonamide groups (preferably those having 1 to 30 carbon atoms),
There are ureido groups (preferably those having 1 to 30 carbon atoms) and the like.

The alkyl group represented by R ₂ preferably has 1 carbon atom.
~ 4 alkyl groups, a halogen atom, a cyano group,
It may have a substituent such as a carboxy group, a sulfo group, an alkoxy group and a phenyl group.

The optionally substituted aryl group represented by R ₂ is a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group or the like.

The optionally substituted alkoxy group represented by R ₂ is an alkoxy group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aryl group or the like.

The optionally substituted aryloxy group represented by R ₂ is preferably a monocyclic group, and examples of the substituent include a halogen atom and the like.

Among the groups represented by R ₂ , preferred is a hydrogen atom, a methyl group, a methoxy group, an ethoxy group or a substituted or unsubstituted phenyl group when G is a carbonyl group, and a hydrogen atom is particularly preferred.

When G is a sulfonyl group, R ₂ is a methyl group,
An ethyl group, a phenyl group and a 4-methylphenyl group are preferable, and a methyl group is particularly preferable.

When G is a sulfolyl group, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly preferably a phenoxy group.

When G is a sulfoxy group, preferred R ₂ is a cyanobenzyl group, methylthiobenzyl group and the like, and when G is an N-substituted or unsubstituted iminomethylene group, preferred R ₂
Is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

R ₁ or R ₂ may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more which is relatively inactive to photographic properties, and includes, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can choose from.

R ₁ or R ₂ may have a group incorporated therein to enhance adsorption to the surface of the silver halide grain. Examples of the adsorptive group include groups described in US Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

A carbonyl group is most preferable as G in the general formula (I).

Specific examples of the compound represented by formula (I) are shown below.
However, the present invention is not limited to the following compounds.

Examples of the hydrazine derivative used in the present invention include RESEARCH DISCLOSURE Item 23516 (1983
November issue, p.346) and other documents cited therein,
U.S. Patents 4,080,207, 4,269,929, 4,276,364
, 4,278,748, 4,385,108, 4,459,347,
4,560,638, 4,478,928, British Patent 2,011,391B,
Those described in JP-A-60-179734 can be used.

The compound represented by the general formula (I) is preferably contained in an amount of 1 × 10 ⁻⁶ to 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol per mol of silver halide. The range is the preferable addition amount.

When the compound represented by the general formula (I) is contained in a photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (for example, methanol or ethanol) or esters (for example, ethyl acetate) when it is water-insoluble. As a solution of an organic solvent miscible with water such as ketones (for example, acetone), it may be added to a silver halide emulsion (emulsion composed of coarse particles, emulsion composed of fine particles) solution or a hydrophilic colloid solution.

When it is added to the silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferable to add it after the completion of chemical ripening, especially the coating prepared for coating. It is preferably added to the liquid.

The sensitizing dyes described in JP-A-55-52050, pages 45 to 53, such as cyanine dyes and merocyanine dyes, may be added to the light-sensitive material used in the present invention. it can.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are not limited to those mentioned above, Research Disclosure 176, 17643 (issued in December 1978), page 23. It is described in A to J of IV.

Here, the sensitizing dye and the like can be added to any step of the production process of the photographic emulsion for use, or can be added at any stage after production and immediately before coating. Examples of the former include grain formation, physical ripening, and chemical ripening.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes) ), Pentaazaindenes, etc .; many compounds known as anti-capry agents or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. are added. Rukoto can. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium deuterium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-). Triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid etc.), etc. can be used alone or in combination. Among them, JP-A-53-41221 and 5
The active vinyl compounds described in 3-57257, 59-162546 and 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferred.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in smoothness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl). Nonionic surfactants such as amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulphonates, alkyl benzene sulphonates Salts, alkylnaphthalene sulfonates, alkyl sulfate esters, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfuric ester group, a phosphoric ester group such as phosphates; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocycles such as pyridinium and imidazolium Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

When it is used as an antistatic agent here, a surfactant containing fluorine (for example, US Pat.
0-80849) is particularly preferable.

The photographic light-sensitive material of the present invention may contain an amine or quaternary onium salt compound as described in Japanese Patent Application No. 61-94044 for the purpose of promoting development or nucleation.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethylmethacrylate in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of preventing adhesion.

The light-sensitive material used in the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, use of a polymer having a monomer component of alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, or the like. You can

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Mention may be made of polymers or copolymers having repeating units of acid monomers such as phthalic acid. Regarding these compounds, Japanese Patent Application Nos. 60-66179 and 60-68873.
Nos. 60-163856 and 60-195655 can be referred to. Of these compounds, ascorbic acid is particularly preferable as the low molecular weight compound, and an acid monomer such as acrylic acid is used as the high molecular weight compound and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene is used. It is a water dispersible latex of the copolymer.

As the binder or protective colloid used for the light-sensitive material,
Although it is advantageous to use gelatin, hydrophilic synthetic polymers and the like can also be used. As the gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin and the like can also be used. Specifically, research
RESEARCH DISCLOSURE No. 176
Volume 17643 (December 1978), Section IX.

The light-sensitive material used in the present invention may be provided with a hydrophilic colloid layer such as a surface protective layer, an intermediate layer, a filter layer and an anti-halation layer in addition to the silver halide emulsion layer.

U.S. Pat.No. 2,992,101 as a matting agent for the protective layer,
Homopolymers of polymethylmethacrylate described in U.S. Pat. Nos. 2,701,245, 4,142,894, and 4,396,706, copolymers of methylmethacrylate and methacrylic acid, and fine particles (for example, 2 to 5 μm) such as starch and silica can be used. Further, the above-mentioned surfactant may be used in combination.

Further, in the surface protective layer, as a slip agent, U.S. Pat.
No. 4,047,958 silicone compounds, Japanese Patent Publication Sho 56
In addition to the colloidal silica described in No. 23139, paraffin wax, higher fatty acid ester, den powder.

Further, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer.

In order to obtain super-high contrast and high-sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, conventional infectious phenomenon liquids and US Pat.
It is not necessary to use the highly alkaline developing solution close to pH 13 described in 2,419,975, and a stable developing solution can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ion as a preservative in an amount of 0.15 mol / or more and has a pH of 10.5 to
With a developer having a pH of 12.3, particularly pH 11.0 to 12.0, a sufficiently high-contrast negative image can be obtained.

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5
-Dimethylhydroquinone, etc., but hydroquinone is particularly preferable.

Examples of the developing agent for 1-phenyl-2-pyrazolidone or its derivative used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,
4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4
-Dimethyl-3-pyrazolidone, 1-p-tolyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). glycine,
2-Methyl-p-aminophenol, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

The developing agent is preferably used usually in an amount of 0.05 mol / -0.8 mol /. Also with dihydroxybenzenes 1
When using a combination with -phenyl-3-pyrazolidones or p-amino-phenols, 0.05 mol / both of them are used.
It is preferable to use -0.5 mol / l and the latter in an amount of 0.06 mol / l or less.

As a preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite and the like. The amount of sulfite is preferably 0.3 mol / or more, more preferably 0.4 mol / or more. The upper limit is preferably 2.5 mol / particularly 1.2.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
It contains pH adjusting agents and buffers such as sodium triphosphate, potassium triphosphate, sodium silicate and potassium silicate.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve Organic solvents such as hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-mercapto compounds such as sodium salt of sulfonic acid, indazole compounds such as 5-nitroindazole, An antifoggant such as 5-methylbenztriazole or a benztriazole compound, or a black pepper inhibitor: may be contained, and if necessary, a toning agent, a surfactant, a defoaming agent, a water softener. , Hardener, JP-A-56-106244 The amino compounds listed above may be included.

In the developer used in the present invention, a compound described in Japanese Patent Application No. 56-24347 as a silver stain inhibitor, a compound described in Japanese Patent Application No. 61-56629 as a development unevenness inhibitor, and a Japanese Patent Application as a dissolution aid. The compounds described in JP-A-60-109743 can be used.

In the developer used in the present invention, Japanese Patent Application No.
Boric acid described in -28708, saccharides described in JP-A-60-93433 (such as Sutcalose), oximes (such as acetoxime), phenols (such as 5-sulfosalicylic acid), and tertiary phosphate (such as salt). Sodium salt, potassium salt) and the like are used, and boric acid is preferably used.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or salts thereof), if necessary, in addition to the fixing agent,
It preferably has a pH of 3.8 or higher, more preferably 4.0 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed, and is generally about 0.1 to about 5 mol /.

The water-soluble aluminum salt, which mainly acts as a hardening agent in the fixing solution, is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. These compounds are the fixer 1
Amounts of 0.005 mol or more are effective, and 0.01 mol / -0.03 mol / is particularly effective.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate,
Ammonium potassium tartrate, etc.

Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like.

The fixer may further contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, boric acid), if desired.
A pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Here, the pH buffer is 10 to 40 g /
, And more preferably about 18 to 25 g / amount.

The fixing temperature and time are the same as in the case of development.
10 seconds to 1 minute at about 50 ° C is preferred.

In addition, anti-mold agents (for example, compounds described in Horiguchi's "Chemistry of antibacterial and antibacterial", Japanese Patent Application No. 60-253807), washing accelerators (sulfites, etc.), chelating agents, etc. May be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out to almost completely remove the silver salt dissolved by fixing, and it is carried out at about 20 ° C to about 50 ° C for 10 seconds to
3 minutes is preferred. Drying is performed at about 40 ℃ ~ 100 ℃,
The drying time can be appropriately changed depending on the ambient conditions, but it is usually about 5 seconds to 3 minutes and 30 seconds.

U.S. Pat. No. 3025 for a roller transport type automatic processor
No. 779, No. 3545971, etc., and is referred to simply as a roller transport type processor in the present specification. The roller-conveying processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four fixing steps. . Here, in the water washing step, a water-saving treatment can be performed by using a two- or three-stage countercurrent water washing method.

The developer used in the present invention is preferably stored in a packaging material having a low oxygen permeability as described in Japanese Patent Application No. 59-196,200. The developing solution used in the present invention is disclosed in Japanese Patent Application No. 60-232,47.
The replenishment system described in No. 1 can be preferably used.

Since the silver halide photographic light-sensitive material of the present invention gives a high Dmax, when it is subjected to a reduction treatment after image formation, it retains a high density even if the halftone dot area is reduced.

There is no particular limitation regarding the reducing liquid used in the present invention,
For example, Mies, “The Theory of the Photographic P
"Rocess" pp. 738-744 (1954, Macmillan), Tetsuo Yano "Photo Processing: Theory and Practice" pp. 166-169 (1978)
, Kyoritsu Shuppan) and Japanese Patent Laid-Open No. 50-27543.
52-68429, 55-17123, 55-79444, 57
Those described in -10140, 57-1442639, Japanese Patent Application No. 59-182456 and the like can be used. That is, as an oxidant,
Permanganate, persulfate, ferric salt, cupric salt, cerium salt, red blood salt, dichromate, etc., alone or in combination, and further inorganic acids such as sulfuric acid as necessary, A reducing solution containing alcohols, an oxidizing agent such as red blood salt or ferric ethylenediaminetetraacetic acid salt, and a silver halide solvent such as thiosulfate salt, rhodan salt, thiourea or their derivatives, and if necessary. Accordingly, a reducing liquid containing an inorganic acid such as sulfuric acid is used.

Typical examples of the reducer used in the present invention are so-called Farmer reducer, ferric ethylenediaminetetraacetic acid salt, potassium permanganate, ammonium persulfate reducer (Kodak R-5), and cerium cerium. Salt-reducing liquid may be used.

The conditions for reducing treatment are generally 10 ° C to 40 ° C, especially 15 ° C to 30 ° C.
It is preferable that the heating can be completed within a time of several seconds to several tens of minutes, especially several minutes. By using the plate-making photosensitive material of the present invention, a sufficiently wide reduction range can be obtained within the range of these conditions.

The reducer acts on the silver image formed in the emulsion layer through the non-photosensitive top layer containing the compound of the invention.

Specifically, there are various methods. For example, the photosensitive material for plate making is dipped in a reducing liquid to stir the liquid, or the reducing liquid is applied to the surface of the photosensitive material for plate making with a brush or a roller. You can use methods such as

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 Emulsions [A], [B] and [C] were prepared as shown below.

[Emulsion A) An aqueous silver nitrate solution and an aqueous potassium iodide / potassium bromide solution were simultaneously added to an aqueous gelatin solution kept at 50 ° C. in the presence of 4 × 10 ⁻⁷ mol of iridium hexachloride and ammonia per mol of silver for 60 minutes. By keeping the pAg at 7.8 during that period, the average grain size is 0.3 μm and the average silver iodide content is 1 mol%.
A cubic monodisperse emulsion of was prepared.

[Emulsion B] In the same manner as in Emulsion A, the amounts of potassium iodide and ammonia were adjusted to prepare a cubic monodisperse emulsion having an average grain size of 0.22 μm and an average silver iodide content of 0.1 mol%. Both emulsions A and B were desalted by the flocculation method.

[Emulsion C] Similar to Emulsion B, after grain formation and desalting, sulfur sensitization was performed with hypo to prepare a cubic monodisperse sulfur sensitized emulsion having an average grain size of 0.19 μm and an average silver iodide content of 0.1 mol%. .

In these silver iodobromide emulsions, sodium salt of 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine was used as a sensitizing dye, and 4-hydroxy- was added as a stabilizer. After adding 6-methyl-1,3,3a, 7-tetrazaindene, ascorbic acid, a dispersion of polyethyl acrylate, 1,3-divinylsulfonyl-2-propanol, emulsions A, B and A, C were added. After mixing so that the weight ratio of silver halide is as shown in Table 1, and further converting the compound I-12 of the general formula (I) of the present invention as shown in Table 1, silver was formed on a polyethylene terephthalate film. The application was performed so that the amount became 3.4 g / m ² . Each sample was exposed and developed to measure photographic characteristics.

Here, a dispersion coefficient (standard deviation / average grain size × 100) representing the degree of size distribution of emulsions A, B, and C, and
The following table shows the sensitivity increase of the coating size samples 1, 3, and 5 of A, B, and C due to the gold intensification. The gold assisting force was tested by the method described in the specification.

The reduction ability was evaluated as follows. A commercially available negative contact gray screen (150 lines / inch) was brought into close contact with the sample, a step wedge with a step of 0.1 was weighed and exposed with white tungsten, and then each sample was developed at 38 ° C for 30 seconds, usually Was fixed, washed with water and dried to form a halftone dot image.

The obtained halftone dot strips were cerium-based reducing liquid (20
C.) and washed with water.

Reducer The change in the halftone dot area of the halftone dot strips thus obtained and the density per one halftone dot were measured with a microdensitometer. The halftone dot area was calculated when the individual concentration was 2.5, and the difference between the two was calculated as the reduction width value.

As is clear from Table 1, Samples 9 to 12 of the present invention have high sensitivity, gradation and Dmax, good black spots, and remarkably improved reducing ability.

Here, the relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5 at development at 38 ° C. for 30 seconds, and the value of Sample 1 is 100.

Black spots are evaluated on a scale of 5 by microscope observation.
"5" represents the best quality and "1" represents the worst quality.
"5" or "4" is practical, "3" is poor, but it is practically practical and "2" or "1" is not practical. "4"
The one between "3" and "3" was evaluated as "3.5". The evaluation of black spots is the result of development at 38 ° C. for 40 seconds.

The developer having the following formulation was used.

Developer formulation Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 9.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Disodium ethylenediaminetetraacetate 1.0 g 3.Diethyl-amino- 1-Propanol 15.0g 5 ・ Methylbenzotriazole 0.5g Sodium bromide 3.0g Add water and adjust to pH = 1.11.60.

(Example 2) 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) was added to silver iodobromide emulsions A, B and C prepared in Example 1 as a sensitizing dye. Oxacarbocyanine sodium salt, 4-hydroxy-6-methyl- as stabilizer
1,3,3a, 7-Tetrazaindene, polyethyl acrylate dispersion, aqueous latex represented by the following structural formula
After the addition of (a), 1,3-divinylsulfonyl-2-propanol, the emulsions A, B and A, C were mixed so that the weight ratio of silver halide was as shown in Table 2. After the compound I-28 of the formula (I) was added as shown in Table 2, 3.2 g of silver was added on the polyethylene terephthalate film.
The coating was performed as it became / m ² . Example 1)
In the same manner as described above, exposure and development were performed and photographic characteristics were measured. The results are shown in Table 2.

Washable latex (a) As is clear from Table 2, the samples 2 to 5 of the present invention have a high feeling without causing deterioration of black spots, as compared with the comparative samples 13 to 20.
High γ and high Dmax can be obtained.

Example 3 Large size emulsion D, small size emulsions E, F, G, H, I, J and K were prepared by the following method.

[Emulsion D] An aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added to an aqueous gelatin solution kept at 50 ° C in the presence of a silver halide solvent (1.8-bihydroxy-3.6-dithiaoctane) for 40 minutes, during which time. By maintaining the pAg at 7.8, a cubic monodisperse emulsion having an average grain size of 0.28 μm and an average silver iodide content of 2 mol% was prepared. This emulsion was desalted by the flocculation method.

[Emulsion E] Potassium iodide, 1,8 was prepared in the same manner as Emulsion D.
The amount of -dihydroxy-3,6-dithiaoctane was adjusted to prepare a cubic monodisperse emulsion having an average grain size of 0.23 µ and an average silver iodide content of 1 mol%, and desalting was carried out by the flocculation method.

[Emulsion F] In the same manner as in Emulsion E, 4 × 10 1 per mol of silver
Grain formation was carried out in the presence of ^-7 mol of iridium hexachloride to prepare a cubic monodisperse emulsion having an average grain size of 0.23 µ and an average silver iodide content of 1 mol% and desalted by the flocculation method. .

[Emulsion G] In the same manner as for Emulsion E, 1.8-dihydroxy-
3.6- Adjust the amount of dithiaoctane, 0.20 average particle size
A cubic monodisperse emulsion containing .mu.m and 1 mol% of average silver iodide was prepared and desalted by the flocculation method. Then, it was subjected to sulfur sensitization with hypo, and a 1% KI aqueous solution corresponding to 0.1 mol% was added, followed by 10 minutes of conversion.

[Emulsion H] To a gelatin aqueous solution kept at 70 ° C, an aqueous solution of silver sulfate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added in 80 minutes in the absence of a silver halide solvent, and the pAg between them was 7.6.
A cubic monodisperse emulsion having an average silver iodide content of 1 mol% was prepared by maintaining the above temperature, and desalting was carried out by the flocculation method. After that, it was sensitized with sulfur by hypo.

[Emulsion I] An aqueous solution of nitrate and a mixed aqueous solution of sodium chloride and potassium bromide containing 2.7 × 10 ⁻⁷ mol of rhodium ammonia chloride per 1 mol of silver were simultaneously and uniformly mixed in a gelatin aqueous solution of pH = 4.0 kept at 40 ° C. 30 at speed
By adding for 1 minute, a silver chlorobromide monodisperse emulsion having an average grain size of 0.23μ was prepared. (Br composition 30 mol%) This emulsion is desalted by the flocculation method,
After that, it was sensitized with sulfur by hypo.

[Emulsion J] An aqueous solution of silver nitrate, an aqueous solution of potassium iodide and an aqueous solution of potassium bromide were simultaneously added in the same manner as in Emulsion F, and the pAg was maintained at 8.3 during that period to obtain an average grain size of 0.2 μ and an average silver iodide. An octahedral monodisperse emulsion having a content of 1 mol% was prepared, desalted, and then subjected to sulfur sensitization with hypo.

[Emulsion K]

In the same manner as in Emulsion E, the amount of 1,8-dihydroxy-3,6-dithiaoctane was adjusted to prepare a cubic monodisperse emulsion having an average grain size of 0.25 μm and an average silver iodide content of 1 mol%, and the flocculation Desalting was carried out by the method. After that, it was sensitized with sulfur by hypo.

After the same additives as in Example 1 were added to these emulsions, the emulsions A and D, E, F, H, I, J, and K of Example 1 were used as shown in Table 3 in terms of silver halide weight ratio. The mixture is mixed in a ratio such that the compound I-12 of the general formula (I) of the present invention is added to silver 1.
After adding 5 × 10 ⁻³ mol per mol, coating was performed on the polyethylene terephthalate film at a silver amount of 3.0 g / m ² . Each sample was tested in the same manner as in Example 1 and the results are shown in Table 3. As is clear from Table 3, the samples 35 to 39 and 41 to 45 of the present invention have better black spots, higher feeling, higher Dmax and better reducing ability than the comparative samples. Emulsion K (Sample 3) with increased sensitivity and Dmax with sulfur sensitized emulsion alone
In 3), the black spots are significantly worse. The iridium-sensitized emulsion does not reach the sulfur sensitization but shows the same effect. (Samples 35, 41) (Example 4) In Example 1, instead of the hydrazine of I-12, I-
Similar results were obtained when using 36 adsorbed hydrazine I-36 or I-19 having no ballast group.

Example 5 Emulsion C of Example 1 was set to a temperature of 50 ° C. in the latter period of sulfur sensitization, and the sensitizing dye 5,5′-dichloro-9-ethyl-3,3′-bis (3 -Sulfopropyl) oxacarbocyanine was added to prepare Emulsion (I). When this emulsion was combined with Emulsion A and the same test as in Example 1 was carried out, good results of black spots, Dmax and reduction were obtained.

(Example 6) In Emulsion C used in Example 1, good results were obtained even when the sulfur sensitizer was replaced with triethylthiourea or 5-benzylidene-3-ethylrhoddanine instead of hypo.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein said emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative. Monodisperse silver halide containing two kinds of monodisperse silver halide grains having different mean grain sizes, each of the two kinds of monodisperse silver halide grains having an average grain size of 0.1 to 0.4 μm, and having a small size. A silver halide photographic light-sensitive material characterized in that grains are chemically sensitized.