JPH03167545A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material high in sensitivity and capable of forming an image small in black spots, high in contrast and blackened density by incorporating iron in an amount of >=60% of the total iron content of all the silver halide grains in all the silver halide grains of a silver halide emulsion layer in the range from the surface of each grain to the depth corresponding to a volume of 50% of the total grain volume. CONSTITUTION:The emulsion layer is composed of a silver halide emulsion containing an iron salt in an amount of at least 1X10<-7> mole per mole of silver and the >=60% of the total iron content is contained in all the silver halide grains in the range from the surface of each grain to the depth corresponding to the 50% of the total grain volume. The emulsion layer or another hydrophilic colloidal layer contains a hydrazine derivative represented by formula I in which R1 is an aliphatic, aromatic, or a heterocyclic group; R2 is H, alkyl, or the like; G1 is carbonyl, sulfonyl, or the like; and each of A1 and A2 is both H or one is H and the other is alkylsulfonyl or the or the like, thus permitting sensitivity to be enhanced, black spots to be reduced, and contrast and blackened density to be enhanced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applied to silver halide photographic materials (particularly negative materials) that are used in the field of photoengraving and are capable of rapidly forming ultra-high contrast images using a highly stable processing solution. (type).

(Prior Art) In order to improve the reproduction of continuous tone images or line images using halftone images in the field of photoengraving,
There is a need for an image format or system that exhibits photographic characteristics of ultra-high contrast (especially gamma greater than 1O).

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is kept extremely low (usually 0). .l mol/l or less). Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

A method for obtaining high contrast photographic properties using a stable developer is described in U.S. Pat. No. 4,224. No. 401, No. 4,168,977, No. 4,166,742
No. 4,311,781, No. 4,272,60
No. 6, No. 4, 221. No. 857, No. 4, 2
There is a method using a hydrazine derivative described in No. 43,739, No. 4,269,929, etc. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and since it is allowed to add a highly sensitive sulfite to the developer, the stability against air oxidation of the developer is better than that of the lithium developer. A dramatic improvement in comparison.

However, in general, in silver halide photographic light-sensitive materials, the image blackening density obtained per unit amount of developed silver increases as the size of the silver halide grains decreases, but the sensitivity of silver halide generally increases due to the size of the silver halide grains. The larger the value, the higher the value. Therefore, in order to obtain a light-sensitive material that provides high sensitivity and high blackening density, it is necessary to contain a larger amount of 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 time to fix, wash, and dry during the development process, impairing rapid processing. Furthermore, since silver is expensive and has limited production and reserves, there is a need to produce photosensitive materials using as little silver as possible.

For this reason, research has been carried out for many years on silver halide photosensitive materials that have high image density and high sensitivity while using less silver.

On the other hand, with this new high-contrast negative image system, if you try to increase the maximum density by changing the amount of hydrazine derivative added, it is possible to increase the maximum density and achieve a remarkable high-sensitivity contrast.
per), which is a problem in the photolithography process.

A black spot is a black spot made of minute developed silver that occurs in an unexposed, non-image area.

Black spots occur frequently due to a decrease in sulfite ions, which are generally used as a preservative in a developing solution, and an increase in pH value, significantly reducing the commercial value of the photolithographic material. Therefore, although great efforts are being made to improve these black spots, the improvement of black spots is often due to sensitivity and gamma (γ).
), there has been a strong desire for a system that maintains high contrast and improves black spots. As one such method, Japanese Patent Laid-Open No. 61-77274 describes particle size 0.
．． A silver halide photographic material containing two types of monodispersed emulsions and a hydrazine derivative with a particle size of 5 μm or less is disclosed.

Furthermore, in the field of photolithography, in order to deal with the versatility and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment.

Particularly in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction.

On the other hand, enlarging (stretching) or reducing (shrinking) net photographs is widely used in the making of catalogs and large posters.
In plate making that uses enlarged halftone dots, the number of lines becomes coarser, resulting in blurred dots. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain photographic sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and original reproducibility, a system with further improved original reproducibility is desired in order to cope with the diversity of printed matter in recent years.

Examples of using silver halide grains characterized by the distribution of Group 8 metals in the grains in combination with hydrazine derivatives are described in JP-A-63-296031 for rhodium and in Japanese Patent Application No. 1-128385 for iridium. There is no example for iron.

Further, examples of silver halide grains having a characteristic iron distribution are disclosed in JP-A-62-260137 and JP-A-63-191145, but there are no examples of their use in combination with hydrazine derivatives.

Examples of systems using hydrazine containing a redox compound that releases a development inhibitor upon oxidation are disclosed in JP-A-61-213847 and JP-A-64-72140.

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

A second object of the present invention is to provide a silver halide photographic material with excellent line image quality and extremely high sensitivity and ultra-high contrast with γ exceeding 10.

(Means for Solving the Problems) The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the emulsion layer has at least one silver halide emulsion layer per mole of silver. ×10-
% silver halide grains of the silver halide emulsion contain 60% of the iron content in the total grains from the grain surface to a portion corresponding to 50% of the total grain volume. Achieved by a silver halide photographic light-sensitive material, which is characterized in that it is grains containing iron in an amount of % or more, and contains a hydrazine derivative represented by the following general formula (I) in the emulsion layer or other hydrophilic colloid layer. We were able to.

General formula (I) R. -N-N-G, -R2 [AIAI] In the formula, R1 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R2 is a hydrogen atom, an alkyl group, an aryl group,
A. , At both represent a hydrogen atom, one hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

A second object of the present invention is to provide the negative-working silver halide photographic light-sensitive material characterized in that the emulsion layer or other hydrophilic colloid layer contains a redox compound that releases a development inhibitor upon oxidation. It got even better.

The silver halide grains of the present invention will be explained in detail below.

The present invention is characterized by the distribution of iron in the silver halide grains. That is, 60% or more, preferably 80% or more of the total iron content in all particles is present in the area from the particle surface to a portion corresponding to 50% of the particle volume within the total volume of the particles.

That is, it is characterized by the presence of a larger amount of iron in a portion closer to the particle surface than in the interior of the particle.

In particular, it is preferable that 60% or more of the total iron content in all particles is present in a portion corresponding to 30% of the total particle volume from the particle surface. In particular, it is preferable that the particles be localized on the surface of the particles.

Regarding the iron content, the silver halide grains of the present invention may have a multiple structure with a double structure or more, or a structure in which the iron content changes continuously, but a double structure is preferable.

In the case of a double structure, the iron content in the inner core, which is the layer closer to the center of the particle, is lower than that in the outer shell, which is the layer closer to the particle surface, and the iron content is localized in the outer shell. Preferably.

In addition, in the case of a multilayer structure, it is preferable that the layer closest to the particle surface has the highest iron content, and in the case of a structure that changes continuously, the iron content of the layer closest to the particle surface is 20% of the total particle volume. Preferably, there is a portion of the volume with the highest iron content.

The average particle size of the host crystal in the present invention is 0.7μ
m or less is preferable, more preferably 0.2 μm to 0.5
It is μm. The particle size distribution is preferably monodisperse.

Monodisperse grains herein mean a silver halide emulsion having a grain size distribution with a coefficient of variation defined below of 20% or less, particularly preferably 15% or less.

When the silver halide has a double structure, the average grain size of the silver halide constituting the core with low iron content of the present invention is
0.03-0.45μ, preferably 0.1-0.35μ
Preferably, the particles have a narrow distribution, and the deviation of the particle size from the average particle size is within ±40%, preferably less than ±20%.

The final average particle diameter after the outer shell portion with a high iron content of the present invention is laminated on the core portion is preferably 0.5μ or less, more preferably 0.2μ to 0.4μ.

The distribution of iron in silver halide is determined by the concentration of (NH4L
It can be determined by sequentially etching the StC)+ solution several times, quantifying the amounts of silver and iron in each solution, and converting them into particle volumes. Quantification can be performed by atomic absorption method or the like.

When the silver halide has a double structure, the iron content in the inner core is 0 to 5 x 10-' mol/mole silver, and the iron content in the outer shell is 1. OXIO-'~5. Preferably it is OX10-4 mole/mole silver.

The structure of the core with low iron content and the shell with high iron content has a volume ratio of 1+
Can be arbitrarily selected between 100 and 100:1, but 1:
Preferably, the ratio is in the range of 10 to 10:1.

In order to incorporate iron atoms into the grains, it is desirable to add iron salts before completing physical ripening in the silver halide emulsion manufacturing process, especially when forming the grains.

The iron salt used here is a water-soluble iron salt or iron complex salt, for example, iron sulfate (II) Fe S 0,5 8gO
; iron(III) chloride FeC1. ; Hexacyanoiron (II
) acid potassium K+F e (CN)s' 3 H20
; Potassium hexacyanoferrate (III) K h F
e(CN)s, etc.

The amount of these water-soluble iron salts added is 1.5 g/mol of silver halide. OX10-' mole or more, preferably 1×
It ranges from 10-' to 5X10-' moles.

In order to make the water-soluble iron salt present during the formation of silver halide grains, it is preferable to add it to the water-soluble silver salt or halide solution when simultaneously mixing the water-soluble silver salt and the water-soluble halide solution. . Alternatively, when silver salt and halide solutions are mixed simultaneously, silver halide grains may be prepared by a method of simultaneous mixing of three solutions as a third solution. Further, a required amount of an aqueous solution of iron salt may be introduced into the reaction vessel during or immediately after particle formation, or during or at the end of physical ripening.

The total amount of silver coated is preferably 1 g/n to 8 g/d.

The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape.
gu far) crystals, or a composite form of these crystal forms.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc., but 70 mol% or more, especially 90 mol% or more of silver bromine. Silver halides are preferred.

The content of silver iodide is 10 mol% or less, especially 0. It is preferably 1 to 5 mol%.

The silver halide grains used in the present invention are P. Glaf
Chimie et Physique by kids
Photography (Paul Monte1)
Publishing, 1967), G. F. Pho by Duffin
tographic Emulsion Che+ni
stry (The Focal Press, l96
6 years), V. L. Written by Zelikman et al.
making and coating photogr
aphic Emulsion (The Focal
Press, 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed using any of the one-sided mixing method, simultaneous mixing method, and a combination thereof. good.

It is also possible to use a method in which particles are formed under an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, in order to make the particle size uniform, British patent 1,
No. 535, 016, Special Publication No. 4 8-3 6 8
90, No. 52-16364,
A method of changing the addition rate of silver nitrate or alkali halide depending on the particle growth rate, and British Patent No. 4,242,44
It is preferable to use a method of changing the concentration of an aqueous solution as described in No. 5, JP-A No. 55-158124, to grow rapidly within a range that does not exceed the critical saturation level.

As the silver halide solvent used in the present invention, (a) organic thioethers described in U.S. Pat. No. 3,271,157, U.S. Pat. , Japanese Patent Publication No. 53-82408, 5
(b) Thiourea derivatives described in JP-A-53-144319
(Silver halide solvent having Cl oxygen or carbonyl group, described in JP-A-54-100717 (d)
Examples include imidazoles (e) sulfites (f) thiocyanates. Among these, thioethers are particularly preferred.

Specific compounds are shown below.

CH. -NHCOCH2CH2COH C H t S C H 2 C H 2 S C
t H sf{O-(CH*)*-S-(CH!)t
-S-(C}It)t-OH The silver halide suitable for use in the present invention is a silver halide iodide in which the silver iodide content on the grain surface is larger than the silver iodide content on the grain average. When an emulsion containing such silver haloiodide is used, photographic characteristics with higher sensitivity and higher gamma can be obtained.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. You can.

The emulsion of the present invention may not be chemically sensitized, but may be chemically sensitized. As a chemical sensitization method, known methods such as sulfur sensitization, reduction sensitization, gold sensitization, etc. can be used, and these methods are used alone or in combination. A preferred chemical sensitization method is sulfur sensitization.

As the sulfur increaser, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, No. 278.947, No. 2,410,689, No. 2,
No. 728,668, No. 3,501.313, No. 3,
No. 656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds,
The pAg during chemical sensitization is preferably 8.3 or less, more preferably in the range of 7.3 to 8.0.

Furthermore, Moisar, Klein Gelatine
．． Proc. Symp. 2nd, 301-309
(1970) et al. also give good results using a combination of polyvinylpyrrolidone and thiosulfate.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. A specific example is U.S. Patent No. 2,448,06
No. 0, British Patent No. 6l8,061, etc.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include U.S. Pat. No. 2,487,850,
No. 2,518,698, No. 2,983,609, 2,9
No. 83.610 and No. 2,694,637.

The silver halide emulsion in the light-sensitive material used in the present invention is
One type may be used alone, or two or more types (for example, those with different average particle sizes, those with different halogen compositions, those with different crystal habits, and those with different chemical sensitization conditions) may be used in combination.

In the present invention, the silver halide emulsion layer is
It is preferable to include two types of monodisperse emulsions with different average grain sizes as disclosed in No. 3734 and No. 62-90646, from the viewpoint of increasing the maximum density (Dmax), and The particles are preferably chemically sensitized, and the most preferred chemical sensitization method is sulfur sensitization. The large size monodisperse emulsion does not need to be chemically sensitized, but it may be chemically sensitized. Since large-sized monodisperse particles generally tend to generate black spots, it is particularly preferable that chemical sensitization is not performed, or when chemical sensitization is applied, the chemical sensitization is applied shallowly to the extent that black spots do not occur. Here, "shallow application" means that chemical sensitization is performed by shortening the time, lowering the temperature, or suppressing the amount of chemical sensitizer added compared to chemical sensitization of small-sized particles. There is no particular limit to the sensitivity difference between large-sized monodispersed emulsions and small-sized monodispersed emulsions, but △j7
ogE is 0.1-l. O, more preferably <0.2
~0.7, and the higher the value is, the more preferable it is for large-sized monodispersed emulsions.

Here, the sensitivity of each emulsion is obtained when it is coated on a support containing a hydrazine derivative and processed using a developer with a pH of 10.5 to 12.3 containing 01.5 mol/l or more of sulfite ions. It is something.

More specifically, the evaluation method described in Example 1 was followed.

The average grain size of the small monodisperse grains is 90% or less, preferably 80% or less, of the average grain size of the large monodisperse silver halide grains.

The average grain size of the silver halide emulsion grains is preferably 0.02μ to 1.0μ. More preferably 0.1μ to 0
．． It is preferable that the average particle size of the large-sized and small-sized monodisperse particles is 5μ and included within this range.

In the present invention, when two or more emulsions of different sizes are used, the coating silver amount of the small-sized monodisperse emulsion is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total coating silver amount. be.

In the present invention, monodispersed emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into separate layers.

When introduced in separate layers, it is preferred that the large emulsion be in the upper layer and the small emulsion in the lower layer.

The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by I).

General formula (I) In the formula, R1 represents an aliphatic group, an aromatic group, or a heterocycle, and R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarponyl group. group, O 11 or hydrazino group, G1 is 101 groups, 1 group,
Represents a thiocarbonyl group or iminomethylene group, A1
, A2 both represent a hydrogen atom, one a hydrogen atom and the other a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula CI), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

In general formula (I), R. The aromatic group represented by is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be fused with an aryl group.

R. Preferred is an aryl group, particularly preferred is one containing a benzene ring.

The aliphatic group or aromatic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide R2 Preferred substituents are alkyl groups (preferably carbon atoms
~20 carbon atoms), aralkyl groups (preferably 7~20 carbon atoms),
30), alkoxy group (preferably 1 to 2 carbon atoms)
0), substituted amino groups (preferably 1 to 20 carbon atoms), substituted amino groups (preferably 1-20 carbon atoms)
(an amino group substituted with an alkyl group), an acylamino group (preferably one having 2 to 30 carbon atoms), a sulfonamide group (preferably one having 1 to 30 carbon atoms), a ureido group (preferably one having 1 carbon number) 30), a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms), and the like.

In general formula (I), R. The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring).

When O 11 G, -C is one group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxyprobyl group,
3-methanesulfonamidoprobyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidopropyl group, etc.), enyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

R2 may be substituted, and examples of the substituent include R. The substituents listed for are applicable.

O 11 G in general formula (I) is most preferably -C group.

Also, R2 is G. - Splitting the R2 part from the remaining molecule,
-G, -R. It may be one that causes a cyclization reaction to produce a cyclic structure containing atoms of the moiety, and examples thereof include those described in JP-A-6329751.

A. , A2 is most preferably a hydrogen atom.

R1 or R2 in the general formula (I) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group,
It can be selected from phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, etc. Examples of the polymer include those described in JP-A-1-100530.

R1 or R2 in general formula (I) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
No. 200,231, No. 59-201,045, No. 59
-201.046, 59-201.047, 5
9-201,048, 59-201,049, JP-A-61-170,733, JP-A-61270,744, JP-A-62-9-4-8, JP-A-62-67,508
No. 62-67,501 and No. 62-67,510.

Specific examples of the compound represented by general formula (I) are shown below.

However, the present invention is not limited to the following compounds.

I-1 I-4 I-6 0 ■ 8 ■ 10 I-1 1 0 0 ■-1 2 I-1 3 A1 4 I-1 5 0 H ■ l6 QM I-18 ■-2 0 H ■ 23 ■ 24 ■ 25 ■-2 6 S}l In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCH DISCLOSURE
Item23516 (November 1983 issue, P.3
46) and the documents cited therein, as well as U.S. Pat.
No. 080,207, No. 4,269,929, No. 4,2
No. 76,364, No. 4,278,748, No. 4,38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, No. 4,478, 928, British Patent No. 2, Oil, 391B, JP-A-60-179734,
No. 62-270,948, No. 63-29.751,
61-170,733, 61-270,744, 62-948, EP217,310, or U
S 4,686,167, JP-A-62-178,24
No. 6, No. 63-32,538, No. 63-104,04
No. 7, No. 63-121, No. 838, No. 63-129, 3
No. 37, No. 63-223, 744, No. 63-234,
No. 244, No. 63-234, 245, No. 63-234
, No. 246, No. 63-294, 552, No. 63-30
6.438, JP-A No. 1-100,530, JP-A No. 1-1
No. 05,941, No. 1-105,943, JP-A-64
-lO, No. 233, Japanese Patent Application Publication No. 1-90,439, Japanese Patent Application No. 105,682/1982, No. 114,118/1983,
No. 63-110,051, No. 63-114,119, No. 63-116,239, No. 63-147,339
No. 63-179,760, No. 63-229.16
No. 3, Patent Application No. 1-18,377, No. 1-18,378
No. 1-18,379, No. 1-15,755, No. 1-16,814, No. 1-40,792, No. 1-4
No. 2,615, No. 1-42.616, No. 1-123.
693 and 1-126,284 can be used.

The amount of the hydrazine derivative added in the present invention is from 1 x 10-' mol to 5 x 10-' mol per mol of silver halide.
-2 mol is preferable, and a particularly preferable addition amount is in the range of 1×10-' mol to 2×10-'' mol.

The redox compound of the present invention that can release a development inhibitor when oxidized will be explained.

Particularly preferred redox compounds of the present invention are compounds represented by the following general formula (n).

General formula (It) In the formula, R represents an aliphatic group or an aromatic group, and O 11 G1 is -C group, -S02 group, -S〇 group, O 11 -P group, or iminomethylene R2R2 represents an alkoxy group, an aryloxy group, or an amino group.

B. , B2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group,
or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Time represents a divalent linking group, and t represents 0 or 1. PUG
represents a development inhibitor.

The compound of general formula (II) will be explained in further detail.

In the general formula (n), the aliphatic group represented by R preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

In the general formula (n), the aromatic group represented by R1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with an aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, and an isoquinoline ring, among which those containing a benzene ring are preferred.

Particularly preferred as R is an aryl group.

The aryl group or unsaturated heterocyclic group of R may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, and a substituted amino group. , ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carponamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc. Preferred substituents include linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), aralkyl group (preferably (having 7 to 30 carbon atoms) alkoxy group (preferably 1 carbon number)
~30) substituted amino group (preferably 1 to 3 carbon atoms)
an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), Examples include those having a number of I to 40, and phosphoric acid amide groups (preferably those having a carbon number of 1 to 40).

O 11 G. of general formula (n) For closing, 101 is the most preferable;
A hydrogen atom is most preferable as A,, A2.

As the divalent linking group represented by Time, for example, U.S. Pat.
No. 135) etc., which release a photographically useful group (PUG) through an intramolecular ring-opening reaction of a p-nitrophenoxy derivative; US Pat.
-53,330) and U.S. Pat. No. 4,358,252, which release PUG by intramolecular ring closure reaction after ring opening; U.S. Pat.
No. 46,216, No. 4,483,919, JP-A-59
U.S. Patent No. 4,409,323, which releases PUG with the production of acid anhydride through the intramolecular ring-closing reaction of the carboxyl group of the succinic acid monoester or its analog described in US Patent No. 121,328, etc. , 4,421,845
No., Research Disclosure Magazine N[12 1,
228 (December 1981), U.S. Patent No. 4,41
6,977 (JP-A-57-135.944), JP-A-58-209,736, JP-A-58-209,738, etc. Generates quinomonomethane or its analogues and releases PUG by electron transfer via heavy bonds; US Pat.
6,640), JP-A No. 57-135,945, No. 5
7-188,035, 58-98,728, 58-209,737, etc., PUG is released from the γ-position of the enamine by electron transfer of the part having the enamine structure of the nitrogen-containing heterocycle. Item: Japanese Patent Application Publication No. 1987-56.8
No. 37, which releases PUG through an intramolecular ring-opening reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle; US Pat. No. 4
．． No. 146, 396 (Unexamined Japanese Patent Publication No. 1973 2-9 0
9 3 2), JP-A-59-93,442, JP-A-59-75475, etc., which release PUG with the production of aldehydes; JP-A-51-146,82
No. 8, No. 57-179,842, No. 59-104,6
PUG with decarbonization of the carboxyl group described in No. 41
-0-COOCR. R. - A substance having the structure of PUG and releasing PUG with decarboxylation and subsequent production of aldehydes; a substance releasing PUG with production of isocyanate as described in JP-A-60-7,429; Examples include those that release PUG through a coupling reaction with an oxidized product of a color developer described in US Pat. No. 4,438,193 and the like.

For specific examples of these divalent linking groups represented by Time, see JP-A No. 61-236,549 and Japanese Patent Application No. 63-Sho.
It is also described in detail in No. 98,803.

PUG represents a group having a development inhibiting effect as (Time-}+PUG or PUG.

The development inhibitor represented by PUG or (T im e+, P UG is a known development inhibitor that has a heteroatom and is bonded via a heteroatom. Mees (C.E.K.Mees)
and T.H. James
Author: “The Theory of Photographic Process”
ap-hic Processes) J 3rd edition, 196
6 Published by Macmillan, pp. 344~
It is described on page 346 etc.

The development inhibitor represented by PUG may be substituted. Examples of substituents include those listed as substituents for R', and these groups may be further substituted.

Preferred substituents include a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

Further, in the general formula (IF), R1 or 10 Time-
)-+PUG contains a ballast group commonly used in immobile photographic additives such as couplers and general formula (II
) may be incorporated with a group that promotes adsorption of the compound represented by () to silver halide.

The ballast group is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the general formula (n) from diffusing into other layers or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, It consists of a combination of one or more of an ether group, a thioether group, an amide group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1, 2.
4-triazoline-3-thione, l, 3. 4-
Oxazoline-2-thione, penzimidazoline-2-
cyclic thioamide group, linear thioamide group, aliphatic mercapto group, aromatic mercapto group, hetero- Cyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group that has a tautomeric relationship with this group, and specific examples of this group are those listed above. ), a group having a disulfide bond, penzotriazole, triazole, tetrazole, indazole, penzimidazole, imidazole, penzothiazole, thiazole, thiazoline, penzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, Examples include a 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur, and carbon such as azaindene, and a heterocyclic quaternary salt such as penzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those mentioned as the substituent for R1.

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

It-1 S [-3 q Not n-5 11-6 n-7 n-8 ■-1 1 ■ l2 q ■-1 4 ■-1 5 Now [[-17 ■-1 8 ■ l9 q H IF -20 I1-2 1 ■ 22 ■ 23 ■-2 4 0 NO, ■-2 5 ■-2 6 ■-2 7 0 0 ) . llU3Na ■-2 8 ■29 In addition to the above-mentioned redox compounds used in the present invention, for example, JP-A-61-213,847 and JP-A-61-213,847,
No. 2-260,153, patent application No. 1-102.393,
Those described in No. 1-102.394, No. 1-102,395, and No. 1-114,455 can be used.

Examples of the synthesis method of the redox compound used in the present invention include JP-A-61-213.847 and JP-A-62-260.15.
No. 3, U.S. Pat. No. 4,684. No. 604, Japanese Patent Application No. 63-98.803, U.S. Patent No. 3,379,52
No. 9, No. 3,620,746, No. 4,377,634
No. 4, 332, 878, JP-A-49-12
No. 9,536, No. 56-153.336, No. 56-1
53.342 etc.

The redox compound of the present invention is used in an amount of IXlO'' to 5X10-'' mol, more preferably 1 x 10-5 to 1 x 10-' mol, per mol of silver halide.

The redox compound of the present invention can be dissolved in a suitable water-miscible organic solvent, such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used as

In addition, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate can be dissolved using oils, auxiliary solvents such as ethyl acetate or cyclohexanone, and mechanically An emulsified dispersion can also be prepared and used.

Alternatively, by a method known as solid dispersion method,
The redox compound powder can also be dispersed in water using a pole mill, colloid mill, or ultrasonic wave.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinyl alcohol partial acetal, polyN-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylvirazole, etc. can.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products may also be used.

Sensitizing dyes (e.g., cyanine dyes, merocyanine dyes, etc.) described in JP-A No. 55-52050, pages 45 to 53, can be added to the light-sensitive material used in the present invention for the purpose of increasing sensitivity. .

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure+ (Re
Search Disclosure) 176 Vol. 17643 (published December 1978), page 23, Section J.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. Namely, azole agents such as penzothiazolium salts, nitroindazoles, chlorobenzimidazole agents, promobenziξ'dazoles, mercabutotetrazoles, mercaptothiazoles, mercabutobenzothiazoles, mercabutothiadiazoles, aminotriazole agents, penzothiazoles, nitrobenzotriazoles, etc.; mercaptovirimidine vX: mercaptotriazine; thioketo compounds, such as oxazolinthione; azaindenes, such as triaziindenes, tetraazaindene vR (particularly 4-hydroxy-substituted (1 , 3, 3a, 7) tetrazaindenes), pentaazaindenes, etc.; many known antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. and hardware can be added. Among these, preference is given to penzotriazole (e.g. 5-
methyl-benzotriazole) and nitroindazoles (eg, 5-ditroindazole). Furthermore, these compounds may be included in the treatment liquid. Furthermore, a compound that releases an inhibitor during development as described in JP-A No. 62-30243 may be included for the purpose of stabilizing or preventing black spots. The photographic material of the present invention may contain developing agents such as hydroquinone derivatives and phenidone derivatives for various purposes such as stabilizers and accelerators. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium acetate, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (1,3.5-triacryloyl-hexahydro) S-}riazine, l,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, etc.)
, etc. can be used alone or in combination.
The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
It may contain various surfactants for various purposes such as development acceleration, contrast enhancement, sensitization, etc. For example, sabonin (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbicne esters, Non-ionic compounds such as alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, etc. Surfactant; alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate ester, alkyl phosphate!, N-acyl-N-alkyl taurine, sulfosuccinate, Carboxy groups, such as sulfoalkylborioxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphate M, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phosphorus groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, idazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 58-9412. Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A No. 60-80849. The photographic light-sensitive material of the present invention contains hydroquinone derivatives (so-called DIR-
may contain hydroquinone). Specific examples thereof include U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620.746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Samurai Kaisho 49-1
29,536, JP 54-67.419, JP 56-153,336, JP 56-153,342
No., JP-A No. 59-278,853, JP-A No. 59-9043
Examples include compounds described in No. 5, No. 59-90436, and No. 59-138808. The photographic material of the present invention may contain a matting agent such as silica, magnesium oxide, or polymethyl methacrylate 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-insoluble or poorly soluble synthetic or polymer for the purpose of dimensional stability. For example, polymers containing alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. as monomers. It can be used. It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymer having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, see JP-A-61-223834 and JP-A-61-2.
No. 28437, No. 62-25745, and No. 62-5
The record in Specification No. 5642 can be referred to. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. This is a water-dispersible latex of cobolimer. The emulsions used in this invention are coated onto a suitable support such as glass, acetic acid, cellulose film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin coated paper, and the like. In order to obtain photographic characteristics of ultra-high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 as described in U.S. Pat. No. 2,419,975. There is no need to use a stable developer; instead, a stable developer can be used. That is, the silver halide photosensitive material of the present invention contains 0.15 mol/sulfite ion as a preservative.
1 or more, pH 0.5 to 12.3, especially pH 11.
A sufficiently high-contrast negative image can be obtained using a developing solution of 0 to 12.0. Although there are no particular restrictions on the developing agent used in the developer used in the present invention, it is preferable that it contains dihydroxybenzenes, since it is easy to obtain a good halftone score. - A combination of virazolidones or a combination of dihydroxybenzenes and P-aminophenols may be used. The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, promhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred. As the developing agent for 1-phenyl-3-virazolidone or its derivative used in the present invention, 1-phenyl-3-virazolidone, 1-phenyl-4,4-dimethyl-4-virazolidone, 1-phenyl-4-methyl-4-hydroxymethyl -3-virazolidone, 1-7enyl-4,4-dihydroxymethyl-3-virazolidone, 1-phenyl-5
Examples include -methyl-3-virazolidone, 1-p-aminophenyl-4,4-dimethyl-3-virazolidone, and l-p-tolyl-4,4-dimethyl-3-virazolidone. Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-anophenol, and N-(4-hydroxyphenyl). glycine,
2-Methyl-p-aminophenol, p-benzyl ξ
Among them, N-methyl-P-aξnophenol is preferred. The developing agent is usually O. It is preferably used in an amount of OS mol/l to 0.8 mol/l. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-virazolidones or P-amino-phenols, the former is 0.
05 mol/2 to 0.5 mol/1, the latter 0.06 mol/1
It is preferable to use it in an amount of 1 liter or less. Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.15 mol/l or more, particularly 0.5 mol/l or more. The upper limit is preferably 2.5 mol/Il. Alkaline agents used to set pH include pHlliffing agents and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. The pH of the developer is lO. It is set between 5 and 12.3. Additives used in addition to the above ingredients include 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, and methyl cellosol. , hexylene glycol, ethanol, methanol, and other organic solvents. It may contain an inhibitor or a black pepper inhibitor, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-10
It may also contain the amino compounds described in No. 6244. The developing solution of the present invention contains a silver stain preventive agent.
．． The compounds described in No. 347 can be used. Patent application 1987-109.74 for a solubilizing agent added to the current imitation liquid
The compounds described in No. 3 can be used. ．． In addition, as a pH41 buffer for use in developing solutions, JP-A-80-93.4
Compounds described in No. 33 or Japanese Patent Application No. 61-28708
Compounds described in this issue can be used. As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water-soluble aluminum (eg, aluminum sulfate, alum, etc.) as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0. 4-2
, Og-All1. Furthermore, a trivalent iron compound can be used as an oxidizing agent in the form of a complex with ethylenediaminetetraacetic acid.

The development temperature is usually selected between 18°C and 50°C, more preferably between 25°C and 43°C.

(Examples) Next, the present invention will be described in more detail based on Examples. The developer used in Example 1 had the formulation described below.

(Developer formulation) Hydroquinone 45, Og N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18, Og Potassium hydroxide
55.0g 5-sulfosalicylic acid 4
5.0 g Boric acid 25, Og Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g Potassium bromide 6.0 g 5-Methylbenzotriazole 0. 6gn
-Butyldiethanolamine 15.
Add Og water to 1l (pH=
1 1.6) (Example 1) Emulsion (A) CB) (C3CD) was prepared by the following method.
(E) (F) (G) (H) were prepared.

[Emulsion A]

A monodisperse silver iodobromide emulsion (average grain size 0.26μ, silver iodide content 2
(mol%) was prepared.

This emulsion was washed with water in a conventional manner to remove soluble salts, and then chemical sensitization was performed by adding sodium thiosulfate. Further, potassium iodide was added to the emulsion to convert the grain surface, thereby obtaining a silver iodobromide emulsion having a grain average silver iodide content/grain surface silver iodide content=1/3. To this was added Proxel as a preservative at 70 μm per mole of silver.

This emulsion was designated as A.

[Conventional B]

Silver nitrate aqueous solution and silver l in gelatin aqueous solution kept at 50℃
An aqueous solution of potassium iodide and potassium bromide containing potassium hexacyanoferrate(n) corresponding to 6×10 − mol per mol was added simultaneously over 60 minutes, during which time the pAg increased to 7.
5, a monodisperse silver iodobromide emulsion having an average grain size of 0.26 μm, a silver iodide content of 2 mol %, and a uniform iron content was prepared.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical sensitization, potassium iodide was added, and a preservative was added.

The emulsion thus produced was designated as B.

[Emulsion C]

Silver nitrate aqueous solution and silver l in gelatin aqueous solution kept at 50℃
5X10-' moles of hexacyanoferrate(II) per mole
By simultaneously adding an aqueous solution of potassium iodide and potassium bromide containing acid potassium for 30 minutes and maintaining pAg at 7.5 during this period, an average grain size of 0.20μ and a silver iodide content of 2 were obtained.
Mol% monodispersed silver iodobromide core grains were prepared. Thereafter, a silver nitrate aqueous solution and a halogen salt aqueous solution containing potassium hexacyanoferrate (n) at a concentration of 1 x 10-' mol per mol of silver were simultaneously added for 30 minutes, and the pAg was maintained at 7.5 during this period, resulting in an average particle size of 0. .26μ, silver iodide content 2
A double-structured, monodisperse silver iodobromide was prepared for iron content in mole %, total iron content of 4×10 −′ mole silver.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical sensitization, and potassium iodide and a preservative were added. The emulsion thus made is
And so.

[Emulsion D]

Silver nitrate aqueous solution and silver 1 in gelatin aqueous solution kept at 50℃
An aqueous solution of potassium iodide and potassium bromide containing IXlO-' moles of potassium hexacyanoferrate(n) per mole was added simultaneously over a period of 30 minutes, during which time the pAg was maintained at 7.5, resulting in an average particle size of 0.20μ. , monodispersed silver iodobromide core grains having a silver iodide content of 2 mol % were prepared. Thereafter, an aqueous silver nitrate solution and an aqueous halide solution containing potassium hexacyanoferrate (II) in an amount of sxto-' mol per mol of silver were simultaneously added for 30 minutes, during which time the pAg was maintained at 7.5, resulting in an average particle size of 0.26μ. A double-structured, monodisperse silver iodobromide was prepared in terms of iron content, with a silver iodide content of 2 mol% and a total iron content of 4XlO-7 mol/mole silver.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical sensitization, and potassium iodide and a preservative were added. The emulsion thus produced was designated as D.

[Emulsion E]

A silver nitrate aqueous solution, potassium iodide and potassium bromide aqueous solutions were simultaneously added to an aqueous gelatin solution kept at 50°C for 30 minutes, and the pAg was maintained at 7.5 during that time, resulting in an average particle size of 0.20μ and a silver iodide content. Monodisperse silver iodobromide core grains containing 2 mol% iron were prepared. Thereafter, an aqueous silver nitrate solution and an aqueous halide solution containing potassium hexacyanoferrate(II) at 6XlO-' mol per mol of silver were simultaneously added for 30 minutes, during which the pAg was maintained at 7.5, so that the average size was 0.26μ. A monodisperse silver iodobromide with a double structure in terms of iron content was prepared with a silver iodide content of 2 mol % and a total iron content of 4XlO-' mol/mole silver.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical sensitization, and potassium iodide and a preservative were added. The emulsion thus made is
And so.

[Emulsion F]

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 for 60 minutes, during which time the pAg was adjusted to 1/2. I kept it at 5. Then, 6 minutes after the start of the addition, 6X10-' per mol of gold/silver particles
A molar amount of potassium hexacyanoferrate(II) aqueous solution was added, the average particle size was 0.26μ, and the silver iodide content was 2.
A silver iodobromide emulsion was prepared in which iron was localized at 10% of the total grain volume from the grain center.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical sensitization, potassium iodide was added, and a preservative was added.

The emulsion thus produced was designated as F.

[Emulsion G]

Emulsion F except that an aqueous solution of potassium hexacyanoferrate(II) corresponding to 6×10 −' mol per mol of silver in the finished emulsion was added 54 minutes after the start of addition of the aqueous solution of silver nitrate, potassium iodide, and potassium bromide. A silver iodobromide emulsion was prepared in the same manner, washed with water, chemically sensitized, potassium iodide and a preservative were added, and silver iodobromide emulsion in which iron was localized from the grain center to 90% of the total grain volume was designated as G.

[Emulsion H]

When mixing silver nitrate aqueous solution, potassium iodide and potassium bromide aqueous solution in a gelatin aqueous solution kept at 50℃ for 60 minutes, simultaneously add a potassium hexacyanoferrate (II) aqueous solution as a third solution, and adjust the addition rate at the start of addition. , increasing linearly from 0 until the total iron content is 6X10-' per mole of silver
Add in molar amounts over 60 minutes. Thus, a silver iodobromide emulsion with an average grain size of 0.26μ, a silver iodide content of 2 mol %, a total iron content of 6X10-5 mol per mol of silver, and an iron content increasing from the grain center to the grain surface was prepared. Prepared.

This emulsion was washed with water and chemically sensitized in the same manner as Emulsion A, and after addition of potassium iodide, a preservative was added. The emulsion thus produced was designated as H.

Table 1 summarizes the iron content of emulsions A to H, the structure of the iron content, the position of iron content, and the iron content.

*mol/silver mole 3 x 10-4 per mole of silver as sensitizing dye in this emulsion
mol of 5,5'-dichloro-9-ethyl-3,3'-bis(3-sulfoprobyl)oxacarpocyanine and 4-hydroxy-6-methyl- as a stabilizer.
1. 3. 3a, 7-tetrazaindene, 5
-Methylbenzotriazole, the following compounds (al and (
bl was added at a coating rate of 5 ml/bo.

(Al 2CI" hydrazine compound ■-19 or I-7 was added as shown in Table 2. Furthermore, polyethylene glycol with an average molecular weight of 600 was added at a rate of 75 ■/po, and the dispersion of polyethyl acrylate was and gelatin ratio 30*
t%, l, 3-divinylsulfonyl-2 as dura mater
-Propanol was added and coated onto a polyethylene terephthalate film at a silver concentration of 3.5 g/m. (2 g/n of gelatin) 1.2 g of gelatin as a protective layer on top of this
/rd, amorphous SiOz matting agent with particle size of about 3μ 40■/po, methanol silica 0.1g/m, polyacrylamide lOO■/rrr, hydroquinone 200■
/ silicone oil, Proxel and phenoxyethanol as preservatives, and a fluorosurfactant represented by the following structural formula as a coating aid C. F. , S.O. NCH. C.O.
OK C. Samples 1 to 20 were prepared as shown in Table 2 by simultaneously applying a layer containing H, and sodium dodecylbenzenesulfonate.

The back layer was coated using the following recipe.

[Back layer prescription]

Gelatin 4g/anti-matting agent
Polymethyl methacrylate (particle size 3.0 to 4.0 μ) 10 μ/d latex Polyethyl acrylate surfactant Sodium p-dodecylbenbensulfonate Fluorine surfactant C. F.ISO. NCH2COOK C 3 H 7 Gelatin hardener 2 glrd 40■/d 5■/Dye-resistant Dye [a], Dye [a) Dye [b] Dye [c] 110■/d Mixture of (b) and [c] 50 ■/d 100■/Po50■/Dye resistance [a] SO. K dye [b] SO3K dye [c] SO. K SO3K SO. K SO. K Also, Proxel and phenoxyethanol were added as preservatives to the back layer coating solution.

In addition, the following test method was used for evaluation in each example.

Test method l. Evaluation of image quality (1) Creation of manuscript Monochrome scanner SCA manufactured by Fuji Photo Film Co., Ltd.
A transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed in stages were created using NART30 and special photosensitive material SF-100. At this time, the number of screen lines was 150 lines/inch.

(2) Photography After setting the above-mentioned original on a Dainippon Screen (manufactured by Dainippon Screen Co., Ltd.) camera C-440 so that the magnification was 1:1, the evaluation sample was exposed to light by irradiating it with a Xe lamp.

At this time, exposure was performed such that 95% of the step wedge of the original was exposed to 5%.

(3) Small dot side (highlight area) with exposure adjusted as in evaluation (2)
A five-grade evaluation (5 to 1) was performed in descending order of the gradation reproducibility (difficulty of halftone dot collapse) in the shadow portion of the samples, which combined the halftone dot percentages.

2. Copy dot evaluation (11 Manuscript creation Monochrome scanner-SCA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special paper SP-1oowp, a step wedge in which the dot percentage was changed in stages was created. The number of screen lines during exposure was 150 lines/inch.

(2) Photography The above manuscript and sample were set in predetermined positions in a Dainippon Screen ■ plate-making camera C-690 (Auto Companica), and a Xe lamp was irradiated onto the reflective manuscript and photographed.

At this time, the exposure time is 80% of the step wedge on the original.
It was adjusted so that the portion was 10% on the sample.

(3) Tone reproducibility of the shadow part of the sample with halftone percentage on the small dot side by adjusting the exposure time as described in (2) (2)
Relative evaluation was performed on a five-level scale, with 5 being good and 1 being bad in terms of halftone dot shift difficulty.

The obtained sample was exposed to light using a xenon light source, and Fuji Photo Film (Kiki GR-DL) was used as a developer and fixer.
Development was performed at 34° C. for 30 seconds using GR-F 1 and an automatic processor FG-660F, and the eye stretching performance and copy dot performance were evaluated.

Here, the sensitivity is the density l. The value of sample 1 was set to 100 based on the relative value of the reciprocal of the exposure amount giving 5.

Dmax is expressed as a concentration equivalent to Dmax in practical skill.

(On the characteristic curve, j!og for the sensitivity point of density 0.1
The results are shown in Table 2. As is clear from Table 2, the samples of the present invention have higher sensitivity, γ, and maximum density Dmax, have better black spots, and have better image quality than the comparative samples.

(Example 2) The compound of general formula (II) of the present invention was added to the emulsions DSE, G, H used in Example 1 as shown in Table 3, and further
Samples 2l to 34 were prepared by adding the same compound as above and coating.
was created. These samples were evaluated in the same manner as in Example 1. The results are shown in Table 3. As is clear from the table, the presence of the compound of general formula (II) of the present invention further improves the image quality.

(Example 3) Instead of the compound used in Example 2 as the compound of general formula (n), II-1 was used at 5 x 10-5 mol per mol of silver or ■-27 was added at 5 x 1O per mol of silver. Samples were prepared in exactly the same manner as in Example 2, except that -5 mol or II-25 was used at 5 x IO-5 mol per mol of silver, and evaluation was performed in the same manner as in Example 2. Samples with the configuration of the present invention showed good image quality.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the emulsion layer contains a halogen containing at least 1 x 10^-^7 moles of iron salt per mole of silver. A grain consisting of a silver halide emulsion, in which the silver halide grains of the silver halide emulsion contain iron in an amount corresponding to 50% of the total grain volume from the grain surface in an amount of 60% or more of the iron content in the whole grain. 1. A silver halide photographic light-sensitive material comprising a hydrazine derivative represented by the following general formula (I) in the emulsion layer or other hydrophilic colloid layer. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group, aromatic group, or heterocyclic group, and R_2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, amino group, carbamoyl group or oxycarbonyl group, G_1 is carbonyl group, sulfonyl group, sulfoxy group, ▲ formula,
Chemical formulas, tables, etc. are available ▼ - group, ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ - group, thiocarbonyl group, or iminomethylene group, A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is substituted or represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. (2) The negative-working silver halide photographic material according to claim 1, wherein the emulsion layer or other hydrophilic colloid layer contains a redox compound that releases a development inhibitor upon oxidation.