JP2739368B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention forms an extremely hard negative image, a highly sensitive negative image, a silver halide photographic light-sensitive material giving good halftone image quality, or a direct positive photographic image. More particularly, the present invention relates to a photographic light-sensitive material containing a novel compound as a nucleating agent for silver halide.

(Prior art) Addition of a hydrazine compound to a silver halide photographic emulsion or a developing solution is disclosed in US Pat. Nos. 3,730,727 (a developing solution combining ascorbic acid and hydrazine) and 3,227,552 (for directly obtaining a positive color image). No. 3,386,831 (containing β-mono-phenylhydrazide of an aliphatic carboxylic acid as a stabilizer for silver halide photographic materials), No. 3,419,975 and Mees
By Theory of Photographic Process, 3rd edition (19
It is known on pages 281 and 66.

Of these, in particular, U.S. Pat.No. 2,419,975,
It is disclosed that a hard negative image is obtained by adding a hydrazine compound.

The patent describes that when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH such as 12.8, extremely hard photographic characteristics with a gamma (γ) exceeding 10 can be obtained. Have been. However, a strong alkaline developer having a pH close to 13 is liable to be oxidized by air and is unstable, and cannot withstand long-term storage or use.

Ultra-hard photographic characteristics with gammas exceeding 10 include negative images,
Any of the positive images is extremely useful for photographic reproduction of a continuous tone image or reproduction of a line drawing using a dot image useful for printing plate making. For this purpose, conventionally, a silver chlorobromide photographic emulsion having a silver chloride content of more than 50 mol%, preferably more than 75 mol%, is used, and the effective concentration of sulfite ion is extremely low (usually 0.1 mol%). /Less than)
A method of developing with a hydroquinone developer thus obtained has been generally used. However, in this method, since the sulfite ion concentration in the developer is low, the developer is extremely unstable and cannot be stored for more than three days.

Furthermore, all of these methods required the use of a silver chlorobromide emulsion having a relatively high silver chloride content, so that high sensitivity could not be obtained. Accordingly, there has been a strong demand for obtaining ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings using a high-sensitivity emulsion and a stable developer.

U.S. Pat.Nos. 4,224,401, 4,168,977, and 4,243,73
No. 9, 4,272,614, 4,323,643, etc.
Although silver halide photographic emulsions have been disclosed which provide extremely hard negative photographic properties using a stable developer, the acylhydrazine compounds used in them have been found to have several disadvantages.

That is, it is known that these conventional hydrazines generate nitrogen gas during the development processing, and these gases gather in the film to form bubbles and impair the photographic image. The effect on other photographic light-sensitive materials is to leak to the photographic material.

It has been known that the nucleating agent has a large molecular weight and is resistant to diffusion as a means of preventing the nucleating agent from flowing out into the processing solution. It turns out that there is a problem. That is, when the coating solution containing the nucleating agent is aged, a precipitate is formed in the coating solution, the filterability is deteriorated, and the photographic performance is also changed.

In addition, these conventional hydrazines are required in large amounts for sensitization and high contrast, or when it is required that the sensitivity of the photosensitive material be particularly high, other sensitization techniques (for example, chemical sensitization) To increase the particle size, adding a compound that promotes sensitization as described in U.S. Patent Nos. 4,272,606 and 4,241,164). Increased fog may occur.

Therefore, a compound which can reduce generation of such bubbles and outflow into a developing solution, does not have a problem in stability over time, and can obtain extremely hard photographic characteristics with a very small amount of addition has been desired. .

Also, U.S. Pat.Nos. 4,385,108, 4,269,929,
No. 243,739 describes that hydrazines having a substituent easily adsorbed to silver halide grains can be used to obtain extremely hard negative gradation photographic properties. Among the hydrazine compounds, those specifically described in the above-mentioned known examples have a problem that they cause desensitization with time during storage. Therefore, it is necessary to select a compound that does not cause such a problem.

On the other hand, there are various types of direct positive photographic methods. A method in which silver halide grains which have been fogged in advance are exposed in the presence of a desensitizer and then developed, and a method in which a silver halide grain having a photosensitive nucleus mainly inside the silver halide grains is used. After exposure of the silver halide emulsion, a method of developing in the presence of a nucleating agent is most useful. The present invention relates to the latter. A silver halide emulsion having a photosensitive nucleus mainly in the inside of a silver halide grain and forming a latent image mainly in the inside of the grain is called an internal latent image type silver halide emulsion. It is distinguishable from image forming silver halide grains.

There is known a method of directly obtaining a positive image by developing a surface of an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent, and a photographic emulsion or a photographic material used in such a method.

In the method for obtaining a direct positive image described above, the nucleating agent may be added to the developer, but the nucleating agent is adsorbed on the surface of silver halide grains by adding it to the photographic emulsion layer or other appropriate layer of the light-sensitive material. Sometimes, better inversion characteristics can be obtained.

Examples of the nucleating agent used in the method for obtaining a direct positive image include hydrazines described in U.S. Pat.Nos. 2,563,785 and 2,588,982, and hydrazide and hydrazine-based compounds described in U.S. Pat. Patent Nos. 3,615,615, 3,719,494, 3,734,738
Nos. 4,094,683 and 4,115,122; British Patent 1,
283,835, heterocyclic quaternary salt compounds described in JP-A-52-3426 and JP-A-52-69613, U.S. Pat.No.4,030,925,
4,031,127, 4,139,387, 4,245,037, 4,2
Nos. 55,511 and 4,276,364, thiourea-bonded acylphenylhydrazine-based compounds described in British Patent No. 2,012,443, compounds having a heterocyclic thioamide as an adsorptive group described in U.S. Pat.No.4,080,207, British Patent No.
Phenylacyl hydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in 2,011,397B, a sensitizing dye having a substituent having a nucleation function described in U.S. Pat.No.3,718,470 in the molecular structure, JP-A-59-200,23
No. 0, No. 59-212,828, No. 59-212,829, Research Di
Hydrazine compounds described in Sclosure No. 23510 (November 1953) are known.

For the purpose of solving these drawbacks, Japanese Patent Application Laid-Open No. 60-179,734
Nos. 61-170,733, 61-270,744, 62-65,034
Nos. 62-948, 63-223,744, 63-234,24
No. 4, 63-234,245, 63-234246, 63-306438
, Japanese Patent Laid-Open No. 1-10233, European Patent Publication (EP) No. 3
Although nucleating agents described in 450450 have been proposed, it is necessary to lower the pH of the processing solution in order to enhance the stability of the processing solution (that is, to prevent the deterioration of the developing agent), or to reduce the processing time of development. If you want to shorten it or use the developer composition (for example, p
(H, sodium sulfite, etc.) In order to reduce the dependence of the change, higher nucleation activity was desired.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is, first, to provide a silver halide photographic light-sensitive material capable of obtaining photographic characteristics of a hard negative gradation by using a stable developer. It is to be.

A second object of the present invention is to provide a novel highly active hydrazine which can provide a desired high contrast negative tone photographic characteristic with a small amount of addition and a low pH developer without adversely affecting photographic characteristics. Another object of the present invention is to provide a negative silver halide photographic material.

(Constitution of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, wherein the photographic emulsion layer or at least one other hydrophilic colloid layer has at least one of the following: This was achieved by containing a compound represented by the general formula (I).

General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group or an oxycarbonyl group.

Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Y ₁ represents a divalent organic group.

 Next, the general formula (I) will be described in detail.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein.

In the general formula (I), 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 pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like.

The aliphatic group, aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and examples of the typical substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, Substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl 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 group, And the like. Preferred substituents are a straight-chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or 2-alkyl group having 1 to 3 carbon atoms in the alkyl portion). Ring), 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 having 2 to 20 carbon atoms) 30), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Things).

The alkyl group represented by R ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms,
For example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group, an acyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, sulfamoyl group, nitro group, heteroaromatic group, And the like, and these groups may be further substituted.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted, and examples of the substituent are the same as those in the case of the alkyl group.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably a monocyclic one, and the substituent includes a halogen atom.

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Preferred among the groups represented by R ₂ are those wherein G ₁ is Is an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (for example, an o-hydroxybenzyl group) ), Aryl group (for example, phenyl group, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc., and a hydrogen atom is particularly preferable.

When G ₁ is a —SO ₂ — group, R ₂ represents an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group), or A substituted amino group (for example, a dimethylamino group) is preferred.

When G ₁ is a —SO— group, preferred R ₂ includes a cyanobenzyl group, a methylthiobenzyl group and the like, and G ₁ is In the case of R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group,
Phenoxy groups are preferred.

When G ₁ is an N-substituted or unsubstituted aminomethylene group,
Preferred R ₂ is a methyl group, an ethyl group, a substituted or unsubstituted phenyl group.

As the substituent of R _2, the substituents listed for R ₁ can also be applied.

As G _{1 in the} general formula (I), Is most preferred.

Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
-R ₂ moiety of atoms may be filed such to rise to cyclization reaction to form a cyclic structure containing a is such that it can specifically represented by the general formula (a).

In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, is a group capable of splitting the G ₁ -R ₃ -Z ₁ moiety from the remainder molecule, R ₃ than that removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, G _1,
A cyclic structure can be formed by R ₃ and Z ₁ .

More specifically, Z ₁ easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound of the general formula (I) generates the next reaction intermediate by oxidation or the like (reaction intermediate) R ₁ -N = N -G ₁ -R ₃ -Z ₁ R ₁ -N = N is a group capable of splitting an N group from G ₁ , specifically, OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ or —SO ₂ R ₅ , wherein R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), a functional group that directly reacts with G ₁ such as COOH, etc. well (here, OH, SH, NHR _4, -COOH may be temporarily protected so as to generate these groups by hydrolysis of an alkali, etc.), or, (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group capable of performing the above.

The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c).

General formula (b) Wherein, R ¹ _b ~R ⁴ _b represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), (those of preferably 2 to 12 carbon atoms) alkenyl group, an aryl group (preferably having a carbon number of 6 ~
12) and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n
+ M) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
A cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₁ has the same meaning as in formula (a).

General formula (c) In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or the like, and may be the same or different.

R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

 p represents 0 or 1 or 2, and q represents 1 to 4.

R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on G ₁ .

R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, p is 1 or 2 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is In the case of 2 or 3, a plurality of (CR _c ¹ R _c ² ) may be the same or different. Z ₁ has the same meaning as in formula (a).

A ₁ and A ₂ are a hydrogen atom, an alkylsulf or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of the substituent constants of Hammett is -0.5 or more; ), An acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, or a straight-chain, branched or cyclic unsubstituted or substituted And an aliphatic acyl group (for example, a substituent includes a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group).

A ₁ and A ₂ are most preferably hydrogen atoms.

The divalent organic group represented by Y ₁ in the general formula (I) is an aliphatic group, an aromatic group, and a group represented by the following structural formula.

(Wherein, Y ₁ represents an aromatic group or a heterocyclic group, R ₀ ¹
To R ₀ ⁴ each represents a hydrogen atom, a halogen atom or an alkyl group, r and s represents 0 or 1. The aliphatic group represented by Y ₁ is a linear, branched or cyclic alkylene group, alkenylene group and alkynylene group.

The aromatic group represented by Y ₁ is a monocyclic or bicyclic arylene group, such as a phenylene group and a naphthylene group, and a phenylene group is particularly preferred.

Y ₁ is more preferably an arylene group, particularly preferably a phenylene group.

Y ₁ may have a substituent. As the substituent, for example, those listed as the substituent of R ₁ can be applied.

R ₁ , R ₂ or Y _{1 in the} general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups and the like.
Examples of the polymer include those described in JP-A-1-100530.

R ₁ , R ₂ or Y _{1 in the} general formula (I) may have a group in which a group which enhances adsorption to the surface of silver halide grains is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Pat. −201,045
Nos. 59-201,046, 59-201,047, 59-201,04
No. 8, 59-201, 049, JP-A-61-170,733, 61-2
Nos. 70,744, 62-948, 63-234244, 63-23424
The groups described in No. 6 can be mentioned.

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

The hydrazine derivative of the present invention is generally synthesized by reacting a corresponding chloroacetamide-substituted hydrazine compound with a thiol in the presence of a base as shown in the following reaction formula.

Representative synthesis examples are shown below.

(Synthesis Example: Synthesis of Compound 2) Under a nitrogen atmosphere, a mixture of dodecanethiol (4.2 g), methanol (100 ml), and sodium ethylate (28% ethanol solution, 5.1 g) was added under ice-cooling. (7.0 g) was added as a solid in small portions. After the addition, the mixture was stirred overnight while gradually warming to room temperature, and then volatile components were distilled off under reduced pressure. Compound 2 was obtained by purification by silica gel chromatography.

(Yield 5.2 g) The chemical structure was confirmed by nmr spectrum, in spectrum and elemental analysis.

In order to incorporate the compound of the present invention into a photographic emulsion layer or a hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary, alkali hydroxide or trihydric acid). May be dissolved by adding a secondary amine to form a salt), a hydrophilic colloid solution (for example, a silver halide emulsion,
The pH may be adjusted by adding an acid or an alkali, if necessary.

The compounds of the present invention may be used alone or in combination of two or more. The addition amount of the compound of the present invention is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, per 1 mol of silver halide. An appropriate value can be selected according to the properties of the silver halide emulsion.

The compound represented by formula (I) of the present invention can form a negative image having high contrast when used in combination with a negative emulsion. On the other hand, it can be used in combination with an internal latent image type silver halide emulsion.

When used for forming negative images with high contrast,
The average grain size of the silver halide used is preferably fine grains (for example, 0.7 μm or less), particularly preferably 0.5 μm or less. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% of the weight or the number of particles is ±
It is composed of particles having a size within 40%.

Silver halide grains in photographic emulsions are cubic, octahedral, diamond
It may have a regular crystal such as a dodecahedron or a tetrahedron, a crystal having an irregular crystal such as a sphere or a plate, or a complex form of these crystals. May be one having.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide and the like.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

The silver halide used in the present invention is 10 ^-8 to 1 mol per mol of silver.
It is a silver haloiodide prepared in the presence of 10 ^-5 mol of an iridium salt or a complex salt thereof and having a silver iodide content on the grain surface larger than the average silver iodide content of the grains. Use of an emulsion containing such a silver haloiodide provides photographic characteristics with higher sensitivity and higher gamma.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and rhodium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in, for example, British Patent No. 618,016. As a sulfur sensitizer, in addition to sulfur compounds contained in gelatin,
Various sulfur compounds, such as thiosulfates, thioureas,
Thiazoles, rhodanines and the like can be used.

In the above, it is preferable to use an iridium salt or a rhodium salt before the completion of physical ripening in the production process of the silver halide emulsion, particularly at the time of grain formation.

In the present invention, the silver halide emulsion layer is disclosed in Japanese Patent Application No. 60-6419.
No. 9 and Japanese Patent Application No. 60-232086 preferably contain two types of monodisperse emulsions having different average grain sizes from the viewpoint of increasing the maximum density (Dmax). It is preferably sensitized, and the method of chemical sensitization is most preferably sulfur sensitization. The large-size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Generally, large-sized monodispersed particles are not subjected to chemical sensitization because black spots are easily generated. However, when chemically sensitized, it is particularly preferable to apply the grains so shallow that black spots are not generated. Here, "shallow application" refers to shortening the time for performing chemical sensitization, lowering the temperature, or suppressing the amount of chemical sensitization to be added, as compared with the chemical sensitization of small-sized grains. The difference in sensitivity between the large-size monodisperse emulsion and the small-size monodisperse emulsion is not particularly limited, but is 0.1 to 1.0, more preferably 0.2 to 0.7, as ΔlogE, and the higher the large-size monodisperse emulsion, the more preferable. Here, the sensitivity of each emulsion was such that a hydrazine derivative was contained and coated on a support, and the sulfite ion was 0.15 mol / mol.
It is obtained when processing is carried out using a developer having a pH of from 10.5 to 12.3 containing the above components. The average grain size of the small-sized monodispersed grains is 90% or less, preferably 80% or less of the average size of the large-sized silver halide monodispersed grains. The average grain size of the silver halide emulsion grains is preferably 0.
It is preferable that the average particle size of the large-sized and small-sized monodispersed particles is included in the range of 02 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm.

When two or more kinds of emulsions having different sizes are used in the present invention, the silver coating amount of the small size monodispersed emulsion is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total silver coating amount. is there.

In the present invention, as a method for introducing monodisperse emulsions having different grain sizes, they may be introduced into the same emulsion or into different layers. When introduced into separate layers, it is preferred that the large size emulsion be the upper layer and the small size emulsion be the lower layer.

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

In the light-sensitive material used in the present invention, sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described in JP-A-55-52050, pp. 45-53 for the purpose of increasing the sensitivity.
Can be added. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure).
Disclosure) Volume 176 17643 (Issued December 1978) Page 23 IV
Section J.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindene) ), Pentaazaindenes; and many other compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfonate, benzenesulfonamide, and the like. 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.

Examples of development accelerators suitable for use in the present invention or accelerators for developing nucleation transmission include JP-A-53-77616 and JP-A-54-77616.
7732, 53-137133, 60-140340, 60-1495
In addition to the compounds disclosed in No. 9, various compounds containing an N or S atom are effective.

The optimal amount of these accelerators varies depending on the type of the compound, but is 1.0 to 10 ^{-3 to} 0.5 g / m ² , preferably 5.0 to 10 ^-3.
It is desirable to use it in the range of 0.1 g / m ² .

The light-sensitive material of the present invention may contain a desensitizer in the photographic emulsion layer and other hydrophilic colloid layers.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, that is, the oxidation-reduction potential determined by polarography, and the sum of the polaro anodic potential and the cathodic potential becomes positive. A method for measuring the oxidation-reduction potential of a polarograph is described in, for example, US Pat. No. 3,501,307. The organic desensitizer preferably contains at least one water-soluble group, and specific examples thereof include a sulfonic acid group, a carboxylic acid group, and a sulfonic acid group. These groups include an organic base (eg, ammonia, pyridine , Triethylamine, piperidine, morpholine, etc.) or an alkali metal (eg, sodium, potassium, etc.).

As organic desensitizers, Japanese Patent Application No. 61-280998, p. 55-
Those represented by the general formulas (III) to (V) described on page 72 are preferably used.

The organic desensitizer in the present invention is contained in the silver halide emulsion layer.
1.0 × 10 ^{-8 to} 1.0 × 10 ^-4 mol / m ² , especially 1.0 × 10 ^{-7 to} 1.0 × 1
0 it is preferable ^{to -5} mol / m ² made present.

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A water-soluble dye may be contained as a filter dye or for various purposes such as prevention of irradiation.
As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the inherent sensitivity range of silver halide, and safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the region of 380 nm to 600 nm are used to increase the light absorption.

These dyes are added to the emulsion layer depending on the purpose,
Alternatively, it is preferable to add and fix a non-photosensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with the mordant before use.

Depending on the molar extinction coefficient of the UV absorber, usually 10
^-2 is added in a range of ^{g / m 2 ~1g / m 2} . Preferably 50mg-5
00 mg / m ² .

The ultraviolet absorber can be dissolved in an appropriate solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof) and added to the coating solution.

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of UV absorbers are described in U.S. Pat.
3,314,794, 3,352,681, JP-A-46-2784, U.S. Pat.Nos. 3,705,805, 3,707,375, 4,045,229,
3,700,455, 3,499,762, West German Patent Application Publication 1,547,
No. 863.

Filter dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cytanine dyes and azo dyes. From the viewpoint of reducing residual color after the development, a dye which is water-soluble or decolorizes by alkali or sulfite ions is preferred.

Specifically, for example, pyrazolone ossanol dye described in U.S. Pat.No. 2,274,782, diarylazo dye described in U.S. Pat.No. 2,956,879, U.S. Pat.
No. 3,384,487, styryl dyes and butadienyl dyes, U.S. Pat.No.2,527,583, merocyanine dyes described in U.S. Pat.No. 3,486,897, U.S. Pat.No. 3,486,897, No. U.S. Pat.Nos. 3,976,661 enaminohemioxonol dyes and British Patents 584,609 and 1,17
No. 7,429, JP-A-48-85130, JP-A-49-99620, JP-A-49-1
No. 14420, U.S. Pat.Nos. 2,533,472, 3,148,187,
No. 3,177,078, No. 3,247,127, No. 3,540,887
And the dyes described in JP-A Nos. 3,575,704 and 3,653,905.

The dye is dissolved in an appropriate solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof), and the coating solution for the non-photosensitive hydrophilic colloid layer of the present invention. Is added during.

The amount of the specific dye can generally be found in desired amounts in the range of ^{10 -3 g / m 2 ~1g /} m 2 , especially ^{10 -3 g / m 2 ~0.5g /} m 2.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layers, for example, chromium salts, aldehydes, (formaldehyde glutaraldehyde, etc.), N-methylol Compounds (such as dimethylol urea) and 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.), mucohalogenic acids and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained. Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Here, when used as an antistatic agent, a surfactant containing fluorine (see US Pat. No. 4,201,586 for details)
And JP-A-60-80849 and JP-A-59-74554 are particularly preferred.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethyl methacrylate for the purpose of preventing adhesion to the photographic emulsion layer and other hydrophilic colloid layers.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. be able to.

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,
Examples thereof include polymers or copolymers having an acid monomer such as phthalic acid as a repeating unit. These compounds are disclosed in Japanese Patent Application Nos. 60-66179 and 60-68873.
No., JP-A-60-163856 and JP-A-60-195655 can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and a high molecular compound composed of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

In order to obtain ultra-high contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in U.S. Patent No. 2,419,975. And a stable developer can be used.

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

The developing agent used in the developer used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in that good halftone dot quality can be easily obtained, and is preferably a mixture of dihydroxybenzenes and 1-phenyl-3-. Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols may be used. Developer is usually 0.05
It is preferably used in an amount of mol / .about.0.8 mol /. Dihydroxybenzenes and 1-phenyl-3-
When a combination with pyrazolidones or p-amino-phenols is used, the former is used in an amount of 0.05 mol / to 0.5 mol /.
The latter is preferably used in an amount of 0.06 mol / or less.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is preferably at least 0.4 mol / mol, particularly preferably at least 0.5 mol / mol.

The developing solution of the present invention is disclosed in JP-A-56-2 as a silver stain inhibitor.
The compounds described in 4,347 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Furthermore, compounds described in JP-A-60-93,433 or compounds described in Japanese Patent Application No. 61-28,708 can be used as a pH buffer used in the developer.

The compound represented by the general formula (I) is used in combination with a negative emulsion as described above for a high-contrast photosensitive material.
Although it can be combined with an internal latent image type silver halide emulsion, its mode is described below. In this case, the compound represented by the general formula (I) is preferably contained in the internal latent image type silver halide emulsion layer, but is contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer. Is also good. Such layers include colorant layers, intermediate layers, filter layers,
A layer having any function, such as a protective layer or an anti-halation layer, may be used as long as it does not prevent the nucleating agent from diffusing into the silver halide grains.

The content of the compound represented by formula (I) in the layer is such that a sufficient maximum density (for example, a silver density of 1.0 or more) is obtained when the internal latent image type emulsion is developed with a surface developer. It is desirable. In practice, the appropriate content can vary over a wide range because it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions. About 1 mole of silver in silver emulsion
A range from 0.005 mg to 500 mg is practically useful, with about 0.01 mg to about 100 mg per mole silver being preferred. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as described above may be contained with respect to the amount of silver contained in the same area of the internal latent image type emulsion layer. The definition of the internal latent image type silver halide emulsion is described in JP-A-61-170733, page 10, upper column and British Patent 2,089,057, pages 18-20.

Preferred internal latent image emulsions usable in the present invention are described in JP-A-61-253716, page 28, line 14 to page 31, line 2.
The preferred silver halide grains are described on page 31, line 3 to page 32, line 11 of the same specification.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by using a sensitizing dye. As sensitizing dyes,
Cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, horopora-cyanine dye, styryl dye, hemicyanine dye,
Oxonol dyes, hemioxonol dyes and the like can be used. These sensitizing dyes include, for example,
And cyanine dyes and merocyanine dyes described in JP-A Nos. 40,638, 59-40,636 and 59-38,739.

The light-sensitive material of the present invention can contain a color image forming coupler as a colorant. Alternatively, development can be performed with a developer containing a color image forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in Research Disclosure (RD) 17643 (December 1978), Sections VII-D and 1871.
7 (November 1979).

Couplers in which the color-forming dye has an appropriate diffusibility, non-color couplers, or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator can also be used.

Typical examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and typical examples thereof include an oxygen atom-eliminable yellow coupler and a nitrogen atom-eliminable yellow coupler. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness, while α-benzoylacetoanilide-based couplers can provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based and pyrazoloazole-based couplers such as pyrazolotriazoles. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.

As a leaving group of 2-equivalent 5-pyrazolone coupler,
Particularly preferred are the nitrogen atom leaving groups described in US Pat. No. 4,310,619 or the arylthio groups described in US Pat. No. 4,351,897. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in 379,899, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (June 1984) Pyrazolotetrazoles and Research Disclosure 24)
230 (June 1984). The imidazo [1,2-b] pyrazoles described in EP 119,741 are preferred from the viewpoint of low yellow side absorption and light fastness of the coloring dye, and EP 119,8
Pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based couplers and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat. Nos. 4,228,233 and 4,296,200
The representative examples are the oxygen-equivalent double-equivalent naphthol couplers described in the above publication. Specific examples of phenolic couplers are described in U.S. Patent Nos. 2,369,929 and 2,80
Nos. 1,171, 2,772,162, and 2,895,826. Humidity and temperature-resistant cyan couplers are preferably used in the present invention, and typical examples thereof include phenols having an alkyl group or more at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, 2,5-diacylamino-substituted phenolic couplers, and phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In order to correct unnecessary absorption in the short wavelength region of the dye formed from the magenta and cyan couplers, it is preferable to use a colored coupler together with the color photographic material for photography.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusing couplers are disclosed in U.S. Pat.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 3,234,533.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,282.

Various couplers used in the present invention can be used in combination of two or more in the same layer of the photosensitive layer, or two or more layers in which the same compound is used in order to satisfy the characteristics required for the photosensitive material. Can also be introduced.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
The amount is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In the present invention, a developing agent such as hydroxybenzenes (for example, hydroquinones), aminophenols, and 3-pyrazolidones may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention may be subjected to an appropriate development processing by combining with a dye image donating compound (coloring material) for a color diffusion transfer method which releases a diffusible dye in accordance with the development of silver halide. Thereafter, it can be used to obtain a desired transfer image on the image receiving layer. Many color materials for such a color diffusion transfer method are known. Among them, although non-diffusible at first, they are formed by an oxidation-reduction reaction with an oxidation product of a developing agent (or an electron transfer agent). It is preferable to use a colorant of the type that releases the diffusible dye upon cleavage (hereinafter abbreviated as DRR compound). Among them, a DRR having an N-substituted sulfamoyl group
Compounds are preferred. Particularly preferred in combination with the nucleating agent of the present invention, U.S. Pat.Nos. It is a DRR compound having a redox nucleus as described in JP-A-53-149,328. When used in combination with such a DRR compound, the temperature dependence during treatment is particularly small.

After imagewise exposure using the light-sensitive material of the present invention, after or while performing fog treatment with light or a nucleating agent, a surface developer having a pH of 11.5 or less containing an aromatic primary amine-based color developing agent It is preferable to directly form a positive color image by performing color development, bleaching and fixing. The pH of this developer is
More preferably, it is in the range of 11.1 to 10.0.

The fogging treatment in the present invention includes a method of applying a second exposure to the entire surface of a photosensitive layer called a so-called "light fogging method" and a method of developing in the presence of a nucleating agent called a "chemical fogging method". Either one may be used. Development processing may be performed in the presence of a nucleating agent and fog light. Further, fog exposure may be performed on a photosensitive material containing a nucleating agent.

The light fogging method is described in the above-mentioned Japanese Patent Application No. 61-253716, page 47, line 4 to page 49, line 5, and the nucleating agent which can be used in the present invention is described in the same specification, page 49-6. Line to page 67 2
In particular, the general formulas [N-1] and [N-
Use of the compound represented by 2] is preferred. Specific examples thereof include [NI-] described on pages 56 to 58 of the same specification.
[1] to [NI-10] and [N-II-1] to [N-II-12] described on pages 63 to 66 of the same specification are preferred.

Regarding the nucleation accelerator that can be used in the present invention,
It is described on page 68, line 11 to page 71, line 3, and specific examples thereof include (A-1) to (A-1) described on page 69 to page 70.
Use of 3) is preferred.

The color developing solution used in the development processing of the light-sensitive material of the present invention is described in the specification, page 71, line 4 to page 72, line 9, and is particularly useful for aromatic primary amine color developing agents. As a specific example, a p-phenylenediamine-based compound is preferable, and a typical example thereof is 3-methyl-4-amino-
N-ethyl-N- (β-methanesulfonamidoethyl)
Aniline, 3-methyl-4-amino-N-ethyl-N-
(Β-hydroxyethyl) aniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfate and hydrochloride.

In order to form a positive color image directly by the color diffusion transfer method using the photosensitive material of the present invention, a black-and-white developing agent such as a phenidone derivative can be used in addition to the above color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be performed by one-bath bleach-fixing simultaneously with the fixing treatment, or may be performed individually. In order to further speed up the processing, a method of performing bleach-fixing after bleaching or a method of performing bleach-fixing after fixing may be used.
In the bleaching solution or the bleach-fixing solution of the present invention, an aminopolycarboxylic acid iron complex is usually used as a bleaching agent. As the additives used in the bleaching solution or the bleach-fixing solution of the present invention, various compounds described in JP-A-61-32462, pages 22 to 30, can be used. After the desilvering step (bleach fixing or fixing), processing such as washing with water and / or stabilization is performed. It is preferable to use softened water for the washing water or the stabilizing solution. Examples of the water softening method include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent Application No. 61-131632. As a specific method thereof, it is preferable to carry out the method described in Japanese Patent Application No. 131632/1986.

Further, as the additives used in the washing and stabilizing steps, various compounds described in Japanese Patent Application No. 32462/1986, pages 30 to 36 can be used.

It is preferable that the amount of replenisher in each processing step is small.
The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 3 times the amount of the pre-bath brought in per unit area of the photosensitive material.
It is 0 times.

Example 1 Silver nitrate and a halogen solution were added to an aqueous gelatin solution kept at 55 ° C. in the presence of ammonia by a control double jet method for 60 minutes to prepare a cubic monodispersed silver iodobromide emulsion having a grain size of 0.32 μm (coefficient of variation). 12%, silver iodide 0.5 mol%, iodine distribution uniform). At the time of preparing this emulsion, K ₃ IrCl ₆ was added to a halogen solution, and was contained at 5 × 10 ⁻⁷ mol / Ag mol so as to be uniformly distributed in the grains.

This emulsion was subjected to desalting by the flocculation method, and then kept at 50 ° C. and used as a sensitizing dye the following compounds as a sensitizing dye: 5 × 10 ⁻⁴ mol per mol of silver and 10 ⁻³ mol per mol of silver of potassium iodide solution. Add 15 minutes and add 4-hydroxy-6-
After adding methyl-1,3,3a, 7-tetrazaindene, the temperature was lowered. (Emulsion A) Sensitizing dye The hydrazine compound shown in Table 1 was added to this emulsion,
Further, the following nucleation accelerators -A and 5-methylbenztriazole were added at 2 × 10 ^-4 mol / Ag mol and 8.6 × 10 ^-3 mol / Ag, respectively.
Nucleation accelerator-A Other polyethyl acrylate and 1,3-divinyl-sulfonyl-2-propanol as a hardener were added, and silver 4.0 g / m 2 on a polyethylene terephthalate film.
² was applied. Gelatin as a protective layer on this
1.2 m / m ² , 40 m irregular SiO ₂ matting agent with particle size of about 3μ
g / m ² , methanol silica 0.1 g / m ² , and a fluorine surfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzenesulfonate.

 The bag layer was applied according to the following formulation.

(Back layer formulation)

Gelatin 4g / m ² mat agent polymethyl methacrylate (particle size 3.0~4.0μ) 10mg / m ² latexes polyethyl acrylate 2 g / m ² Surfactant p- sodium dodecylbenzenesulfonate 40 mg / m ² fluorine based surfactants Agent Gelatin hardener Dye Mixture of dyes [a], [b], and [ch] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ² Dye [a] Dye [b] Dye [c] These samples were exposed to an optical wedge or a wedge and an optical wedge through a contact screen (Fujifilm, 150L chain type) with tungsten light of 3200 ° K, and then developed with the following developer-I at 34 ° C for 30 seconds, and fixed. Washed and dried. The fixer used was Fujifilm GRANDEX Fixer GR-F1.

Table 1 shows the sensitivity, gradation, and halftone dot quality of the obtained sample.

[Developer-I]

Hydroquinone 54 g 4-methyl-4-hydroxymethyl-1-phenyl-
3-pyrazolidone 0.42 g potassium sulfite 90 g disodium ethylenediaminetetraacetate 2.8 g potassium bromide 5 g 2-mercaptobenzimidazole-5-sulfonic acid
0.5 g Boric acid 10 g (KOH is added to adjust the pH to 10.6) H ₂ O is added. One halftone is represented by the following formula.

* Halftone = Exposure to give 95% halftone dot area ratio (logE95
%) — Exposure to give a dot area ratio of 5% (log E5%) The dot quality was visually evaluated on a 5-point scale. In the five-point evaluation, "5" indicates the best quality and "1" indicates the worst quality.
"5" and "4" are practically usable as the halftone dot masters for plate making, "3" is a practically usable limit level, "2",
"1" is a quality that cannot be used.

As can be seen from the results of Table 1, the comparative nucleating agent A has a narrow halftone gradation width, and the comparative nucleating agent B has an insufficient halftone dot quality. Is also good.

Nucleating agents A and B are nucleating agents described in EP345025A.

Example 2 An aqueous gelatin solution maintained at 50 ° C. was added in an amount of 5.0 × 10
^An aqueous solution of silver nitrate and an aqueous solution of sodium chloride are simultaneously mixed in the presence of ^-5 mol of (NH ₄ ) ₃ RhCl ₆ , gelatin is added after removing soluble salts by a method well known in the art, 2-methyl-4 as a stabilizer without aging
-Hydroxy-1,3,3a, 7-tetrazaindene was added. This emulsion was a cubic monodispersed emulsion having an average size of 0.15 μm. (Emulsion B) To Emulsion B, a hydrazine compound shown in Table 2 was added, 2.0 × 10 ⁻⁴ mol / Ag mol of nucleation accelerator-A and 30% by weight of a solid content of polyethyl acrylate latex were added to gelatin. 2.0 wt% of 1,3-vinylsulfonyl-2-propanol as a hardening agent was added to gelatin.

On this, gelatin 1.5 g / m ² as a protective layer and polymethyl methacrylate particles (average particle size 2.5
μ) 0.3 g / m ² , and the following surfactant as a coating aid,
Apply a protective layer containing a stabilizer and a UV absorbing dye,
Dried.

Surfactant UV absorbing dye The sample was exposed to light through a document as shown in FIG. 1 using a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd., developed with a developer II at 38 ° C. for 20 seconds, fixed, washed with water,
After drying, the quality of the blank characters was evaluated.

Character image quality of 5 means that a 30 μm wide character is reproduced when an appropriate exposure is performed so that a halftone dot area of 50% becomes a halftone dot area of 50% on a return photosensitive material using an original as shown in FIG. The image quality is very good and the image quality is very good. On the other hand, the character extraction image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given, and is a poor character extraction quality. Was established. Three or more is a practical level.

The results are shown in Table 2. The sample of the present invention has excellent image quality and high Dmax.

Nucleating agent C is a nucleating agent described in EP345025A.

[Brief description of the drawings]

FIG. 1 shows a configuration at the time of exposure in the case where a character extraction image is formed by overlapping, and the reference numerals indicate the following. (A) Transparent or translucent paste base (b) Line drawing manuscript (black part shows line drawing) (c) Transparent or translucent paste base (d) Halftone manuscript (black part is halftone dot (E) Photosensitive material for return (note that the shaded area indicates the photosensitive layer)

Claims (1)

(57) [Claims] 1. A halogenated composition comprising at least one silver halide photographic emulsion layer, wherein the photographic emulsion layer or another hydrophilic colloid layer contains a compound represented by the following general formula (I). Silver photographic photosensitive material. General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, a carbamoyl group or an oxycarbonyl group. Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Y ₁ represents a divalent organic group.