JPH0679137B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention forms an extremely hard negative image, a highly sensitive negative image, a silver halide photographic light-sensitive material giving a good halftone dot image, or a direct positive photographic image. And 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 described in U.S. Pat. No. 3,730,727 (developing solution combining ascorbic acid and hydrazine) 3,227,552 (auxiliary developing for directly obtaining a positive color image). Using hydrazine as a drug) No. 3,386,831 (containing β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers) No. 2,419,975 and Thees of The Theory of Photographic Process 3 by Mees
It is known as the edition (1966), page 281 etc.

Among these, in particular, U.S. Pat. No. 2,419,975 discloses that addition of a hydrazine compound gives a negative tone image with high contrast.

In the patent specification, when a hydrazine compound is added to a silver chlorobromide emulsion and development is performed with a developer having a high pH of 12.8,
It is described that extremely hard photographic characteristics having a gamma (γ) of more than 10 can be obtained. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use.

The ultra-high contrast photographic characteristics with a gamma of more than 10 are useful for printing plate making, whether it is a negative image or a positive image.
It is very useful for photographic reproduction of continuous-tone images or reproduction of line drawings. For this purpose, the conventional content of silver chloride is 50 mol%, preferably 75 mol%.
Generally, a method of using a silver chlorobromide photographic emulsion having a particle size of more than 100% and developing with a hydroquinone developer having an extremely low effective concentration of sulfite ion (usually 0.1 mol / or less) has been generally used. However, in this method, since the concentration of sulfite ion in the developer is low, the developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, since none of these methods requires the use of a silver chlorobromide emulsion having a relatively high silver chloride content, high sensitivity cannot be obtained. Therefore, there has been a strong demand for obtaining super-high contrast photographic characteristics useful for reproducing halftone images and line images by using a high-sensitivity emulsion and a stable developing solution.

The present inventors U.S. Pat.Nos. 4,224,401 and 4,168,977,
No. 4,243,739, No. 4,272,614, No. 4,323,643, etc., disclosed a silver halide photographic emulsion which gives a very hard negative photographic property by using a stable developing solution.
It has been found that the acylhydrazine compounds used in them have several drawbacks.

That is, these conventional hydrazines are known to generate nitrogen gas during the development process, and these gases gather in the film to form bubbles, which impair the photographic image. That is, it will adversely affect other photographic light-sensitive materials by flowing out to the processing solution.

In addition, when a large amount of these conventional hydrazines are required for sensitizing and hardening, or when high sensitivity is required for the performance of the photosensitive material, other sensitization techniques (for example, chemical sensitization) are used. To increase the particle size, add a compound that promotes sensitization as described in U.S. Pat.Nos. 4,272,606 and 4,241,164, etc.) Increased fog may occur.

Therefore, a compound which can reduce the generation of such bubbles and the outflow to the developing solution, has no problem in the stability over time, and can obtain extremely hard photographic characteristics with the addition of an extremely small amount is desired. Was there.

Further, U.S. Pat.Nos. 4,385,108 and 4,269,929 describe that extremely hard negative photographic properties can be obtained by using hydrazines having a substituent that is easily adsorbed to silver halide grains. However, among the hydrazine compounds having these adsorptive groups, those specifically described in the above-mentioned known examples have a problem that they cause desensitization with time during storage. Therefore, it was necessary to select a compound that does not cause such a problem.

On the other hand, although there are various direct positive photographic methods, there is a method in which pre-fogged silver halide grains are exposed in the presence of a desensitizer and then developed, and a method in which a photosensitive nucleus is mainly present inside the silver halide grains The most useful method is to develop the silver halide emulsion in the presence of a nucleating agent after exposure. The present invention relates to the latter. A silver halide emulsion having a photosensitive nucleus mainly inside the silver halide grain and forming a latent image mainly inside the grain is said to be an internal latent image type silver halide emulsion and is mainly formed on the surface of the grain. It is distinct from the silver halide grains that form the image.

A method for directly obtaining a positive image by surface developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent and a photographic emulsion or a light-sensitive material used in such a method are described in, for example, U.S. Pat.No. 2,456,953. , No. 2,497,875, No. 2,497,876
No., No. 2,588,982, No. 2,592,250, No. 2,675,318,
3,227,552, 3,317,322, British Patent 1,011,062
No. 1,151,363, 1,269,640, 2,011,391,
JP-B-43-29,405, JP-B-49-38,164, JP-A-53-16,6
No. 23, No. 137,133, No. 54-37,732, No. 54-40,629
54, 74-536, 54-74,729, 55-52,055
No. 55-90,940.

In the above method for obtaining a direct positive image, the nucleating agent may be added to the developing solution, but the nucleating agent is added to the photographic emulsion layer of the light-sensitive material or other appropriate layer so as to be adsorbed on the silver halide grain surface. Sometimes better inversion characteristics can be obtained.

As the nucleating agent used in the method for obtaining the above direct positive image, U.S. Pat.Nos. 2,563,785 and 2,588,982, hydrazines, and U.S. Pat.No. 3,227,552, hydrazides and hydrazine compounds described in U.S. Pat. Patents 3,615,615, 3,719,494, 3,734,738,
4,094,683 and 4,115,122, British Patent 1,283,
835, heterocyclic quaternary salt compounds described in JP-A Nos. 52-3426 and 52-69613, U.S. Pat. Nos. 4,030,925 and 4,0
31,127, 4,139,387, 4,245,037, 4,255,51
No. 1 and No. 4,276,364, thiourea-bonded acylphenylhydrazine compounds described in British Patent No. 2,012,443, compounds having a heterocyclic thioamide described in U.S. Pat. 2,01
Phenylacylhydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in 1,397B, a sensitizing dye having a substituent having a nucleating action in the US Pat. No. 3,718,470 in the molecular structure, JP-A-59-200,230,
59-212,828, 59-212,829, Research Disclos
The hydrazine compounds described in Ure No. 23510 (November 1983) are known.

However, all of these compounds have insufficient activity as a nucleating agent, and those with high activity have insufficient storability, and the activity varies after being added to the emulsion and before coating. However, if added in a larger amount, the film quality deteriorates.

(Object of the Invention) Accordingly, the first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining an extremely hard negative gradation photographic characteristic with a gamma of more than 10 using a stable developing solution. Is to provide.

Secondly, an object of the present invention is to provide a negative-type silver halide containing an acylhydrazine compound which can give desired photographic characteristics of extremely high tone negative gradation with a small addition amount without adversely affecting photographic performance. It is to provide a photographic light-sensitive material.

A third object of the present invention is to provide a direct positive type silver halide photographic light-sensitive material containing a highly active nucleating agent.

Fourthly, the object of the present invention is easy to synthesize, small fluctuation in activity during the production of a light-sensitive material, excellent storage stability, and containing hydrazines which do not cause deterioration of film quality when added in a large amount. The object is to provide a good silver halide photographic light-sensitive material.

(Structure of the Invention) It is an object of the present invention to provide a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, wherein at least one kind of photographic emulsion layer or at least one hydrophilic colloid layer is provided. This has been achieved by incorporating a compound represented by the following general formula (I).

General formula (I) (In the formula, Ar represents an aryl group, B represents a formyl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxy group. A sulfonyl group, a thioacyl group, a thiocarbamoyl group or a heterocyclic group, both R ₀ and R ₀₀ are hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group,
It represents an arylsulfonyl group or an acyl group. R ₀ , R
_The alkylsulfonyl group, arylsulfonyl group and acyl group represented by ₀₀ may further have a substituent. However, B, R ₀₀ and the nitrogen atom to which these are bonded may form a partial structure of hydrazone (-N = C).

Further, Ar is at least 1 via a linking group as a substituent.
It has one or more sulfonamide groups or sulfamoyl groups.

Here, the sulfonamide group or the sulfamoyl group is -ZNSO.
₂ or -SO ₂ NZ- (Z is a hydrogen atom, a linear, branched or cyclic substituted or unsubstituted alkyl group having 30 or less carbon atoms, or a substituted or unsubstituted aralkyl having 30 or less carbon atoms A group, a substituted or unsubstituted alkenyl group having 30 or less carbon atoms, or a substituted or unsubstituted aryl group having 30 or less carbon atoms (eg, phenyl group)
Alternatively, it represents a naphthyl group. ) Is a group represented by.

The total number of Ar and B carbon atoms is 21 or more. ) Among the compounds represented by the general formula (I), the following general formula (I
Those represented by I) or (III) are preferred.

General formula (II) General formula (III) (In the formula, A ₁ represents a substituted phenylene group or a substituted naphthylene group; A ₂ represents a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group; X is an aliphatic residue, an aromatic residue or a heterocyclic group. Represents a residue; L ₁ and L ₃ represent an n + 1 valent organic group; L ₂ represents —CO—, —SO, or —SO ₂ —; m represents 0 or an integer of 1 to 3, and n Represents an integer of 1 to 3; B, R ₀ and R ₀₀ are represented by the above general formula ((I)).
Represents a group having the same meaning as defined in.

X has at least one sulfonamide group (-NZSO _2- ; Z has the same meaning as described above) or sulfamoyl group (-SO ₂ NZ; Z has the same meaning as described above) as a substituent, Z
Is preferably a hydrogen atom.

Further, the total number of carbon atoms of X, L ₁ , A ₁ and B is 21 or more.

Preferred among the groups represented by L ₁ are those represented by the general formula (IV)
Is a group having 40 or less carbon atoms.

In the general formula _{(IV) La q Lb r p} ( wherein, La represents a group capable of binding with X in formula (II), a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, carbon atoms 6 ~ 30 substituted or unsubstituted phenylene group or naphthylene group, substituted or unsubstituted aralkylene group having 7 to 30 carbon atoms, or substituted or unsubstituted 5 or 6-membered heterocyclic ring having 1 to 30 carbon atoms Represents a divalent group (containing at least one of N, O and S as a hetero atom); Lb represents -O-, -CONR
−, −NRCO−, −SO ₂ NR−, −NRSO ₂ −, −OCO−, −COO
-, - S -, - NR -, - CO -, - SO -, - SO 2 -, - OCO
O-, -NRCONR'-, -NRCOO-, -OCONR-, or -NRS
O ₂ NR′- (wherein R and R ′ are independently hydrogen atoms,
A linear, branched, or cyclic substituted or unsubstituted alkyl group having 30 or less carbon atoms may be linked to each other to form a ring, or a substituted or unsubstituted phenyl group having 30 or less carbon atoms. Represents a group or a naphthyl group. ); P is 1
Or 2 and q and r represent 0, 1 and 2,
q and r never become 0 at the same time.

Particularly preferred among the groups represented by L ₁ are those having 7 to 40 carbon atoms, and Lb represents —NHCONH—.

Preferred as the substituent on A ₁ are a halogen atom, an alkoxy group having 30 or less carbon atoms in addition to L ₁ (for example, a methoxy group, a 2-hydroxyethoxy group, a 2-methoxyethoxy group, a hexadecyloxy group, etc.). , An aryloxy group (eg, phenoxy group, 4-methylphenoxy group, 2,4
-Ditert-pentylphenoxy group, etc., having 30 or less carbon atoms, a secondary or tertiary amino group having 30 or less carbon atoms (for example, diethylamino group, di (2-hydroxyethyl) amino group, N -Methyl-N-octylamino group, morpholino group, N-methyl-N-phenylamino group, etc.), linear, branched, or cyclic alkyl group having 30 or less carbon atoms (for example, methyl group, tert-pentyl group, A cyclohexyl group, a hexadecyl group, etc.) and a substituted alkyl group (for example, 2-hydroxyethyl group, benzyl group, (2-hydroxyphenyl) methyl group, 3-acetylpropyl group, etc.), a group represented by —COR ¹ (provided that R ¹ represents a group having the same meaning as the above alkyl group, alkoxy group, aryloxy group and amino group), and a group represented by -SO ₂ R ₂ (provided that R ²
Represents a group having the same meaning as the above alkyl group or amino group), and a hydroxy group.

More specifically, R ₀ and R ₀₀ in formulas (I)), (II) and (III) are more specifically a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a hamet). The sum of the substituent constants of is −0.
A phenylsulfonyl group substituted to be 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 the substituent constants of Hamet is -0.5 or more, or Linear or branched or cyclic unsubstituted and substituted aliphatic acyl groups (the substituents include, for example, halogen, ether group, sulfonamide group, carbonamido group, hydroxyl group, carboxyl group, sulfonic acid group). Most preferably, R ₀ and R ₀₀ are hydrogen atoms.

B in the general formulas (II) and (III) is specifically a formyl group, an acyl group (acetyl group, propionyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, 4-chlorobenzoyl group, pyruvoyl group, Methoxalyl group, methyloxamoyl group, etc.), alkylsulfonyl group (methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.), alkylsulfinyl group (methanesulfinyl group, etc.), Arylsulfinyl group (benzenesulfinyl group, etc.), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, methoxyethoxycarbonyl) Group, etc.), aryloxyca Bonyl group (phenoxycarbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl (methoxysulfonyl group, ethoxysulfonyl group, etc.), thioacyl group (methylthiocarbonyl group, etc.), thiocarbamoyl group ((methylthio A carbamoyl group) or a heterocyclic group (pyridine ring, etc.).

A formyl group or an acyl group is particularly preferable as B, and the acyl group is an aliphatic, aromatic, or heterocyclic group which may have a substituent and has 2 to 30 carbon atoms. preferable. Examples of the substituent on the acyl group include a hydroxy group, an alkoxy group, a sulfonamide group, a carbonamide group, a ureido group, a hydroxyphenyl group and an aryloxy group.

Most preferred as B is formyl.

R _{00 in the} general formulas (II) and (III) is a partial structure of hydrazone together with B and the nitrogen atom to which they are bonded. May be formed.

In addition, R ₀₀ in the general formula (III) is L ₂ and the nitrogen atom to which they are bonded together with the partial structure of hydrazone. May be formed.

In the above, R ″ represents an alkyl group, an aryl group or a heterocyclic group. R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of hydrazones formed by R ₀₀ and B or L ₂ are acetone hydrazone, benzaldehyde hydrazone, o
-Hydroxybenzaldehyde hydrazone and the like can be mentioned.

Preferred among the groups represented by L ₃ are groups having 10 to 40 carbon atoms represented by the following general formula (V).

General formula (V) (In the formula, La and Lb represent a group having the same meaning as defined in the general formula (IV), l ₁ is 0 or 1, l ₂ is 0 or 1, l ₃ is 1 or 2
Represents ) Particularly preferred among the groups represented by L ₃ are those having 10 to 40 carbon atoms, and Lb is —CONH—, —SO ₂ NH.
-, -NHCONH-.

Among the groups represented by L ₂ , a particularly preferable one is -CO-.

m is preferably 0 or 1, and n is preferably 1 or 2.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

Next, typical synthetic methods of the compound of the above general formula (I) will be described with reference to synthetic examples. The compound of the present invention can be obtained, for example, from JP-A-56-67843, U.S. Pat.
It can be synthesized with reference to No. 0,638.

Synthesis Example 1. Synthesis of compound 1 (1) Synthesis of 2- [4- [3- (3-nitrophenyl) ureido] phenyl] -1-formylhydrazine 2- (4-aminophenyl) -1-formylhydrazine
To 60.4 g, 200 ml of cetonitrile and 200 ml of N, N-dimethylformamide were added and dissolved, and the mixture was cooled to -5 ° C. 65.6 g of meta-nitrophenyl isocyanate in 200 ml of acetonitrile
And was added dropwise. During this, stirring was performed while cooling so that the liquid temperature did not exceed -5 ° C. After adding 300 ml of acetonitrile and stirring at 0 ° C for 3 hours, the resulting crystals were collected,
Wash with acetonitrile then methanol. The obtained crystals were dissolved in N, N-dimethylformamide (1), the insoluble portion was passed through, methanol 3 was added to the solution, and the mixture was cooled to give crystals. The crystals were collected and washed with acetonitrile and then methanol. Yield 9
8.5g (2) Synthesis of 2- [4- [3- (3-aminophenyl) ureido] phenyl] -1-formylhydrazine Iron powder 138g, ammonium chloride 5g, dioxane 2.45, and water 985ml are mixed on a steam bath. Heated and stirred. To this was added 98 g of the nitro compound obtained in (1), and the mixture was refluxed for 40 minutes. Next, insoluble matter was passed through, the solution was concentrated under reduced pressure, and then water was added. The resulting crystals were collected and washed with acetonitrile. Yield 79g (3) Synthesis of compound 1 Under a nitrogen atmosphere, 26.1g of the amino compound obtained in (2) was added to N, N-
Dissolve in 90 ml of dimethylacetamide, and then add 90 ml of acetonitrile and 10.2 g of N-methylmorpholine at -5 ° C.
Cooled to. To this was added 4- (2,4-di-tert-pentylphenoxy) -1-butylsulphonyl luchloride 42.7
g was added dropwise. During this, cooling and stirring were performed so that the liquid temperature did not exceed 0 ° C. The mixture was continuously stirred at 0 ° C. for 1 hour and then poured into water 1 to separate the organic layer. The organic layer was concentrated, separated and purified by silica gel column chromatography (developing solvent: ethyl acetate), and recrystallized with a mixed solvent of ethanol and n-hexane (vol / vol = 1/10). Yield 32g, melting point 139
-141 ° C (decomposition) Synthesis example 2. Synthesis of compound 3 Under a nitrogen atmosphere, 5 g of 3- {3- (2,4-di-tert-pentylphenoxy) propylsulfamoyl} aniline was added to N,
It was dissolved in 10 ml of N-dimethylacetamide, 2.0 g of pyridine was added, and the mixture was cooled to -5 ° C. To this, 2.1 g of phenylchloroformate was added dropwise. During this, cooling and stirring were performed so that the liquid temperature did not exceed 0 ° C. After stirring for 30 minutes at 0 ℃,
Further, the mixture was stirred at room temperature (about 25 ° C) for 1 hour. To this, 3.5 ml of triethylamine was added, and further, a solution of 2.0 g of 2- (4-aminophenyl) -1-formylhydrazine dissolved in 10 ml of N, N-dimethylacetamide was added dropwise, and the mixture was stirred at 50 ° C for 3 hours.
The mixture was heated and stirred for an hour. After cooling to 30 ° C, 0.5 mol /
Was poured into a mixture of 100 ml of hydrochloric acid and 100 ml of ethyl acetate.
The organic layer was separated, concentrated, and recrystallized with a mixed solvent of ethyl acetate and n-hexane (vol / vol = 2/5). Yield 3.6 g, melting point 100-104 ° C. (decomposition) In order to include the compound of the present invention in the hydrophilic colloid layer, after dissolving the compound of the present invention in water or a water-miscible organic solvent (necessary Alkali hydroxide or tertiary amine may be added according to the requirement to form a salt to dissolve it), or it may be added to a hydrophilic colloid solution (eg, silver halide emulsion, gelatin aqueous solution, etc.) (at this time, if necessary). The pH may be adjusted accordingly by addition of acid or alkali).

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

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

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

The silver halide grains in the photographic emulsion may have a regular crystal such as a cube or octahedron,
Further, it may have irregular crystals such as spheres and plates, or may have a composite form of these crystal forms.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are allowed to coexist in the process of forming silver halide grains or physically ripening. Good.

The silver halide particularly suitable for use in the present invention is prepared in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol of silver, and the silver iodide content on the surface of the grain is the average grain size. The silver haloiodide has a higher silver iodide content.
When an emulsion containing such a silver haloiodide is used, higher sensitivity and high gamma photographic characteristics can be obtained.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, rhodium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin.

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

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), potassium hexachloroiridium (IV), ammonium hexachloroiridium (III), etc. There is.

In the present invention, the silver halide emulsion layer is a Japanese Patent Application No. 60-6419.
9. It is preferable to include two types of monodisperse emulsions having different average grain sizes as disclosed in Japanese Patent Application No. 60-232086, from the viewpoint of increasing the maximum density (Dmax). Small size monodisperse grains are chemically sensitized. The chemical sensitization method is most preferably sulfur sensitization. The large size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Large-sized monodisperse particles generally do not easily undergo black sensitization and therefore are not chemically sensitized. However, when chemical sensitization is performed, it is particularly preferable to apply shallowly so as not to generate black pits. Here, "shallowing" means that the chemical sensitization is performed for a shorter time than the chemical sensitization of small-sized grains, the temperature is lowered, and the addition amount of the chemical sensitizer is suppressed. The difference in sensitivity between the large size monodisperse emulsion and the small size monodisperse emulsion is not particularly limited, but ΔlogE is 0.1 to 1.0, more preferably 0.2 to 0.7, and the large size monodisperse emulsion is preferably high.

Here, the sensitivity of each emulsion is such that a hydrazine derivative is contained in the emulsion and the emulsion is coated on a support to contain sulfite ion of 0.15 mol / mol or more.
It is obtained when processed with a developer having a pH of 10.5 to 12.3. More specifically, the evaluation method described in Example 1 is applied.

The average particle size of the average size of small size monodisperse particles is
90% or less of large-sized silver halide monodisperse grains,
It is preferably 80% or less. The average grain size of the silver halide emulsion grains is preferably 0.02μ to 1.0μ, more preferably 0.1μ to 0.5μ, and the average grain size of large size and small size monodisperse grains may be included in this range. preferable.

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

In the present invention, monodisperse emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into different layers. When they are incorporated in separate layers, it is preferred that the large emulsion is the upper layer and the small emulsion is the lower layer.

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

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

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

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978) Page 23 I
It is described in J of V.

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

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts, aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3
-Vinyl sulfonyl-2-propanol etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids and the like can be used alone or in combination.

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

In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. When used as an antistatic agent, a surfactant containing fluorine (see, for example, U.S. Pat. No. 4,201,586, JP-A-60-80849, 59-59).
74554) is particularly preferred.

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

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer having a monomer component of alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, or the like is used. Can be used.

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

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

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

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

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

As a preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite and the like. Sulfite is preferably 0.4 mol / mol or more, particularly preferably 0.5 mol / mol or more.

In the developer of the present invention, a silver stain preventing agent is disclosed in JP-A-56-24,3.
The compounds described in No. 47 can be used. The compounds described in Japanese Patent Application No. 60-109,743 can be used as dissolution aids added to the developing solution. Further used for developer
The compound described in JP-A-60-93,433 or the compound described in Japanese Patent Application No. 61-28,708 can be used as the pH buffer.

The compound represented by the general formula (I) can be used in combination with a negative-working emulsion as described above for a high-contrast light-sensitive material, and can also be used in combination with an internal latent-image-type silver halide emulsion. Describe. In this case, the general formula (I)
The compound represented by is preferably contained in the internal latent image type silver halide emulsion layer, but may be contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer.
Such a layer is a layer having any function, such as a coloring material layer, an intermediate layer, a filter layer, a protective layer, an anti-halation layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. May be.

The content of the compound represented by the general formula (I) in the layer is such that an internal latent image type emulsion gives a sufficient maximum density (for example, 1.0 or more in silver density) when developed with a surface developer. Is desirable. In practice, the appropriate content may vary over a wide range as it depends on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but internal latent image type halogenation About 0 per mole of silver in the silver emulsion.
A range of 005 mg to 500 mg is practically useful, with about 0.01 mg to about 100 mg per silver mole being preferred. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as the 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, page 18 to page 20.

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 the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Examples of these sensitizing dyes include JP-A-59-4
Cyanine dyes and merocyanine dyes described in Nos. 0,638, 59-40,636 and 59-38,739 are included.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, it can be developed with a developing solution containing a color image forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are RESATE DISCLOSURE (RD) 17643 (December 1978) Item VII-D and 18717 (1).
(November 979).

It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylcetoamide coupler.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and a representative example thereof is an oxygen atom-releasing type yellow coupler or a nitrogen atom-releasing type yellow coupler. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

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

As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole coupler, U.S. Pat.
Pyrazolobenzimidazoles described in 9,899, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230.
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. A cyan coupler which is fast against humidity and temperature is preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, 2,5-diacylamino-substituted phenol couplers, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In order to correct the unnecessary absorption in the short wavelength region which the dyes formed from the magenta and cyan couplers have, it is preferable to use a colored coupler together with the color photosensitive material for photographing.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

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

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

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

The photographic emulsion used in the present invention is combined with a dye image-providing compound (coloring material) for a color diffusion transfer method capable of releasing a diffusible dye in response to the development of silver halide, and subjected to an appropriate development treatment. After that, it can be used to obtain a desired transferred image on the image receiving layer. A large number of such color materials for color diffusion transfer method are known, and among them, although they are initially non-diffusive, they are formed by a redox reaction with an oxidation product of a developing agent (or an electron transfer agent). It is preferable to use a coloring material of a type that cleaves to release a diffusible dye (hereinafter abbreviated as DRR compound). Of these, a DRR compound having an N-substituted sulfamoyl group is preferable. Particularly preferred in combination with the nucleating agent of the present invention, U.S. Pat.Nos. 4,055,428, 4,053,312 and
DRR compounds having an o-hydroxyarylsulfamoyl group as described in US Pat.
It is a DRR compound having a redox nucleus as described in 3-149,328. When used in combination with such a DRR compound, the temperature dependence during treatment is remarkably small.

Specific examples of the DRR compound include those described in the above patent specifications, and as the magenta dye image-forming substance, 1-
Hydroxy-2-tetramethylene sulfamoyl-4-
[[3'-Methyl-4 '-(2 "-hydroxy-4"-
Methyl-5 "-hexadecyloxyphenylsulfamoyl) -phenylzo] -naphthalene, 1-phenyl-3-cyano-42 as a yellow dye image-forming substance,
4-di-tert-pentylphenoxyacetamino)-
Examples thereof include phenylsulfamoyl] phenylazo) -5pyrazolone.

The photosensitive material using the internal latent image type emulsion of the present invention can directly obtain a positive image by developing with a surface developing solution. A surface developer is one in which the development process thereby is substantially induced by latent images or fog nuclei on the surface of the silver halide grains. Although it is preferable not to include a silver halide dissolving agent in the developing solution, a silver halide dissolving agent (for example, sulfurous acid) may be used as long as the internal latent image does not substantially contribute until development by the surface development center of the silver halide grain is completed. Some may be included).

To develop a light-sensitive material using the internal latent image type emulsion of the present invention, various known developing agents can be used.

Examples of the present invention will be shown below, but the present invention is not limited thereto.

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

Example 1 Emulsions [A] and [B] were prepared as follows.

[Emulsion A]

An aqueous solution of silver nitrate, an aqueous solution of potassium iodide and an aqueous solution of potassium bromide are simultaneously added to an aqueous gelatin solution kept at 50 ° C. in the presence of 4 × 10 ^-7 moles of iridium hexachloride and ammonia per 1 mole of silver.
A cubic monodisperse emulsion having an average grain size of 0.3 μm and an average silver iodide content of 1 mol% was prepared by adding the mixture over 60 minutes and keeping the pAg at 7.8.

[Emulsion B]

In the same manner as in Emulsion A, the amounts of potassium iodide and ammonia were adjusted to prepare a cubic monodisperse emulsion having an average grain size of 0.22 μm and an average silver iodide content of 0.1 mol%. For both emulsions A and B,
Desalination was performed by the flocculation method. Emulsion B was then sensitized with sulfur by hypo, and the average grain size was 0.22.
A cubic monodisperse sulfur-sensitized emulsion having a .mu., average silver iodide content of 0.1 mol% was prepared.

In these silver iodobromide emulsions, sodium salt of 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine was used as a sensitizing dye, and 4-hydroxy- was added as a stabilizer. 6-methyl-1,3,3a, 7-tetrazaindene, aqueous latex (a) represented by the following structural formula, aqueous latex (a) A dispersion of polyethyl acrylate and 1,3-divinylsulfonyl-2-propanol were added, and then Emulsions A and B were mixed at a silver halide weight ratio of 1: 4. The compound (I) was added per mol of silver as shown in Table 1, and then coated on a polyethylene terephthalate film at a silver amount of 3.4 g / m ² . Each sample was exposed and developed to measure photographic characteristics. The results are shown in Table 1.

The developer having the following formulation was used.

Developer formulation Hydroquinone 45.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18.0g Potassium hydroxide 55.0g 5-Sulfosalicylic acid 45.0g Boric acid 25.0g Potassium sulfite 110.0g Ethylenediaminetetraacetic acid disodium salt Salt 1.0 g Potassium bromide 6.0 g 5-Methylbenzotriazole 0.6 g n-Butyldiethanolamine 15.0 g Water is added to adjust the pH to 11.60.

From the above results, the compounds of the present invention are comparative compounds a and b.
It can be seen that with a smaller addition amount, a hard gradation is given and the halftone dot quality is excellent.

Example 2 [Preparation of Emulsion C] An aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 5 × 10 ⁻⁶ mol of ammonium hexachlororhodium (III) chloride per mol of silver were adjusted to pH in a gelatin solution at 40 ° C. by a double jet method. The mixture was controlled so as to be 2.3, and a monodisperse silver chloride emulsion having an average grain size of 0.2 micron was prepared.

After the particles are formed, soluble salts are removed by a flocculation method well known in the art, and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 1-phenyl are used as stabilizers. -5-Mercaptotetrazole was added. Gelatin contained in 1 kg of emulsion is 55 g, and silver is 10
It was 5g.

Dye compound C Using Emulsion C, the compounds of the present invention shown in Table 2 and the above-mentioned dye compound C (130 mg / m ² ) were added, and 2,4-dichloro-6-hydroxy-1,3 as a hardener. 1,5 triazine sodium salt was added, and a silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 3.5 g per 1 m ² , and a gelatin layer as a protective layer was further coated thereon. Sample numbers (2-1) to (2-10)
To prepare a light-sensitive material.

Each light-sensitive material was exposed through an optical wedge with a P-617DQ type printer (light source 100V, 1kW quartz halogen lamp) manufactured by Dainippon Screen Co., Ltd., and then developed with a developer having the same composition as in Example 1 at 38 ° C. for 20 seconds. The method of fixing, washing with water and drying were carried out.

The density of each developed sample was measured, and the relative value of the exposure dose that gave a density of 4.0 was determined.

Each of the light-sensitive materials of sample numbers (2-1) to (2-10) is used as a safelight light by Toshiba's anti-fading fluorescent lamp (FLR40SW-DL
After being left for 0 to 60 minutes under the light of -X NU / M) of 200 lux, it was developed with a developer having the same composition as in Example 1 at 38 ° C for 20 seconds, fixed, washed with water and dried.

The density of each obtained sample was measured, and the limit irradiation time at which the fog density of each sample began to increase was determined. (The fog density is
The time to rise by 0.02 was set as the limit. The obtained results are shown in Table 2.

From the results of Table 2, sample numbers (2-4) to
The light-sensitive material (2-10) has a sensitivity capable of being practically exposed and printed with a 1 kW quartz halogen lamp, and is excellent in safelight safety under a fluorescent lamp of an ultraviolet light cut.

Of particular note is that the compound of the present invention has a marked contrast enhancement effect and a strong film strength with respect to an emulsion containing a large amount of Rh as compared with the comparative compounds a and b.

Example 3 Photosensitive elements 1 to 9 were prepared by coating respective layers on a polyethylene terephthalate transparent support in the following order.

(1) A copolymer described in U.S. Pat. No. 3,898,088 containing the following repeating units in the following ratio (3.
0g / m ² ) A mordant layer containing x: y = 50: 50 and gelatin (3.0 g / m ² ).

(2) Titanium oxide 20 g / m ² and the white reflective layer containing gelatin 2.0 g / m ^2.

(3) Carbon black 2.70 g / m ² and gelatin 2.70
Light-shielding layer containing g / m ² .

(4) below the magenta DRR compound (0.45 g / m ^2), diethyllaurylamide (0.10g / m ^2), 2,5- di -t- butyl High hydroquinone (0.0074 g / m ^2), and gelatin (0.76
g / m ² ) containing layer.

(5) Nucleating agent and 5-pentadecyl-hydroquinone-2-sulfone shown in Table 3 containing an internal latent image type emulsion (1.4 g / m ² in silver amount) and a green sensitizing dye (1.9 mg / m ² ). A green-sensitive internal latent image type direct positive silver iodobromide emulsion (2 mol% silver iodide) layer containing sodium acidate (0.11 g / m ² ).

(6) A layer containing gelatin (0.94 g / m ² ).

Processing was carried out by combining the above-mentioned photosensitive elements 1 to 9 and the following respective elements.

Processing liquid A container that can be ruptured under pressure by 0.8 g each of the treatment liquid of the above composition
Filled.

Cover sheet Polyacrylic acid (neutralization layer) of polyacrylic acid (viscosity of about 1,000 cp in 10% by weight aqueous solution) 15 g / m ² on the polyethylene terephthalate support, and acetyl cellulose (100 g of acetyl of 100 g acetyl) as the neutralization timing layer. 3.8 g / m ² of styrene and maleic anhydride (composition (molar) ratio, styrene: maleic anhydride = about 60:40, molecular weight about 50,000) A cover sheet coated with 0.2 g / m ² was prepared.

Forced deterioration condition Two sets of the above-mentioned photosensitive elements 1 to 9 are prepared, and one set is a refrigerator (5
C.) and the other set was left for 4 days at a temperature of 35.degree. C. and a relative humidity of 80%.

Processing step The cover sheet and the photosensitive sheet are overlaid, and after exposing the color test chart from the cover sheet side, the processing solution is spread between both sheets so as to have a thickness of 75 μ I went with the help of a roller). The treatment was carried out at 25 ° C. After the processing, the green density of the image formed on the image-receiving layer was measured with a Macbeth reflection densitometer one hour after the processing through the transparent support of the photosensitive sheet. The results are shown in Table 3.

As is clear from the above results, in the light-sensitive elements 3 to 9 to which the nucleating agent of the present invention is added, Dmax is more likely to occur with the same addition amount than in the light-sensitive element 2 produced by the conventional method, and the light-sensitive element 3 is obtained. ~ 9
From 1, it can be seen that there is less change in sensitivity when the photosensitive material is aged.

Example 4 (1) Preparation of hydrazine compound solution Solution A: Compound 1 was dissolved in methanol containing 10% water to a concentration of 0.8%.

Solution B: Compound 3 was dissolved in methanol containing 10% water so that the concentration was 0.8%.

Solution C: Compound 4 was dissolved in methanol containing 10% water so that the concentration was 0.8%.

Solution D: An equimolar 0.1N sodium hydroxide aqueous solution was added to Compound 6, and then a methanol solution containing 10% of water was added to adjust the concentration of Compound 6 to 0.8%.

Solution E: Compound 7 was dissolved in methanol to a concentration of 0.8%.

Solution F: The comparative compound was dissolved in methanol to a concentration of 2%.

Comparative compound a (2) Preparation of light-sensitive material sample A cubic monodispersed silver iodobromide emulsion having an average grain size of 0.3μ (silver iodide content: 2 mol%) was prepared and washed with water by a conventional method to remove soluble salts. Chemical sensitization was performed by adding sodium thiosulfate and potassium chloroaurate. The emulsion contained gelatin in an amount of 0.30 gelatin / silver nitrate (weight ratio). Anhydro-5,5'-dichloro-9-ethyl-3,3'-bis- (3-
Sulfopropyl) oxacarbocyanine sodium hydroxide salt was added, and 2- (N-methyl-N-oleoylamino) ethanesulfonic acid sodium salt corresponding to 60 mol% of the hydrazine compound was added, and the solution A or One of the solutions E was added so that the amount of each hydrazine compound was 9.0 × 10 ^-4 mol per mol of silver, and the amount of the solution F was 1.6 × 10 ^-3 mol per mol of silver. To prepare a polyethyl acrylate dispersion, and immediately after or stirring at 38 ° C for 6 hours, 2-hydroxy-4,6- The sodium salt of dichloro-1,3,5-triazine was added and coated on polyethylene terephthalate flume so that the coated silver amount would be 3.6 g / m ² . At this time, the protective layer was simultaneously applied.

(3) Evaluation method The sensitivity and gamma were evaluated by sensitometry in which each sample was exposed for 1 second under an optical wedge.

The treatment was carried out by developing the following developing solution at 38 ° C. for 30 seconds, and then stopping, fixing, washing with water and drying.

Developer Hydroquinone 40.0g 4,4-Dimethyl-1-phenyl-3-pyrazolidone 0.4g Sodium hydroxide 13.0g Anhydrous potassium sulfite 90.0g Potassium triphosphate 74.0g Ethylenediaminetetraacetic acid disodium 1.0g Potassium bromide 6.0g 5 -Methylbenzotriazole 0.6 g 1-Diethylamino-2,3-dihydroxypropane 17.0 g Water was added 1 (adjusted to pH 11.5 with potassium hydroxide). The results are shown in Table 4.

As is apparent from Table 4, when the comparative compound is added (No. 4-6), the sensitivity and gamma are remarkably lowered with the passage of time of the coating solution after the addition. On the other hand, the sample of the present invention (No. 4
-1 to 4-5) show good sensitivity and gamma both when added immediately before coating and when added 6 hours before coating. That is, it is understood that the compound of the present invention has excellent stability over time when added to a photographic emulsion.

Example 5 Preparation of Emulsion D An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring at 75 ° C. over about 40 minutes, and the octahedron monodisperse having an average particle size of 0.4 μm was added. A silver bromide emulsion of was obtained. To this emulsion, add 4 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver, and add at 75 ° C.
Chemical sensitization was performed by heating for 80 minutes. The silver bromide grains thus obtained were used as cores for further growth by treating for 40 minutes in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / average particle size of 0.6 μm /
A shell silver bromide emulsion was obtained. After washing and desalting, add 1 silver to this emulsion.
Add 0.9 mg of sodium thiosulfate per mole and add 60 at 65 ° C.
After heating for a minute, chemical sensitization was performed to obtain an internal latent image type silver halide emulsion D.

A multilayer color photographic paper having the layer constitution shown in Table 5 was prepared on a paper support laminated on both sides with polyethylene using the core / shell type autopositive emulsion D. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 10 g of yellow coupler (a) and 2.3 g of color image stabilizer (b) in 10 ml of ethyl acetate and solvent (c)
4 ml was added and dissolved, and this solution was emulsified and dispersed in 90 ml of a 10% gelatin aqueous solution containing 5 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive dye was added to the above silver bromide emulsion D (containing 70 g / kg of Ag) at 2.0 × 1 per mol of silver bromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 ^-4 mol. The emulsified dispersion and emulsion were mixed and the concentration was adjusted with gelatin so that the composition shown in Table 5 was obtained, and the nucleating agent was added in the amounts shown in Table 5 to prepare a coating for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy-3 as a gelatin hardening agent for each layer,
5-Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue sensitive emulsion layer; Green-sensitive emulsion layer; Red-sensitive emulsion layer; The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; Structural formulas of compounds such as couplers used in this example are as follows.

(A) Yellow coupler (B) Color image stabilizer (C) Solvent (isoC ₉ H ₁₉ O ₃ P = O (d) (E) Magenta coupler (F) Color image stabilizer (G) Solvent 2: 1 mixture (weight ratio) (h) UV absorber 1: 5: 3 mixture (molar ratio) (i) Color mixture inhibitor (J) Solvent (isoC ₉ H ₁₉ O ₃ P = O (k) Cyan coupler When 1: 1 mixture (molar ratio) (l) Color image stabilizer 1: 3: 3 mixture (molar ratio) (m) Solvent (N) Nucleating agent: shown in Table 6.

(O) Nucleation accelerator A multilayer silver halide color photographic light-sensitive material can be prepared by simultaneously coating the coating solutions for the first to seventh layers after adjusting the balance of surface tension and viscosity. In this way, the samples shown in Table 6 were prepared.

These samples were subjected to gradation exposure for sensitometry with a stretcher (Fuji Color Head 609 manufactured by Fuji Photo Film Co., Ltd.), and then developed by the following processing steps. Processing temperature Temperature Image developer 33 ° C 3.5 minutes Bleach-fix solution 33 ° C 1.5 minutes Water wash 28-35 ° C 3.0 minutes Developer nitrilotriacetic acid ・ 3Na 2.0g Benzyl alcohol 15ml Diethylene glycol 10ml Na ₂ SO ₃ 2.0g KBr 0.5g Hydroxylamine sulfate 3.0 g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine / sulfate 5.0 g Na ₂ CO ₃ (monohydrate) 30g Add water to make it 1 (pH10.1) Bleach and fixer Ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe (EDTA)] 55g EDTA ・ 2Na 4g Add water to make it 1 (pH 6 .9) From the results shown in Table 6, it is clear that the compound of the present invention is superior to the comparative compound having a similar structure in forming a color image in combination with the autopositive emulsion as shown in this Example.

Example 6 5.0 × 10 ⁻⁶ per mol of silver in a gelatin aqueous solution kept at 40 ° C.
Simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of molar NH ₄ RhCl ₆ and then removing soluble salts by a method well known in the art, and then adding gelatin,
2-Methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer without chemical aging. The emulsion was a cubic monodisperse emulsion having an average grain size of 0.2μ.

To this emulsion were added the compounds of the general formula (I) of the present invention in the amounts shown in Table 7, and desensitizers and nucleation accelerators were added as shown below.

(Desensitizer) 14mg / m ² (Nucleation accelerator) 20mg / m ² (UV absorbing dye) After adding 350 mg / m ^{2 of the} above compound, polyethyl acrylate latex was added to gelatin in an amount of 30 wt% based on the solid content, and 1,3-vinylsulfonyl-2-propanol was added as a hardener to the polyester support. It was applied so that the Ag amount was 3.8 g / m ² . Gelatin was 1.8 g / m ² . A 1.5 g / m ² layer of gelatin was applied as a protective layer thereon.

This sample was exposed through an optical wedge with a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd., exposed to light at 38 ° C. for 30 seconds (developer solution formulation was the same as in Example 1), fixed, washed with water and dried.

The results of the obtained photographic properties are shown in Table 7.

As is clear from Table 7, the compounds of the present invention have a lower sensitivity and a significantly higher contrast image than emulsions containing a desensitizer as compared with Comparative Compounds a and b.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsunori Matsushita 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. Examiner Kayoko Yasuda (56) Reference JP-A-55-62443 (JP, A) JP Patent JP-A-59-212828 (JP, A) JP-A-61-147247 (JP, A) JP-A-61-170733 (JP, A) JP-A-61-259249 (JP, A) JP-A-61-270744 (JP , A) JP-A-63-32538 (JP, A)

Claims (1)

[Claims] 1. A support comprising at least one photosensitive silver halide emulsion layer, and at least one of said emulsion layer and / or other constituent layers is represented by the following general formula (I). A silver halide photographic light-sensitive material containing at least one compound described below. General formula (I) (In the formula, Ar represents an aryl group, B represents a formyl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxy group. A sulfonyl group, a thioacyl group, a thiocarbamoyl group or a heterocyclic group, R ₀ and R ₀₀ are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, or one is a hydrogen atom and the other is an arylsulfonyl group,
Alternatively, one represents a hydrogen atom and the other represents an acyl group. However, B, R ₀₀ and the nitrogen atom to which these are bonded may form a partial structure of hydrazone (-N = C). Further, Ar has at least one group selected from a sulfonamide group and a sulfamoyl group as a substituent via a linking group, and the total number of carbon atoms of Ar and B is 21 or more. However, the case where Ar or B is substituted with a sulfonic acid group, a carboxyl group, a phosphonic acid group or a salt thereof is excluded.