JPH0743515B2 - 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.
No. (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (containing β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizer), No. 2,419,975 Or Mee
s) Known by The Theory of Photographic Process, 3rd edition (1966), p.

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 the photographic reproduction of continuous tone images or the reproduction of line images by the dot image useful for printing plate making, whether it is a negative image or a positive image. Extremely useful. For this purpose, conventionally, a silver chlorobromide photographic agent having a silver chloride content of more than 50 mol%, preferably more than 75 mol%, has been used, and the effective concentration of sulfite ion is extremely low (usually 0.1 mol%). The method of developing with a hydroquinone developing solution (/ l or less) was generally used. However, in this method, since the concentration of sulfite ion in the developer is low, the developer is extremely unstable,
It does not survive storage 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, it is known that these conventional hydrazines generate nitrogen gas during the development processing, and these gases collect in the film and become bubbles to impair the photographic image. The fact that it leaks into the liquid adversely affects other photographic light-sensitive materials.

In addition, these conventional hydrazines cause not only the extremely high sensitivity but also the undesired development of black spots due to the infectious development, which is a serious problem in the photomechanical process. Black spots are, for example, black spots that occur in the non-developed areas between halftone dots, and increase with the passage of time of the light-sensitive material, especially during storage under high temperature and high humidity, fatigue of the liquid over time, etc. However, due to the decrease of sulfite ion, which is generally used as a preservative, and the increase of pH value, it frequently occurs and the commercial value as a photosensitizer for photolithography is remarkably reduced.

Therefore, great efforts have been made to improve this black spot (for example, use of a hydrazine compound having a nitrogen-containing heterocycle described in JP-A Nos. 62-275247 and 63-8715). ), But the black spot improvement often accompanies a decrease in sensitivity and gamma (γ).
Further, it has been desired to develop a silver halide photographic light-sensitive material having photographic characteristics with less black spots.

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, increase the particle size, add a compound that promotes sensitization such as described in U.S. Pat.Nos. 4,272,606 and 4,241,164), and generally sensitize over time during storage and Increased fog may occur.

Therefore, there is a demand for a compound that can reduce the occurrence of such bubbles and the flow into a developing solution, has no problem in stability over time, and can obtain extremely hard photographic characteristics with the addition of an extremely small amount. It was

Also, U.S. Pat.Nos. 4,385,108, 4,269,929, and 4,24
No. 3,739 describes that hydrazines having substituents that are easily adsorbed to silver halide grains can be used to obtain extremely hard negative tone gradation photographic properties. Among the hydrazine compounds, those specifically mentioned 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 photography methods, there is a method of developing after exposure in the presence of pre-fogged silver halide grains and a desensitizing agent, and a method of mainly using a halogen having a photosensitive nucleus inside the silver halide grains. The most useful method is to expose the silver halide emulsion and then develop it in the presence of a nucleating agent. 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 can be distinguished from the image forming silver halide grains.

There is known a method for directly obtaining a positive image by surface-developing an internal latent image 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.

In the above method for obtaining a direct positive image, the nucleating agent may be added to the developing solution, but when added to the photographic emulsion layer of the light-sensitive material or other appropriate layer, it is adsorbed on the surface of the silver halide grain. 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, the heterocyclic quaternary salt compounds described in JP-A Nos. 52-3426 and 52-69613, U.S. Pat. Nos. 4,030,925 and 4,03
1,127, 4,139,387, 4,245,037, 4,255,511
And 4,276,364, thiourea-bonded acylphenylhydrazine compounds described in British Patent No. 2,012,443, etc., compounds having a heterocyclic thioamide described in US Pat. No. 4,080,207 as an adsorption group, British Patent Second 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, the same
59-212,828, 59-212,829, "Research Disclosure" (Research Disclosure) No. 23510 (1953)
The hydrazine compound described in (November, 2013) is 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. It has been found that there are drawbacks such as deterioration of film quality when added in a large amount.

For the purpose of solving these drawbacks, JP-A-60-179,734,
61-170,733, JP-A-60-206,093, 60-19,739,
Various hydrazine derivatives such as the adsorption-type hydrazine derivatives described in JP-A No. 60-111,936 have been proposed and considerably improved. However, in order to further improve the stability of the development processing solution (that is, to prevent the deterioration of the developing agent), it is necessary to lower the pH of the processing solution or to shorten the processing time of the development. Activity was insufficient.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is, firstly, a halogen capable of obtaining an extremely hard negative gradation photographic characteristic with a gamma of more than 10 by using a stable developing solution. A silver halide photographic light-sensitive material is provided.

Secondly, an object of the present invention is to contain highly active hydrazines which can give desired extremely high tone negative gradation photographic characteristics with a small addition amount even in a low pH developer without adversely affecting photographic characteristics. A negative silver halide photographic light-sensitive material is provided.

Thirdly, an object of the present invention is to provide a silver halide photographic light-sensitive material exhibiting super-high contrast photographic characteristics and having less black spots.

A fourth object of the present invention is to provide a direct positive type silver halide photographic light-sensitive material containing highly active hydrazines which can give excellent reversal characteristics even in a low pH developer.

A fifth object of the present invention is to provide a silver halide photographic light-sensitive material containing hydrazines which is easy to synthesize and has excellent storage stability and which is stable with time.

(Means for Solving Problems) 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, the photographic emulsion layer or at least one hydrophilic colloid layer having the following: This has been achieved by containing the compound represented by the general formula (I).

General formula (I) (In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or (Wherein R _o represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group, and n represents 1 or 2), and R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group. Represents an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an azo group, or a heterocyclic group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, (In the formula, R ₂ represents an alkyl group, an arule group, an alkoxy group or an aluroxy group.) Or an iminomethylene group, L ₂ represents a divalent linking group, and X ₁ is adsorbed on silver halide. Represents a accelerating group, m represents 0 or 1, and L ₁ represents a group represented by the following general formula (a).

General formula (a) (In the formula, L ₃ represents a nitrogen-containing heterocyclic group, and ▲ R ¹ _a ▼ to ▲ R ⁴ _a
Represents a hydrogen atom, a halogen atom or an alkyl group, and t and u each represent 0 or 1. ) The present invention has a nitrogen-containing heterocycle as a substituent of hydrazine as represented by the general formula (I), and by simultaneously introducing an adsorption promoting group and a —SO ₂ NH— group into the molecule,
We could find hydrazines with high activity and few black spots, which cannot be predicted from conventional knowledge.

The general formula (I) will be described in detail below.

In the general formula (I), A ₁ and A ₂ are each a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a hamet having a substituent constant sum of −0.5 or more). A substituted phenylsulfonyl group), (Preferably, as R _o , a linear, branched or cyclic alkyl group, alkenyl group or aryl group having 30 or less carbon atoms (preferably a phenyl group or a sum of substituent constants of Hamet is −
A phenyl group substituted to 0.5 or more), an alkoxy group (for example, an ethoxy group), an aryloxy group (preferably a monocyclic group), and the like, which may have a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group, An aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group, an arylthio group, and the like. ), And the sulfinic acid residues represented by A ₁ and A ₂ specifically represent those described in US Pat. No. 4,478,928.

Most preferably, hydrogen atoms are used as A ₁ and A ₂ . G, R ₁ is, if G is a carbonyl group, R ₁ is a hydrogen atom, an alkyl group (e.g. methyl group, a trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamido-propyl), aralkyl Group (for example, o-hydroxybenzyl group), aryl group (for example, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), alkoxy group (for example, , Methoxy group, etc.), aryloxy group (eg, phenoxy group, p-nitrophenoxy group, p
-Chlorphenoxy group, etc.), amino group (eg, methylamino group, phenylamino group, p-nitrophenylamino group, p-methoxyphenylamino group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, etc.), aryloxy Carbonyl group (eg, phenoxycarbonyl group), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), azo group (eg, phenylazo group, etc.), heterocyclic group (eg, pyridyl group, quinoline group, etc.) A nitrogen-containing heterocyclic group), and a hydrogen atom is particularly preferable.

When G is a sulfonyl group, R ₁ is an alkyl group (such as a methyl group), an aralkyl group (such as an o-hydroxyphenylmethyl group), an aryl group (such as a phenyl group), or a substituted amino group ( For example, a dimethylamino group etc.) is preferable.

When G is a sulfoxy group, preferred R ₁ is cyanobenzyl group, methylthiobenzyl group and the like.

G is In this case, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group or a phenyl group, more preferably a phenoxy group.

When G is an N-substituted or unsubstituted iminomethylene group, preferred R ₁ is a methyl group, an ethyl group, a substituted or unsubstituted phenyl group.

Here, examples of the substituent of R ₁ include the following. These groups may be further substituted.

Here, examples of the substituent of R ₁ include the following. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group,
Sulfamoyl group, carbamoyl group, alkylthio group,
Arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, acyloxy group, acyl group, alkyl or aryloxycarbonyl group, alkenyl group, alkynyl group, carbonamido group, nitro group, etc. Is.

Also, if possible, these groups may form a ring linked to each other.

Here, a carbonyl group is most preferable as G.

The divalent linking group represented by L ₂ is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, (R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group), —N
=, —CO—, —SO ₂ — (these groups may have a substituent), etc., or a combination thereof. Specifically, for example, —CH ₂ —, CH _{2 2} , CH _{2 3} , _{-NHCOCH 2 CH 2 CONH -, -} SCH 2 -, And so on.

These may be further substituted with a substituent. Examples of the substituent include those mentioned for R ₁ .

As the adsorption promoting group represented by X ₁ on silver halide,
Specifically, 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione,
1,2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2
-Thion, thiotriazine, 1,3-imidazoline-2-
Cyclic thioamide group such as thione, chain thioamide group,
Aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (--SH group is synonymous with a cyclic thioamide group in a tautomeric relationship with a nitrogen atom next to the bonded carbon atom, Specific examples of the group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline. 5 to 6 consisting of a combination of nitrogen, oxygen, sulfur and carbon such as, thiadiazole, oxathiazole, triazine and azaindene.
Membered nitrogen-containing heterocyclic groups, and heterocyclic quaternary salts such as benzimidazolinium.

These may be further substituted with appropriate substituents.

Examples of the substituent include those mentioned as the substituent for R ₁ .

Among those represented by X ₁ , preferable ones are a mercaptotetrazole group, a 3-mercapto-1,2,4-triazole group, a 2-mercapto-1,3-imidazole group and a 2-mercapto-1,3,4-oxa group. Examples thereof include a diazole group, a 2-mercapto-1,3,4-thiadiazole group, a 2-mercaptobenzimidazole group and a benzotriazole group.

The nitrogen-containing heterocyclic group represented by L ₃ in the general formula (a) is preferably a 5- or 6-membered heterocyclic ring, which may be a monocyclic ring or is condensed with another aromatic ring or heterocyclic ring. You may form a ring. Preferably as L ₃ , for example, pyridyl group, imidazolyl group, benzimidazolyl group, pyrimidinyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, benzthiazolyl group, quinoline group,
Examples thereof include a triazinyl group, and a pyridyl group and a quinoline group are particularly preferable. L ₃ may have a substituent,
As the substituent, in addition to the group represented by X ₁ L _{2 m} SO ₂ NH-, those enumerated as the substituent of R ₁ can be applied.

In the general formula (a), ▲ R ¹ _a ▼, ▲ R ² _a ▼, ▲ R ³ _a ▼ and ▲ R ⁴ _a ▼ may be the same or different from each other,
Each represents a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, etc.) and a substituted or unsubstituted alkyl group (the substituents include those mentioned as the substituents of R ₁ ).

Among the compounds represented by the general formula (I), preferred ones are those represented by the general formula (II).

General formula (II) (In the formulae, R ₁ , G, A ₁ , A ₂ , L ₂ , X ₁ and m are the general formula (I).
Synonymous with those listed above, L ₄ represents a pyridyl group,
Examples of Z include the same as the substituents for L _{3 in} formula (a). In the general formula (II), X ₁ L _{2 m} SO ₂ NH is particularly preferably substituted at the o- or p-position with respect to hydrazine. The compounds represented by formula (I) are shown below. However, the present invention is not limited to the following compounds.

The compounds of the present invention can generally be synthesized as follows.

(Wherein Ar is a substituted or unsubstituted aryl group) In these reactions, a solvent such as acetonitrile, tetrahydrofuran, dioxane, methylene chloride, chloroform, dimethylformamide, dimethylacetamide can be used. Can be triethylamine, N-ethylpiperidine, N-methylmorpholine, pyridine, imidazole, etc., and as the condensing agent for reaction B, dicyclohexylcarbodiimide,
Carbonyl imidazole or the like can be used, and a catalyst such as N, N-dimethylaminopyridine, pyrrolidinopyridine or N-hydroxybenzotriazole or the above base can be used in combination for improving the yield and shortening the reaction time. .

Next, typical synthetic methods of the compound of the general formula (I) will be described with reference to synthetic examples.

Synthesis Example 1 Synthesis of Compound 1 Synthesis of 1- (1) 2- (2-formylhydrazino) -5-nitropyridine "Beilsteins Handbuch Der Organisc"
Hen Chemie) Vol. 22, Vol. 22, p. 487, and added to 154 g of 2-hydrazino-5-nitropyridine, 500 ml of acetonitrile was added, and 100 g of formic acid was added dropwise with stirring. After heating under reflux for 3 hours, the mixture was concentrated under reduced pressure, and the obtained solid was washed with ethanol to obtain the desired product.

Yield 147 g Yield 80.8% 1- (2) Synthesis of 5-amino-2- (2-formylhydrazino) pyridine 1-Nitro compound obtained in 1- (1) 91.0 g methanol 1.8 l
Was added and then hydrogenated (10% Pd / C 8 g, H ₂ 100 psi).
After removing the catalyst, the solvent was distilled off under reduced pressure to obtain the desired amino compound.

Yield 54.5 g Yield 71.7% 1- (3) 2- (2-formylhydrazino) -5-
Synthesis of (3-nitrobenzenesulfonamide) pyridine Under a nitrogen atmosphere, 45.6 g of the amino compound obtained in 1- (1) was converted to N, N-
Dimethylacetamide (120 ml), acetonitrile (100 ml) and triethylamine (33.3 g) were added and dissolved, and after cooling to -5 ° C, metanitrobenzenesulfonyl chloride (66.5 g) was gradually added. During this, stirring was performed while cooling so that the liquid temperature did not exceed -5 ° C. The mixture was further stirred at -5 ° C or lower for 1.5 hours, brought to room temperature, and extracted with 1.2 l of ethyl acetate and 1.2 l of saturated saline. The organic layer was separated and concentrated to 600 ml, 300 ml of n-hexane was added, the mixture was stirred at room temperature for 30 minutes, the generated crystals were collected, and then washed with 50 ml of ethyl acetate.

Yield 78.9 g Yield 78.1% 1- (4) Synthesis of 5- (3-aminobenzenesulfonamide) -2- (2-formylhydrazino) pyridine 1- (3) Nitro compound 33.7 g was added with methanol 700 ml. was added and then hydride (10% Pd / C 3g, H 2, 100psi) and. After removing the catalyst, the solvent was distilled off under reduced pressure to obtain the desired amino compound.

Yield 25.8 g Yield 84.0% 1- (5) Synthesis of compound-1 5-carboxybenzotriazole 1.63 g and 1-
1.63 g of the amino compound obtained in (5) was dissolved in 15 ml of dimethylformamide, and a solution of 2.20 g of dicyclohexylcarbodiimide in 5 ml of dimethylformamide was added dropwise over 15 minutes while stirring at 0 ° C. under a nitrogen atmosphere. After dropping, the mixture was stirred for 1 hour and further at 25 ° C. for 2 hours. The dicyclohexylurea formed was removed by filtration, and the solution was added to 1.5 l of ice water. Take the crude crystals that have precipitated and use them as isopropanol.
Heat dispersion was carried out in 100 ml for 15 minutes. The mixture was cooled to room temperature and filtered to obtain 2.40 g of the desired Exemplified Compound 1.

Yield 53.1% Synthesis example 2 Synthesis of compound 3 Synthesis of 2- (1) 3- (5-mercaptotetrazoyl) phenylsulfonyl chloride Sodium 3- (5-mercaptotetrazoyl) phenyl sulfonate 8.40 g, thionyl chloride 10 ml of NN-dimethylformamide was added dropwise to 8.1 g of the solution under ice-cooling, the temperature was gradually raised to room temperature, and the mixture was stirred for 2 hours. Excessive thionyl chloride was distilled off from the reaction solution under reduced pressure. The obtained residual liquid was poured into ice water, extracted twice with chloroform, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 3
3.15 g of-(5-mercaptotetrazoyl) phenylsulphonyl chloride was obtained.

Yield 38.0% 2- (2) Synthesis of Compound 3 To a solution of 3.04 g of the amino compound obtained in 1- (2) in 10 ml of N, N-dimethylformamide was added ice-cooling, 1.6 g of pyridine was added under a nitrogen stream, and further 3- A solution of 5.52 g of (5-mercaptotetrazoyl) phenylsulphonyl chloride in 5 ml of acetonitrile was added dropwise, and the mixture was stirred for 1 hour under ice cooling. The reaction solution is 100 m of water
1, and poured into an aqueous solution of 3 ml of acetic acid, and the result of precipitation was taken.
The obtained crystals were recrystallized from isopropyl alcohol to obtain 5.02 g of the desired compound.

Yield 64.0% Synthesis Example 3 Synthesis of compound 4 Synthesis of 3- (1) 1- (3-phenoxycarbonylaminophenyl) -5-mercaptotetrazole 1- (3-aminophenyl) -5- under nitrogen atmosphere After dissolving 391 g of mercaptotetrazole hydrochloride in 800 ml of N, N-dimethylformamide, cooling to below 0 ° C.
After adding ml, 294 g of phenyl chloroformate was added dropwise. During this, stirring was performed while cooling so that the liquid temperature did not exceed 0 ° C. After stirring at 0 ° C or lower for 1 hour, the reaction solution was added dropwise to 5 l of saturated saline and stirred for 30 minutes. Remove the resulting crystals, then water
Washed with 2 l. Yield 495 g, 93% yield 3- (2) Synthesis of compound 4 Under a nitrogen atmosphere, 3.07 g of the amino compound obtained in 1- (4) and 2.70 g of imidazole were dissolved in 10 ml of acetonitrile, and 65
Heated to ° C. The urethane compound obtained in 3- (1)
A solution prepared by dissolving 3.40 g in 5 ml of N, N-dimethylacetamide was added dropwise, and the mixture was heated with stirring at 65 ° C for 1.5 hours. After cooling to 30 ° C., the mixture was extracted with 240 ml of ethyl acetate and 240 ml of water, and the aqueous layer was poured into dilute hydrochloric acid water. The generated crystals were taken and washed with water. Yield 3.79 g, yield 72.1% In order to incorporate the compound of the present invention in the photographic emulsifier layer and the hydrophilic colloid layer, after dissolving the compound of the present invention in water or a water-miscible organic solvent (necessary According to the above, alkali hydroxide or tertiary amine may be added to form a salt to dissolve it), a hydrophilic colloid solution (for example, a silver halide emulsion,
Gelatin aqueous solution, etc.) (at this time, the pH may be adjusted by adding acid or alkali, if necessary).

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 preferably 1 × 10 ^{−5 to} 5 × 10 ⁻² mol, and more preferably 2 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, per 1 mol of silver halide, and they are combined. 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 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% by 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 are cubic, octahedral, and rhombo 12
Those with regular (regular) crystals such as tetrahedrons and tetradecahedrons, and those with irregular (irregular) crystals such as spheres and flat plates, or composite forms of these crystal forms You can bring it with you.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

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 formation or physical ripening of silver halide grains. Good.

The silver halide used in the present invention is 10 _-8 to 10 per mol of silver.
It is a halosilver iodide prepared in the presence of _-5 mol of an iridium salt or a complex salt thereof and having a silver iodide content on the grain surface higher than the average silver iodide content of the grain. 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 image-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 No. 618,016. 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 preferable to use an iridium salt or a rhodium salt before the physical ripening in the production process of the silver halide emulsion, especially at the time of grain formation.

In the present invention, the silver halide emulsion layer is provided in Japanese Patent Application No. 60-64199.
Japanese Patent Application No. 60-232086, it is preferable to include two kinds of monodisperse emulsions having different average grain sizes from the viewpoint of increasing the maximum density (Dmax). 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. The term "shallow" means that the time for chemical sensitization is shorter than the chemical sensitization of small-sized grains, the temperature is low, and the amount of chemical sensitizer added is small. 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 was such that a hydrazine derivative was included and coated on a support, and sulfite ion was added at 0.15 mol / l.
It is obtained when processed with a developer having a pH of 10.5 to 12.3. The average particle size of the small size monodisperse grains is 90% or less, preferably 80% or less of the average size of the large size silver halide monodisperse grains. The average grain size of the silver halide emulsion grains is preferably 0.
The average particle size of large-sized and small-sized monodisperse particles is preferably within the range of 02 μ to 1.0 μ, more preferably 0.1 μ to 0.5 μ.

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 layer coated silver ^{amount, 1g / m 2 ~8g / m} 2 is preferred.

The sensitizing dyes described in JP-A-55-52050, pages 45 to 53 (for example, 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.
A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Discloser (Research Discloser).
Closure) Volume 176 17643 (issued in December 1978) Page 23, IV, J
It is described in the section.

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

Suitable development accelerators or accelerators for nucleating infectious development used in the present invention include JP-A Nos. 53-77616 and 54-37732.
In addition to the compounds disclosed in Nos. 53-137133, 60-140340 and 60-14950, various compounds containing N or S atoms are effective. The optimum addition amount of these accelerators varies depending on the type of compound, but 1.0 × 10 ^{−3 to} 0.5 g / m ² ,
It is desirable to use it in the range of 5.0 × 10 ^{−3 to} 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 redox potential determined by polarography, and the sum of the polaro anode potential and the cathode potential is positive. The polarographic redox potential measurement method is described, for example, in US Pat. No. 3,501,307. The organic desensitizer preferably contains at least one water-soluble group, specifically, a sulfonic acid group,
Carboxylic acid groups, sulfonic acid groups, etc. may be mentioned, and these groups form salts with organic bases (eg, ammonia, pyridine, triethylamine, piperidine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.). Good.

As organic desensitizers, Japanese Patent Application No. 61-280998, pages 55 to 7 can be used.
Those represented by the general formulas (III) to (V) described on page 2 are preferably used.

The organic desensitizer in the present invention is 1.
0 × 10 ^{-8 to} 1.0 × 10 ^-4 mol / m ² , especially 1.0 × 10 ^{-7 to} 1.0 × 10
^-5 mol / m ² is preferably present.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further reducing photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and safety against safelight light when handled as a light-sensitive room light-sensitive material A dye having substantial light absorption mainly in the range of 380 nm to 600 nm is used to enhance the light emission.

These dyes are added to the emulsion layer depending on the purpose, or added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use.

It depends on the molar extinction coefficient of the UV absorber, but usually 10 ^-2
It is added in a range of ^{g / m 2 ~1g / m 2} . Preferably 50 mg to 500
It is mg / m ² .

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

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 compound, and an ultraviolet absorbing polymer can be used.

Specific examples of the ultraviolet absorber, U.S. Patent No. 3,533,794, the same 3,3
14,794, 3,352,681, JP-A-46-2784, U.S. Patent
3,705,805, 3,707,375, 4,045,229, 3,70
0,455, 3,499,762, West German patent application publication 1,547,863
No. etc.

Filter dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cytanine dyes and azo dyes. A dye that is water-soluble or that is decolorized by alkali or sulfite ion is preferable from the viewpoint of reducing the residual color after the development treatment. Specifically, for example, pyrazolone oxonol dyes described in U.S. Pat.No. 2,274,782, diarylazo dyes described in U.S. Pat.No. 2,956,879, U.S. Pat.Nos. 3,423,207, and 3,3.
Styryl dyes and butadienyl dyes described in 84,487, merocyanine dyes described in U.S. Pat.No. 2,527,583, U.S. Pat.Nos. 3,486,897, 3,652,284, and 3,718,472.
Merocyanine dyes and oxonol dyes described in No. 3, U.S. Patent No. 3,976,661 and enamino hemioxonol dyes and British Patent No. 584,609, No. 1,177,429, JP-A-48-85130, No. 49-99620, 49-114420, U.S. Pat.Nos. 2,533,472, 3,148,187, and 3,177,078.
No.3, No.3,247,127, No.3,540,887, No.3,575,7
The dyes described in No. 04 and No. 3,653,905 are used.

The dye is a suitable solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone,
It is dissolved in methyl cellosolve or the like or a mixed solvent thereof and added to the coating liquid for the non-photosensitive hydrophilic colloid layer of the present invention.

The amount of the specific dye is generally ^{10 -3 g / m 2 ~1g /} m 2, it is possible to find the preferred amount ranges particularly ^{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 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
-Vinylsulfonyl-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 slipperiness, 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 here, a surfactant containing fluorine (see, for example, U.S. Pat. No. 4,201,586).
And JP-A-60-80849 and 59-74554) are particularly preferable.

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. 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,
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,
Reference can be made to the descriptions in the specifications of No. 61-163856 and No. 60-195655. 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 super-high contrast and high-sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, the conventional infectious developer or US Pat.
It is not necessary to use a 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 / l or more and has a pH of 10.5-1.
With a developer having a pH of 2.3, especially 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 / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / l to 0.5 mol / l and the latter is 0.06 mol / l.
It is preferably used in an amount of less than mol / l.

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 / l or more, and particularly preferably 0.5 mol / l or more.

In the developer of the present invention, a silver stain preventing agent is disclosed in JP-A-56-24,34.
The compounds described in No. 7 can be used. The compounds described in Japanese Patent Application No. 60-109,743 can be used as a dissolution aid added to the developing solution. Further, as the pH buffer used in the developing solution, the compounds described in JP-A-60-93,433 or the compounds described in Japanese Patent Application No. 61-28,708 can be used.

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 may be any layer having any function, such as a color material layer, an intermediate layer, a filter layer, a protective layer and an antihalation layer, 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 should be an amount which gives a sufficient maximum density (eg, silver concentration of 1.0 or more) when the internal latent emulsion is developed with a surface developing solution. 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.

Preferred internal latent image type emulsions that can be used in the present invention are
From Japanese Patent Application No. 61-253716, page 28, line 14 to page 31, line 2, the preferred silver halide grains are described in the same specification, No. 31.
It is described on page 3, line 3 to page 32, line 11.

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, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, phorpolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. These sensitizing dyes include, for example, JP-A-59-40,
The cyanine dyes and merocyanine dyes described in Nos. 638, 59-40,636 and 59-38,739 are included.

The light-sensitive material of the present invention may contain a color-increasing 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 Research Disclosure (RD) 17643 (December 1978) Item VII-D and 18717.
(November 1979).

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

As the leaving group of the 2-equivalent 5-pyrazolone type coupler, the nitrogen atom leaving group or the arylthio group described in US Pat. No. 4,310,619 is particularly preferable. European patent 73,6
The 5-pyrazolone-based coupler having a ballast group described in No. 36 provides 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 and the pyrazolopyrazoles described in Research Disclosure 24230 (June 1984). The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferred in terms of low yellow sub-absorption of the color forming dye and light fastness, and the pyrazolo [1,5 compounds described in European Patent No. 119,860 are preferred. -B] [1,2,
4] Triazole is particularly preferable.

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. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Examples thereof include cyan couplers, 2,5-diacylamino-substituted phenol type couplers, and phenol type 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 in combination 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. Pat.No. 4,366,237 and British Patent 2,12.
Specific examples of magenta couplers are described in 5,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application 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 / 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.
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) -phenylazo] -naphthalene, 1-phenyl-3 as a yellow dye image-forming substance -Cyano-4- (2
, 4-di-tert-pentylphenoxyacetamino)
-Phenylsulfamoyl] phenylazo) -5-pyrazolone and the like.

Details of the color couplers which can be preferably used in the present invention are described on page 33, line 18 to page 40, last line of the same specification.

After imagewise exposure using the light-sensitive material of the present invention, after or while being subjected to fogging treatment with light or a nucleating agent, a surface developer having a pH of 11.5 or less containing an aromatic primary amine color developing agent. It is preferable to directly form a positive color image by performing color development, bleaching, and fixing processing in 1. The pH of this developer is 1
More preferably, it is in the range of 1.0 to 10.0.

The fogging treatment in the present invention is a so-called "light fogging method".
Either of the method of giving a second exposure to the entire surface of the photosensitive layer, which is referred to as "," and the method of developing in the presence of a nucleating agent, which is referred to as "chemical fogging method", may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

The light fogging method is described in the above-mentioned Japanese Patent Application No. 61-253716, p. 47, line 4 to p. 49, line 5, and regarding the nucleating agent usable in the invention, p. 49, 6 of the same specification. Lines to page 67, line 2, particularly the general formulas [N-1] and [N-2].
The use of a compound represented by Specific examples thereof include [NI-1] described on pages 56 to 58 of the same specification.
To [NI-10] and the same specification as described on pages 63 to 66 of [N-
The use of [II-1] to [N-II-12] is preferable.

Regarding the nucleation accelerator that can be used in the present invention, see No. 68 of the same specification.
See page 11, line 71 to page 71, line 3, and specific examples thereof include (A-1) to (A-13) on pages 69 to 70.
Is preferably used.

The color developing solution used for the development processing of the light-sensitive material of the present invention is described in the same specification, page 71, line 4 to page 72, line 9, and particularly, aromatic primary amine color developing agents. As a specific example, a p-phenylenediamine 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 directly form a positive color image by the color diffusion transfer method using the light-sensitive 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 process may be carried out simultaneously with the fixing process by one-bath bleach-fixing process or separately. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after bleaching processing or a method of performing bleach-fixing processing after fixing processing may be used. Aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or the bleach-fixing solution of the present invention. As the additive used in the bleaching solution or the bleach-fixing solution of the present invention,
Various compounds described on pages 22 to 30 of Japanese Patent Application No. 61-32462 can be used. After the desilvering process (bleach-fixing or fixing), a treatment such as washing with water and / or stabilization is performed. It is preferable to use softened water as 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 concrete method of these, it is preferable to carry out the method described in Japanese Patent Application No. 61-131632.

Furthermore, various compounds described on pages 30 to 36 of Japanese Patent Application No. 61-32462 can be used as additives used in the washing and stabilizing steps.

It is preferable that the amount of replenisher in each processing step is small. The replenishing liquid flow is preferably 0.1 to 50 times, and more preferably 3 to 30 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.
Double.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 A multilayer color light-sensitive material No. A having the following layer structure was prepared on a paper support laminated on both sides with pyriethylene.

(Layer constitution) The composition of each layer is shown below. The number is the amount applied per m ² in g
Express with. The silver halide emulsion and colloidal silver are expressed in terms of silver, and the spectral sensitizing dye is expressed in terms of mol per mol of silver halide.

Support Polyethylene laminated paper [Ethylene on the E1 layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] E1 layer Halogenated emulsion A 0.26 Spectral sensitizing dye (ExSS-1) 1.0 × 10 ^-4 Spectral sensitizing dye (ExSS-1) 6.1 × 10 ^-5 Gelatin 1.11 Cyan coupler (ExCC-1) 0.21 Cyan coupler (ExCC-2) 0.26 UV absorber (ExUV-1) 0.17 Solvent (ExS-1) 0.23 Development control agent (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation accelerator (ExZS-1) 3.0 × 10 ^-4 Nucleation agent (ExZK-1) 8.0 × 10 ^-5 Layer E2 Gelatin 1.41 mixed Inhibitor (ExKB-1) 0.09 Solvent (ExS-1) 0.10 Solvent (ExS-2) 0.10 E3 layer Silver halide emulsion A 0.23 Spectral sensitizing dye (ExSS-3) 3.0 × 10 ^-4 Gelatin 1.05 Magenta coupler ( ExMC-1) 0.16 Color image stabilizer (ExSA-1) 0.20 Solvent (ExS-3) 0.25 Development control agent (ExGC-1) 0.02 Stabilizer ExA-1) 0.006 Nucleation accelerator (ExZS-1) 2.7 × 10 -4 nucleating agent (ExZK-1) 1.4 × 10 -4 second E4 layer Gelatin 0.47 mixing inhibitor (ExKB-1) 0.03 solvent (ExS- 1) 0.03 Solvent (ExS-2) 0.03 Layer E5 Colloidal silver 0.09 Gelatin 0.49 Mixing inhibitor (ExKB-1) 0.03 Solvent (ExS-1) 0.03 Solvent (ExS-2) 0.03 E6 layer Same as E4 layer E7 layer Halogenated emulsion A 0.40 Spectral sensitizing dye (ExSS-4) 4.2 × 10 ^-4 Gelatin 2.17 Yellow coupler (ExYC-1) 0.51 Solvent (ExS-2) 0.20 Solvent (ExS-4) 0.20 Development modifier ( ExGC-1) 0.06 Stabilizer (ExA-1) 0.001 Nucleation accelerator (ExZS-1) 5.0 × 10 ^-4 Nucleating agent (ExZK-1) 1.2 × 10 ^-5 Layer E8 gelatin 0.54 Ultraviolet absorber (ExUV) -2) 0.21 Solvent (ExS-4) 0.08 Layer E9 Gelatin 1.28 Polyvinyl alcohol acrylic modified copolymer (Degree of modification 17%) 0.17 Fluid paraffin 0.03 Polymer Methyl acrylic acid latexes particles (average particle diameter 2.
8 μm) 0.05 Layer B1 Gelatin 8.70 Layer B2 Same as Layer E9 In addition to the above composition, a gelatin hardener ExGK-1 and a surfactant were added to each layer.

Silver halide emulsion A Gelatin prepared by adding 0.5 g of 3,4-dimethyl-1,3-thiazoline-2-thione and 0.3 g of lead acetate to a mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate per 1 mol of Ag. While stirring vigorously in the aqueous solution, it was added simultaneously at 55 ° C over about 5 minutes, and the average particle size was about 0.2 µm (silver bromide content 40%).
(Mol%) of monodispersed silver chlorobromide emulsion was obtained. To this emulsion, 35 mg of sodium thiosulfate and 20 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 55 ° C. for 60 minutes to carry out a chemical increasing treatment.

The silver chlorobromide grains thus obtained were used as cores for further growth by treatment for 40 minutes in the same precipitation environment as the first time, and finally a monodisperse core / shell silver chlorobromide emulsion having an average grain size of 0.4 μm. Got The coefficient of variation of particle size is about
It was 10%.

To this emulsion, 3 mg of sodium thiosulfate and 3.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 50 minutes for chemical sensitization to form an internal latent image type haloene compound. A silver emulsion A was obtained.

Compound used to prepare the sample (ExUV-2) UV absorber 2: 9: 8 mixture of (1) :( 2) :( 3) above (weight ratio) (ExA-1) Stabilizer 4-hydroxy-5,6-trimethylene-1,3,3a, 7-tetrazaindene (ExZS-1) Nucleation accelerator 2- (3-dimethylaminopropylthio) -5- Mercapto-1,3,4-thiadiazole hydrochloride Nucleating agent (Explained in JP-A-63-8715) (ExGK-1) Gelatin hardening agent 1-oxy-3,5-dichloro-s-triazine sodium salt Treatment process time Temperature Color development 100 seconds 38 ° C Bleach fixing 30 seconds 38 ° C Wash with water 30 seconds 38 ℃ Washing with water 30 seconds 38 ℃ Washing water was replenished by a so-called countercurrent replenishment method in which the washing bath was replenished and the overflow solution of the washing bath was introduced into the washing bath.

[Color developer]

Mother liquor Diethylenetriamine pentaacetic acid 0.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5 g Diethylene glycol 8.0 g Bennyl alcohol 10.0 g Sodium bromide 0.5 g Sodium chloride 0.7 g Sodium sulfite 2.0 g N, N-diethylhydroxylamine 3.5 g 3 -Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline 6.0g Potassium carbonate 30.0g Fluorescent brightener (stilbene type) 1.0g Pure water is added 1000ml pH 10.50 pH is It was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer]

Mother liquor Ammonium thiosulfate 110g Sodium bisulfite 10g Ethylenediaminetetraacetic acid (III) ammonium dihydrate 4
0 g Ethylenediaminetetraacetic acid disodium dihydrate 5 g 2-Mercapto-1,3,4-triazole 0.5 g Pure water was added and 1000 ml pH 7.0 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water] Pure water was used.

Here, the pure water is obtained by removing all cations other than hydrogen ions and all anions other than hydroxide ions in the water-conducting water to 1 ppm or less by ion exchange treatment.

A multilayer color light-sensitive material N was prepared in the same manner as Sample No. A except that the nucleating agent (ExZK-1) was changed to the compound shown in Table 1.
o.1 to 5 were prepared.

The sample prepared in this manner was wet exposed (1 /
After 10 seconds and 10 CMS), processing step A was performed to measure the cyan color image density. The obtained results are shown in Table 1.

The amount of the nucleating agent added was equivalent to ExZK-1.

Sample Nos. 1 to 5 using the nucleating agent of the present invention are Comparative Example Nos.
The maximum image density (Dmax) was higher than that of A and B, which was preferable. Similar results were obtained for magenta and yellow densities.

Example 2 Photosensitive elements Nos. 1 to 7 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 ) And a mordant layer containing 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) Magenta DRR compound of the following (0.45 g / m ^2), diethyllaurylamide (0.10g / m ^2), 2,5- di -t- butyl hydroquinone (0.0074 g / m ^2), and gelatin (0.
A layer containing 76 g / m ² ).

(5) Nucleating agent and 5-pentadecyl-hydroquinone-2-sulfone shown in Table 2 containing an internal latent image type emulsion (1.4 g / m ² in silver amount) and a green sensitizing dye (1.9 g / m ² ). Green-sensitive internal latent sensitized direct positive silver iodobromide emulsion (2 mol% silver iodide) layer containing sodium acidate (0.11 g / m ² ) (6) Layer containing gelatin (0.94 g / m ² ).

Processing was carried out by combining the above-mentioned photosensitive elements Nos. 1 to 7 and the following respective elements.

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. Hydrolyze cellulose to generate 39.4g acetyl group) 3.8g / m ² and copolymer of styrene and maleic anhydride (composition (molar) ratio, styrene: maleic anhydride = 60: 40, molecular weight about 50,000) 0.2 A cover sheet coated with g / m ² was prepared.

Forced deterioration conditions Two sets of the above-mentioned photosensitive elements No. 1 to 7 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 by a Macbeth reflection densitometer after 1 hour through the transparent support of the photosensitive sheet.
The results are shown in Table 2.

▲ D ^F _max ▼: Maximum density of the positive image part of the refrigerator storage product S ^F : Relative sensitivity of the density of the positive image part of the refrigerator storage product 0.5 (assuming S ^{F of the} photosensitive element 1 is 100) S ^W : 35 ℃ as the relative relative sensitivity of 80% humidity for 4 days standing samples of positive image of the concentration of 0.5 (when the S ^F of the photosensitive element 1 was 100) is clear from the above results, the addition of nucleating agents of the present invention The photosensitive elements 3 to 7 are more likely to produce Dmax with the same addition amount than the photosensitive element 1 produced by the conventional method.
2 indicates that there is less change in sensitivity when the photosensitive material is aged.

Example 3 In carrying out the present invention, the following emulsion X was prepared.

Emulsion X 20 mg of thioether (1,8-dihydroxy-3,6-dithiaoctane) was added to each of the silver nitrate aqueous solution and the potassium bromide aqueous solution at a constant rate while maintaining the silver electrode potential at a potential for growth of octahedral grains. 1/8 mol of silver nitrate corresponding to 1/8 mol of silver nitrate was added in 5 minutes to the contained gelatin aqueous solution (pH = 5.5) at 75 ° C. with stirring to obtain a spherical AgBr monodisperse emulsion having an average particle size of about 0.14 μm. . To this emulsion were added 20 mg of sodium thiosulfate and 20 mg of chloroauric acid (tetrahydrate) per mol of silver halide, the pH was adjusted to 7.5, and the mixture was chemically stirred at 75 ° C for 80 minutes. The sensitized product was used as the core emulsion. Next, at the same temperature, the silver nitrate aqueous solution (7 /
(Including 8 mol of silver nitrate) and an aqueous solution of potassium bromide, under well-stirred conditions, while maintaining the silver electrode potential at which the regular octahedron grains grow, simultaneously added over 40 minutes to grow the shell. A shell emulsion was obtained. This emulsion was washed with water and desalted in a conventional manner, heated and dissolved, and then the pH was adjusted to 6.5, and 5 mg of sodium thiosulfate and 5 mg of chloroauric acid (tetrahydrate) were added per mol of silver halide. Plus 7 each
After ripening at 5 ° C. for 60 minutes, the surface of the shell was chemically sensitized to finally obtain an internal latent image type monodisperse octahedral core shell emulsion (Emulsion X). As a result of measuring the grain size distribution of this emulsion from an electron micrograph, the average grain size was 0.30 μm and the coefficient of variation (average grain size × 100 / standard deviation) was 10%.

The above emulsion X was mixed with panchromatic sensitizing dye 3,3'-diethyl-9-
Methyl thiacarbocyanine per mol of silver halide
After adding 5 mg, the exemplified compound (1) as a nucleating agent
(2) (3) (4) and comparative compound-A were added in the amounts shown in Table 3, and compound-Z as a nucleation accelerator was 1 ×.
10 ^-3 mol and 1 mol of silver halide were added per mol of silver halide, and the amount of silver was 2.
A direct positive photographic light-sensitive material sensitive to red light was prepared by simultaneously coating the protective layer composed of gelatin and a hardener at 8 g / m ² so that a protective layer composed of gelatin and a hardener was simultaneously coated thereon.

1kw tungsten lamp (color temperature 2854 °
K) Exposure with a sensitometer for 0.1 seconds through a step wedge.

Next, use Kodak Proster I Processor, an automatic processor.
Using Proster Plus processor (developer pH 10.7), 38 ℃
Develop for 18 seconds, continue with the same developing machine, wash with water, fix,
It was washed with water and dried.

The maximum density (Dma
x), the minimum concentration (Pmin) and the relative sensitivity were measured, and the results shown in Table 3 were obtained.

As is clear from the results in Table 3, the exemplified compound (1),
It can be seen that the nucleating agents of (2), (3) and (4) not only exhibit excellent reversal characteristics as compared with the control nucleating agent of Comparative Compound-A, but also have high sensitivity. That is,
It can be seen that the novel nucleating agents of the exemplified compounds have extremely high nucleating activity.

Further, it was found that when the developer pH was adjusted to 10.0 with an acid and these samples were similarly developed, the same excellent reversal characteristics were exhibited.

Example 4 An aqueous solution of silver nitrate, an aqueous solution of potassium iodide and an aqueous solution of potassium bromide were simultaneously added to an aqueous gelatin solution kept at 50 ° C. in the presence of 4 × 0 ^-7 mol of potassium iridium (III) hexachloride and ammonia per mol of silver. The average grain size is 0.25μ and the average silver iodide content is 1 mol% by keeping the PAg at 7.8 during the addition.
A cubic monodisperse emulsion of was prepared. Chemical sensitization never happened. These silver iodobromide emulsions contained 5,5'-
Sodium salt of dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer, poly A dispersion of ethyl acrylate, polyethylene glycol, 1,3-vinylsulfonyl-2-propanol and the compound of the present invention shown in Table 4 were added, and the amount of silver was 3.4 g / m 2 on the polyethylene terephthalate base.
Application was performed as it became ² . Gelatin was 1.8 g / m ² .

As a protective layer, a layer containing gelatin 1.5 g / m ² , polymethylmethacrylate particles (average particle size 2.5 μm) 0.3 g / m ² , and the following surfactant was applied thereon.

As a comparative example, instead of the compound of the present invention, compounds A, C,
Samples using D and E were made. Examples of those compounds are shown in Table 4.

These samples were exposed to tungsten light of 3200 ° K through an optical wedge, developed with the following developer for 30 seconds at 34 ° C, fixed, washed with water and dried.

The photographic properties obtained are shown in Table 4.

[Developer-I]

Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 g 4-methyl-4-hydroxymethyl-1-phenyl-3
-Pyrazolidone-Sodium hydroxide 18.0 g Boric acid 54.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.
3g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2g N-n-butyldiethanolamine 15.0g Sodium toluenesulfonate 8.0g Add water to adjust to 11 pH = 11.6 (add potassium hydroxide) pH 11. 6 * 1 Sensitivity: The sensitivity (logE) of Comparative Example-1 is used as a standard, and the difference is shown. Therefore, for example, +1.0 means that the altitude is 1.0 in logE, that is, 10 times higher than Planck.

* 2 Gradation (γ): The slope of the straight line connecting the point of density 0.3 on the characteristic curve. The larger the value is, the harder the image is.

* 3 Halftone quality: The halftone quality is visually evaluated on a scale of 5, with "5" being the best and "1" being the worst. As halftone dot original plate for plate making, halftone dot quality "5", "4"
Is practical, and 3 is poor, but practically practical,
"2" and "1" are halftone dots of impractical quality.

* 4 Black spots: Black spots are evaluated on a scale of 5 by microscopic observation. "5" indicates the best quality and "1" indicates the worst quality. "5" or "4" is practical, "3" is poor, but it is practically practical and "2" or "1" is not practical.

From the above results, it is understood that when the compound of the present invention is used, remarkably high sensitivity and high contrast are obtained, and the halftone dot quality and the black spot are both improved.

Example-5 The sample of Example-4 was then developed with a developer at 38 ° C for 30 seconds,
It was fixed, washed with water and dried.

[Developer-II]

Hydroquinone 25g 4-methyl-4-hydroxymethyl-1-phenyl-3
-Pyrazolidone 0.5g Ethylenediaminetetraacetic acid disodium 10.8g Sodium hydroxide 10.5g Potassium carbonate (monohydrate) 11.0g Sodium sulfite (anhydrous) 66.7g Potassium bromide 3.3g 5-Methylbenzotriazole 0.4g 3- (5-mercapto) Tetrazole) Sodium benzenesulfonate 0.2g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3g β-Phenethyl alcohol 2.0ml Water added 1 pH = 10.7 (combined with potassium hydroxide) Is shown in Table-5. By using the compound of the present invention, high sensitivity and high contrast can be obtained even with a developing solution having a low pH of 10,7.

Example-6 5.0 × 10 ⁻⁶ per mol of silver in a gelatin aqueous solution kept at 40 ° C.
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of a molar amount of (NH ₄ ) ₃ RhCl ₆ , the soluble salt was removed and gelatin was added and chemically ripened by a method well known to those skilled in the art. Instead, 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. This emulsion was a cubic monodisperse emulsion having an average grain size of 0.18 μm.

In this emulsion, the hydrazine compound and polyethyl acrylate latex shown in Table 6 were added to the solid content of 30 wt% of gelatin.
Added, as a hardener, 1,3-vinylsulfonyl-2-
Propanol was added and 3.8 g / m ² on the polyester support.
Was applied so that the amount of Ag would be. Gelatin was 1.8 g / m ² . On top of this, 1.5 g / m ² of gelatin was used as a protective layer.

This sample was exposed through an optical wedge with a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd., and developed with Developer-I of Example 4 at 38 ° C. for 20 seconds, fixed, washed with water, and dried.

The results of the obtained photographic properties are shown in Table-6.

The compound of the present invention gives high tonality and sensitivity even in a small amount.

Example 7 (Preparation of emulsion) An aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 0.5 × 10 ⁻⁴ mol of ammonium hexachlororhodium (III) chloride per mol of silver were adjusted to pH in a gelatin solution at 35 ° C. by the double jet method. Mix while controlling to 6.5.
A monodisperse silver chloride emulsion having an average grain size of 0.07 μm 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.

(Preparation of Photosensitive Material) In the emulsion, the nucleating agents of the invention and comparative examples shown in Table 7,
And the following nucleation accelerators and safelight dyes were added.

Next, polyethyl acrylate latex (14mg /
m ² ), and as a hardening agent, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt was added, and the amount of silver was 3.5 g per m ² on a polyethylene terephthalate transparent support. A silver halide emulsion layer is coated, and then a protective layer containing gelatin (1.3 g / m ² ), the following three surfactants as a coating aid, a stabilizer, and a good matting agent is further coated, Dried.

Stabilizer thioctic acid 6.0 Matting agent Polymethylmethane acrylate (average particle size 2.5 μ) 9.0 This sample was exposed through an optical wedge with a bright room printer P-607 manufactured by Dainippon Screen Co., Ltd.
I was developed at 38 ° C. for 20 seconds, fixed, washed with water and dried.

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

In the comparative example, only the characteristic that γ was soft was obtained, but with the compound of the present invention, an excellent high-contrast image with γ of 10 or more was obtained. Further, in the comparative example, while the increase in sensitivity is small,
A significant increase in sensitivity was obtained with the samples of the invention.

Claims (1)

[Claims] 1. A photographic emulsion layer having at least one silver halide photographic emulsion layer, and the photographic emulsion layer or at least one other hydrophilic colloid layer containing a compound represented by the following general formula (I). A silver halide photographic light-sensitive material. General formula (I) (In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or (Wherein R _o represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group, and n represents 1 or 2), and R ₁ represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group. Represents an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an azo group, or a heterocyclic group, and G represents a carbonyl group, a sulfonyl group, a sulfoxy group, (In the formula, R ₂ represents an alkyl group, an alur group, an alkoxy group or an aryloxy group.) Or an iminomethylene group, L ₂ represents a divalent linking group, and X ₁ is adsorbed on silver halide. Represents a accelerating group, m represents 0 or 1, and L ₁ represents a group represented by the following general formula (a). General formula (a) (In the formula, L ₃ represents a nitrogen-containing heterocyclic group, and ▲ R ¹ _a ▼ to ▲ R ⁴ _a
Represents a hydrogen atom, a halogen atom or an alkyl group, and t and u each represent 0 or 1. )