JP2515151B2 - Silver halide photographic 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 silver halide engraving agent.

(Prior Art) Addition of a hydrazine compound to a silver halide photographic emulsion is described in U.S. Pat. No. 3,730,727 (developing solution combining ascorbic acid and hydrazine) and 3,227,552.
No. (using hydrazine as an auxiliary developing solution 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 sensitizers), No. 2,419,975 and , Mee
s) By The Theory of Photographic Process, 3rd edition (1966), p.281.

Among these, especially in U.S. Pat.No. 2,419,975,
It is disclosed to obtain a high-tone negative image by adding a hydrazine compound.

The patent specification states that when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH of 12.8, a gamma (γ) of 10 or more and extremely hard photographic characteristics are obtained. Has been done. 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 over 10 are negative images,
Any positive image is extremely useful for photographic reproduction of continuous-tone images or reproduction of line drawings by means of a dot image useful for printing plate making. For such a purpose, conventionally, a chlorinated photographic emulsion having a silver chloride content of more than 50 mol%, preferably more than 75 mol% was used, and the effective concentration of sulfite ion was extremely low (usually 0.1 mol / min). The method of developing with a hydroquinone phenomenon solution described below was 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, it has been strongly desired to obtain a super-high contrast photographic property in which a halftone dot image is useful for reproducing a line drawing by using a high-sensitivity emulsion and a stable developing solution.

U.S. Patent Nos. 4,224,401, 4,168,977, 4,243,73
In No. 9, No. 4,272,614, No. 4,323,643, etc.,
Although silver halide photographic emulsions have been disclosed which provide very hard negative photographic properties with stable developers, it has been found that the acylhydrazine compounds used therein 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 to form bubbles and impair the photographic image. That is, it will adversely affect other photographic materials.

As a means for preventing outflow to the developing solution, it has been known to increase the molecular weight of the engraving agent to make it anti-diffusion, but the conventional anti-diffusion engraving agent has a problem in stability over time of the emulsion. I found out that there is. That is, when the coating liquid containing the engraving agent is aged, precipitates are generated in the coating liquid to deteriorate the filterability and also change the photographic performance.

Further, when a large amount of these conventional hydrazines are required for enhancing the sensitizing contrast, or when it is required that the sensitivity of the photosensitive material is particularly high, another sensitizing technique (for example, chemical sensitization) is 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 has been a demand for a compound capable of reducing the generation of such bubbles and the outflow to a developing solution, having no problem in stability over time, and obtaining extremely hard photographic characteristics with the addition of an extremely small amount.

Also, U.S. Pat.Nos. 4,385,108, 4,269,929, and 4,
No. 243,739 describes that using hydrazines having a substituent that is easily adsorbed to silver halide grains, it is possible to obtain extremely hard negative tone 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 is necessary to select a compound that does not cause such a problem.

On the other hand, although there are various direct positive photography methods, 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 halogen having a photosensitive nucleus inside the silver halide grains is mainly used. 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 of directly developing a positive image by surface-developing an internal latent-agent type silver halide photographic emulsion in the presence of an engraving 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 engraving agent may be added to the developing solution, but it is adsorbed on the surface of the silver halide grain by adding it to the photographic emulsion layer of the light-sensitive material or other appropriate layer. Sometimes better inversion characteristics can be obtained.

As the engraving 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. 3,227,522, hydrazides and hydrazine compounds described in U.S. Pat. Patents 3,615,615, 3,719,494, 3,734,738
No. 4,094,683 and 4,115,122, British Patent No. 1,
283,835, heterocyclic quaternary salt compounds described in JP-A Nos. 52-3426 and 52-69613, U.S. Pat. No. 4,030,925,
4,031,127, 4,139,387, 4,245,037, 4,2
55,511 and 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.
Phenylacyl hydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in 2,011,397B, a sensitizing dye having a substituent having a nucleating action in the molecular structure described in U.S. Pat. Kaisho 59-200,23
0, 59-212,828, 59-212,829, Research Di
The hydrazine compound described in sclosure magazine 23510 (November 1953) is known.

However, all of these compounds have insufficient activity as an engraving agent, and those with high activity do not have sufficient storage, or the activity varies after being added to the emulsion and before coating. However, it has been found that there is a defect that the film quality deteriorates when a larger amount is added.

For the purpose of solving these drawbacks, JP-A-60-179,734
No. 61-170,733, Japanese Patent Application No. 60-206,093, No. 60-1
9,739, adsorption hydrazine derivatives described in 60-111,936, hydrazine derivatives having a heteroaromatic ring residue in the molecule described in JP-A-62-275247, or JP-A-62-270948, Although hydrazine derivatives having a modifying group such as those described in JP-A-63-29,751 have been proposed, all of them are intended to enhance the stability of the development processing solution (that is, to prevent deterioration of the developing agent). The engraving activity is insufficient to meet the demands of lowering the processing solution pH, shortening the processing time of development, or reducing the dependence of changes in the composition of the developing solution (eg pH, sodium sulfite, etc.). However, there are adverse effects such as adverse effects due to the presence or absence of spillage in the developing solution.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to provide a halogenated compound capable of obtaining extremely hard negative gradation photographic characteristics having a gamma exceeding 10 using a stable developer. An object of the present invention is to provide a silver photographic light-sensitive material.

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.

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

A fourth 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.

The fifth object of the present invention is to provide a silver halide photographic light-sensitive material which has good emulsion stability over time and has little activity fluctuation during the production of a light-sensitive material.

(Structure of the Invention) The 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 other affinity colloid layer having the following general formula: This has been achieved by containing the compound represented by (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 sulfonyl group or (In the formula, R ₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group, and l 1 represents 1 or 2.)

G is (M1 represents 1 or 2) or a sulfonyl group.

X represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted.

R represents an aliphatic group substituted with a group represented by the following general formula (a).

General formula (a) In formula (a), Y _a1 and Y _a2 are Alternatively, it represents —SO ₂ — and may be the same or different. R _a1 and R _a2 represent an aliphatic group, an aromatic group or a heterocyclic group and may be the same or different.

Further, R _a1 and R _a2 may be substituted and may be bonded to each other to form a ring.

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

In the general formula (I), A ₁ and A ₂ are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms and arylsulfonyl groups (preferably substituted so that the sum of the substituent constants of the phenylsulfonyl group or Hammett is −0.5 or more). Phenylsulfonyl group), (R ₀ is preferably a straight-chain, branched or cyclic alkyl group, alkenyl group, or aryl group having 30 or less carbon atoms (preferably, the sum of the substituent constants of phenyl group or Hammett is-
A phenyl group substituted to have a value of 0.5 or more), an alkoxy group (eg, an ethoxy group), an aryloxy group (preferably a monocyclic group such as a phenyl group), etc., each of which has a substituent The substituent may be, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an 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, alkyl or aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, Carbonamide group, sulfonamide , A nitro group, an alkylthio group, and arylthio groups. ), And
The sulfone groups represented by A ₁ and A ₂ are specifically described in U.S. Pat.
Represents those described in No. 4,478,928.

A ₁ and A ₂ are most preferably hydrogen atoms.

Of the groups represented by G in the general formula (I), preferably Is.

In the general formula (I), the aliphatic group represented by X is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by X is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group.

The heterocyclic ring of X is a saturated or unsaturated heterocyclic ring containing at least one of N, O, or S atoms on pages 3 to 10, which may be a single ring or may be another aromatic group. A condensed ring of a group or a hetero ring may be formed. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, for example, pyridine, imidazolyl, quinolinyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolinyl, thiazoline,
Those containing a benzthiazolyl group are preferred.

X is preferably an aromatic group, a nitrogen-containing heterocyclic ring or a group represented by the general formula (b).

General formula (b) (Wherein X _b represents an aromatic group or a nitrogen-containing heterocyclic group,
_{^{▲ R 1 b ▼ ~ ▲ R}} 4 b ▼ each hydrogen atom, a halogen atom or an alkyl group,, X _b and _{^{▲ R 1 b ▼ ~ ▲ R}} 4 b ▼
May have a substituent if possible. r and s represent 0 or 1. X is more preferably an aromatic group, and particularly preferably an aryl group.

X may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Group, hydroxy group, halogen atom,
Cyano group, sulfo group, carboxyl group, alkyl and aryloxycarboxyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, nitro group, alkylthio group, arylthio group, etc. The group represented by (c) may be mentioned.

General formula (c) In the formula (c), Y _C is (Wherein R _C3 represents an alkoxy group or an aryloxy group), L represents a single bond, —O—, —S—, or (In the formula, R _C4 represents a hydrogen atom, an alkyl group, or an aryl group).

R _C1 and R _C2 represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and may be the same or different, or may be bonded to each other to form a ring.

X can include one or more general formulas (c).

In the general formula (c), the aliphatic group represented by R _C1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R _C1 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic ring of R _C1 is a saturated or unsaturated heterocyclic ring containing at least one of N, O, or S atoms on pages 3 to 10, which may be a single ring, or other heterocyclic ring. A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable.

R _C1 may be substituted with 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. Groups, sulfonyl groups, sulfinyl groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group.

When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R _C2 in the general formula (c) is
It is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R _C2 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group.

R _C2 may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R _C1 in the general formula (c).

If possible, R _C1 and R _C2 may be linked to each other to form a ring.

R _C2 is more preferably a hydrogen atom.

As Y _C in the general formula (c), —SO ₂ — is particularly preferable, and L is a single bond and Is preferred.

The aliphatic group represented by R _C4 in the general formula (c) is
It is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R _C4 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group.

R _C4 may be substituted with a substituent. Examples of the substituent include those listed as the substituent of R _C1 in the general formula (c).

A hydrogen atom is more preferable as R _C4 .

The aliphatic group represented by R in the general formula (I) is a linear, branched or cyclic alkyl group, alkenyl group or aryl group.

R may be substituted with a substituent. Examples of the substituent include the followings in addition to the substituent represented by the general formula (a). 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. Groups, sulfonyl groups, sulfinyl groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group.

When possible, these groups may be linked to each other to form a ring.

R may include one or more of general formula (a).

In the general formula (a), the aliphatic group represented by R _a1 and R _a2 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R _a1 and R _a2 is a monocyclic ring or 2
A ring aryl group, and examples thereof include a phenyl group and a naphthyl group.

The hetero ring of R _a1 and R _a2 is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, or S atoms, and these may be a single ring, Further, a condensed ring may be formed with another aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable.

R _a1 and R _a2 may be substituted with 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. Groups, sulfonyl groups, sulfinyl groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group.

In the general formula (a), Y _a1 and Y _a2 are Alternatively, —SO ₂ — is preferable, and at least one is particularly preferable. It is preferred that

R _a4 and R _a2 in the general formula (a) are linked to each other to form N
It is preferred to form a heterocycle with the atoms. Further, this ring may have a hetero atom other than the N atom of the general formula (a) as an atom forming the ring, or may form a condensed ring structure together with another ring.

In the general formula (I), either or both X and R may have an adsorption promoting group for silver halogelation.

R or X is a substitutable silver halide adsorption-promoting group, which can be represented by ZLz _t , Z is a silver halide adsorption-promoting group, and L _Z is a divalent linking group. t
Is 0 or 1.

Preferred examples of the adsorption accelerating group represented by Z on silver halide include a thioamide group, a group having a mercapto group disulfite bond, or a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Z is A divalent group represented by amino-1, which may be a part of a ring structure or an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
030,925, 4,031,127, 4,080,207, 4,245,0
No. 37, 4,255,511, 4,266,013, and 4,276,36
No. 4 and "Research Disclosure" (Res
earch Disclosure, Volume 151, No. 15162 (November 1976)
176), and those disclosed in Vol. 176, No. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, a thioureido group, a thiourethane group, a dithiocarbamate group, and a specific example of the cyclic thioamide group.
For example, 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-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione and benzthiazoline- 2-thione and the like can be mentioned, which may be further substituted.

The mercapto group represented by Z is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, a cyclic thioamide group having a tautomeric relationship with the nitrogen atom) And specific examples of this group are the same as those listed above).

The 5- or 6-membered nitrogen-containing heterocyclic group represented by Z is composed of a combination of nitrogen, oxygen, sulfur and carbon.
And a 6- to 6-membered nitrogen-containing heterocycle. Among these, bezotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole and triazine are preferable.
These may be further substituted with appropriate substituents.

Examples of the substituent include those described as the substituent of X. Among those represented by Z, preferred are cyclic thioamide groups (that is, mercapto-substituted nitrogen-containing hetero groups, for example, 2-mercaptothiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.) or nitrogen-containing heterocyclic group (for example, benzotriazole group,
Benzimidazole group, indazole group, etc.). Further, two or more ZLz _t groups may be substituted and may be the same or different.

Examples of the divalent linking group represented by L _Z include C, NS and
An atom or atomic group containing at least one of O.
Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH.
-, - N =, - CO -, - SO 2 -, Luo groups are those consisting of a single or combination of even or) or the like have a substituent.

Specific examples include, for example, -CONH-, -NHCONH-, -SO
₂ NH-, -COO-, -NHCOO-, _{-CH 2 -, CH 2 2 -} , CH 2 3, NHCONHCH ₂ CH ₂ CONH−, _{-CH 2 CH 2 SO 2 NH -} , - CH 2 CH 2 CONH- , and the like.

These may be further substituted with appropriate substituents. Examples of the substituent include those described as the substituent of X.

Further, X or R may contain a ballast group which is commonly used in a non-moving photographic additive such as a coupler.

The ballast group is an organic group that gives a sufficient molecular weight to prevent the compound represented by the general formula (I) from substantially diffusing into another layer or the treatment liquid, and is an alkyl group, an aryl group, a heterocyclic group, Ether group, thioether group, amide group, ureido group, urethane group, sulfonamide group,
And one or more other combinations. The ballast group is more preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

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

The hydrazine derivative of the present invention was synthesized by reacting the corresponding hydrazine with a carboxylic acid in the presence of a condensing agent such as dicyclohexylcarbodiimide, or by reacting the corresponding hydrazine with an acid chloride of a carboxylic acid or a sulfonic acid in the presence of a base.

 A typical synthesis example is shown below.

(Synthesis example 1 ... Synthesis of compound 4) A mixture of p-tolylhydrazine hydrochloride (12.0 g), N-methyl-morpholine (16.7 ml) and acetonitrile (150 ml) was added to succinimide acetyl chloride (13.3) under ice cooling.
A solution of g) in acetonitrile (80 ml) was added dropwise over 30 minutes. After stirring for 30 minutes under ice-cooling and returning to room temperature for 1 hour, volatile components were distilled off under reduced pressure. 1N Hydrochloric acid was added, the mixture was extracted with ethyl acetate, washed with water, dried and concentrated. The residue was recrystallized from ethyl acetate to obtain the desired product. (Yield 5.8 g) The chemical structure was confirmed by nm spectrum, ir spectrum and elemental analysis. (Synthesis example 2 ... Synthesis of compound 8) Agricultural hydrochloric acid (4 ml) was added to the mixture with methanol (50 ml), and the mixture was stirred at room temperature overnight. After completely removing the volatile components under reduced pressure,
Acetonitrile (80 ml), DMF (20 ml), pyridine (8 m
l) was added, followed by succinimidoacetyl chloride (5.5 g). After stirring overnight at room temperature, the volatile matter was distilled off again under reduced pressure, and the product was purified by silica gel chromatography to obtain the desired product. (Yield 4.7 g). The chemical structure was confirmed by nm spectrum, ir spectrum and elemental analysis.

 Other compounds were synthesized by the same method.

In order to incorporate the compound of the present invention into a photographic emulsion layer or a hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary, alkali hydroxide or trihydric acid). May be dissolved by adding a secondary amine to form a salt), a hydrophilic colloid solution (for example, a silver halide emulsion,
(Eg, gelatin aqueous solution) may be added (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 ^{−6 to} 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol per mol of silver halide, and they are combined. An appropriate value can be selected according to the properties of the silver halide emulsifier.

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 to form a negative image with high contrast,
The average grain size of silver halide used is preferably fine grains (for example, 0.7 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" used here 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 regular crystal grains such as cubes, octahedra, rhombohedrons and tetrahedra, and irregular grains such as spheres and tabular grains. ), Or 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.

The silver halide emulsion used in the present invention includes a cadmium salt in the process of formation or physical ripening of silver halide grains,
Sulfite, lead salt, thallium salt, rhodium salt or complex salt thereof, iridium salt or complex salt thereof may coexist.

The silver halide used in the present invention is 10 ^-8 to 1 mol per mol of silver.
A silver haloiodide prepared in the presence of 10 ^-5 mol of an iridium salt or a complex salt thereof and having a silver iodide content on the grain surface 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 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 U.S. Pat.No. 2,448,060,
It is described in, for example, British Patent No. 618,016. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin,
Various sulfur compounds such as thiosulfates, thioureas,
Thiazoles, rhodanines and the like can be used.

In the above, it is preferable to use an iridium salt or a rhodium salt before the 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 a Japanese Patent Application No. 60-6419.
No. 9 and 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). Sensitization is preferable, and sulfur sensitization is the most preferable method of chemical sensitization. The large size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Large-sized monodisperse agents generally do not undergo chemical sensitization because black spots are likely to occur, but when chemically sensitized, it is particularly preferable to apply shallowly to the extent that black spots do not occur. As compared with the chemical sensitization of small-sized grains, the chemical sensitization time is shortened, 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 monodispersant 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 using a developer having a pH of 10.5 to 12.3 containing the above. 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 0.02
It is preferable that the average particle size of large-sized and small-sized monodisperse particles be included in this range from 0.1 to 0.5 μ, more preferably from 0.1 to 0.5 μ.

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

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

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

In the light-sensitive material used in the present invention, sensitizing dyes (for example, cyanine dyes and merocyanine dyes) described in JP-A-55-52050, pages 45 to 53, for the purpose of increasing sensitivity.
Can be added. 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 (Research
Disclosure) 176 Volume 17643 (Published December 1978) Page 23 IV
J section of.

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

Suitable development accelerators or nucleation infectious development accelerators for use in the present invention are disclosed in JP-A Nos. 53-77616 and 54-3.
7732, 53-137133, 60-140340, 60-1495
In addition to the compounds disclosed in No. 9 and the like, various compounds containing an N or S atom 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 , preferably 5.0 × 10 ^−3.
It is preferably used in the range of 0.1 g / m ² .

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

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

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

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

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

For these dyes, an emulsion layer is added depending on the purpose,
Alternatively, it is preferably added and fixed together with a mordant in the upper portion of the silver halide emulsion layer, that is, the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support.

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

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

Examples of the ultraviolet absorber include a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenenone compound, a cinnamic acid ester compound,
A butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of the ultraviolet absorber, U.S. Pat.
3,314,794, 3,352,681, JP-A-46-2784, U.S. Patents 3,705,805, 3,707,375, 4,045,229, and
3,700,455, 3,499,762, West German patent application publication 1,547,
No. 863, 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, pyrazolooxonol dyes described in U.S. Pat.No. 2,274,782, diarylazo dyes described in U.S. Pat.No. 2,956,879, U.S. Pat.No. 3,423,207,
Styryl dyes and butadienyl dyes described in No. 3,384,487, merocyanine dyes described in U.S. Pat.No. 2,527,583, U.S. Pat.Nos. 3,486,897, 3,652,284, and 3,
No. 718,472, merocyanine dyes and oxonol dyes, U.S. Pat.No.3,976,661, enaminohemioxonol dyes described in U.S. Pat.No. 3,976,661 and British Patent Nos. 584,609 and 1,177,429.
No. 48-85130, No. 49-99620, No. 49-114420
U.S. Pat.Nos. 2,533,472, 3,148,187, and 3,
No. 177,078, No. 3,247,127, No. 3,540,887, No. 3
The dyes described in 3,575,704 and 3,653,905 are used.

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

The specific amount of dye used is generally 10 ⁻³ g / m ^{2 to} 1 g / m ² ,
In particular it is possible to find the preferred amount in the range of ^{10 -3 g / m 2 ~0.5g /} m 2.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. 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 and the like), 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, development acceleration, high contrast) Various surfactants may be included for various purposes such as sensitization 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 Nos. 60-80849 and 59-7455).

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, alkyl (meth) acrylate, alkoxy acrylate (meth) acrylate, glycidyl (meth) acrylate, alone or in combination,
Alternatively, a polymer having a monomer component of a combination of these and acrylic acid, methacrylic acid, or the like 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 super-high contrast and high-sensitivity photographic characteristics using the halogelated silver light-sensitive material of the present invention, it is necessary to use a conventional infectious phenomenon solution or a highly alkaline developing solution close to pH 13 described in U.S. Pat.No. 2,419,975. However, 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 to 10.
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 developer used in the present invention, but it is preferable to contain dihydrosibenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3 are preferable. -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.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
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, as a silver stain preventing agent, JP-A-56-1
The compound described in 4,347 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, the compounds described in JP-A-60-93,433 or the compounds described in Japanese Patent Application No. 61-28,708 can be used as the pH buffer used in the developing solution.

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, or can be combined with an internal latent image type silver halide emulsion. I will 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 1 mol per mol of silver in silver emulsion
A range of 0.005 mg to 500 mg is practically useful, with about 0.01 mg to about 100 mg per silver mole being preferred. When the emulsion layers are contained in the adjacent hydrophilic colloid layers, the internal latent image type halogen may be contained in the same amount as the amount of silver contained in the same area of the internal latent image type emulsion layer. The definition of 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.

The preferable internal latent image type emulsion which can be used in the present invention is described in Japanese Patent Application No. 61-253716, page 28, line 14 to page 31, line 2, and preferable silver halide grains are described in the same specification.
It is described on page 31, 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 a sensitizing dye,
Cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, styryl dyes, hemicyanine dyes, oquinonol dyes, hemioxonol dyes 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 Research Disclosure (RD) 17643 (December 1978), Sections VII-D and 1871.
7 (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 coupler is excellent in the fastness of the color-developing color foundation, particularly the light fastness, while the α-benzoyl acetanilide type coupler can obtain a high coloring 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 a leaving group of 2-equivalent 5-pyrazolone-based coupler,
Particularly preferred are nitrogen atom leaving groups described in US Pat. No. 4,310,619 or arylthio groups described in US Pat. No. 4,351,897. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As the pyrazoloazole-based coupler, US Pat.
379,899 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat.No. 3,725,067, Research Disclosure 24220 (June 1984). ) And the research discloser 24
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of less yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 119,8
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferable.

Cyan couplers that can be used in the present invention include oil-protective naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,80.
1,171, 2,772,162, 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 having the dye formed from the magenta and cyan couplers, 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. Patent No. 4,366,237 and British Patent No.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a duplex or more. 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 2,102,173 and US Pat. No. 4,367,282.

The various couplers used in the present invention may be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound may be used in two or more different layers. 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 photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In the present invention, a developing agent such as hydroxybenzenes (for example, hydroquinones), aminophenols, 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 are known, and among them, although they are initially non-diffusible, they can be oxidized 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-hydroxyalurulsulfamoyl group as described in 4,336,322, etc.
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 particularly small.

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

Details of the color couplers 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
More preferably, it is in the range of 11.0-10.0.

The fogging treatment in the present invention includes a so-called "light fogging method" for giving a second exposure to the entire surface of the photosensitive layer and a "chemical fogging method" for developing in the presence of a nucleating agent. Either 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, page 47, line 4 to page 49, line 5, and regarding the nucleating agent that can be used in the present invention, the same specification, page 49, line 6. Line to page 67 2
In particular, the general formulas [N-1] and [N-
Use of the compound represented by 2] is preferred. Specific examples thereof include [NI] described on pages 56 to 58 of the same specification.
1] to [NI-10] and [N-II-1] to [N-II-12] described on pages 63 to 66 of the same specification are preferably used.

With respect to the nucleation accelerator that can be used in the present invention, see
P. 68, line 11 to p. 71, line 3, and specific examples thereof include (A-1) to (A-1) on pages 69 to 70.
Use of 3) is preferred.

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-amine-
N-ethyl-N- (β-methanesulfonamidoethyl)
Aniline, 3-methyl-4-amino-H-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.

After color development, the photographic emulsion layer 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 treatment 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 for these, it is preferable to carry out the method described in Japanese Patent Application No. 61-131632.

Further, as the additive used in the washing and stabilizing steps, various compounds described in Japanese Patent Application No. 61-32462, pp. 30-36 can be used.

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

Example 1 4 × 10 ⁻⁷ per mol of silver was added to an aqueous gelatin solution maintained at 50 ° C.
In the presence of a molar amount of potassium iridium (III) hexachloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodopotassium bromide are simultaneously added for 60 minutes, and the pAg between them is kept at 7.8 to obtain an average particle size of 0.28 μm. A cubic monodisperse emulsion having an average silver iodide content of 0.3 mol% was prepared. This emulsion was desalted by the flow curation method, and then 40 g of inactive gelatin was added per mol of silver, followed by 50 ° C.
5,5'-dichloro-9-ethyl- as a sensitizing dye
3-3'-bis- (3-sulfopropyl) oxacarbocyanine and KI solution of 10 ^-3 mol per mol of silver were added,
The temperature was lowered for 15 minutes and then lowered. Redissolve this emulsion,
At 40 ° C, 0.02 mol of methylhydroquinone / mol of silver,
And a hydrazine derivative of the present invention or a comparative example shown in Table 1 is further added, and 5-methylbenzotriazole, 4-hydrazine-1,3,3a, 7-tetrazaindene, the following development accelerator (a), (roth) ), And a polyethyl acrylate dispersion of 0.4 g / m ² , and a mixture of the following compounds (C), (D), and (E) as a gelatin hardener to prevent the formation of vinylidene chloride copolymer: Silver amount on polyethylene terephthalate support (150μ) with subbing layer (0.5μ)
It was applied so as to be 3.4 g / m ² .

(D) CH ₂ = CHSO ₂ CH ₂ SO ₂ CH = CH ₂ (e) CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ CH ₂ NHCOCH ₂ SO ₂ CH = CH ₂ On top of this, gelatin 1.5 g / m 2 ^2. A layer containing polymethylmethacrylate particles (average particle diameter 2.5 μm) 0.3 g / m ² and the following surfactant was applied.

Surfactant [I] Evaluation of contrast enhancement performance These samples were exposed to tungsten light of 3200 ° K through an optical wedge, developed with the following developer at 34 ° C for 30 seconds, fixed, washed with water and dried. The sensitivity and gradation of the obtained photographic properties are shown in Table-1. When the nucleating agent of the present invention is used,
High sensitivity and high contrast were obtained.

[2] Photographic evaluation with fatigued developer Automatic plate making machine FG660F type (Fuji Photo Film Co., Ltd.)
Manufactured by the above-mentioned developer-I, and then at 3 ° C. under 3 conditions.
It was developed for 30 seconds, fixed, washed with water and dried.

[A] Immediately after the temperature of the developer filled in the automatic processor reaches 34 ° C., development processing is performed. (Development with fresh liquid).

[B] The developing treatment is carried out with the liquid left for 4 days while the automatic developing machine is filled with the developing liquid. (Development with air fatigue liquid).

[C] After the developer was packed in an automatic processor, Fuji Film GRNDEX GA-100 film was exposed to a size of 50.8 cm x 61.0 cm so that 50% of the area could be developed.
Processing is performed on one sheet, and development processing is performed with a solution which is repeated for 5 days. Add 100 cc of Developer-I for each processed sheet. (Development with large amount of fatigue fluid). The photographic properties obtained are shown in Table-I. In terms of processing running stability, it is desirable that the photographic properties obtained by [B] and [C] are not different from those of [A]. As can be seen from the results of Table-I, when the nucleating agent of the present invention is used, the fluctuation in photographic sensitivity is small even when the developer is fatigued.

Example-2 5.0 × 10 5 per mol of silver in a gelatin aqueous solution kept at 50 ° C.
-Simultaneously mix aqueous silver nitrate solution and aqueous sodium chloride solution in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , then remove soluble salts by a method well known in the art, and then add gelatin to chemically 2-methyl-4 as a stabilizer without aging
-Hydroxy-1,3,3a, 7-tetraazaindene was added. This emulsion was a cubic dispersion monodisperse emulsion having an average grain size of 0.15μ.

A hydrazine compound was added to this emulsion as shown in Table 2, and polyethyl acrylate latex was added in an amount of 30% by weight based on the solid content of gelatin. In addition, it was coated on a polyester support so that the Ag amount was 3.8 g / m ² . 1.8 for gelatin
It was g / m ² . Gelatin 1.5 g / m ² as a protective layer on this
And a protective layer containing 0.3 g / m ^{2 of} polymethylmethacrylate particles (average particle size 2.5 μm) as a matting agent, and the following surfactants, stabilizers, and UV absorbing paints as coating aids, and dried. did.

Surfactant Stabilizer thioctic acid 2.1 mg / m ² This sample was exposed through an optical wedge with a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd. and exposed at 38 ° C. for 20 minutes.
Second development processing, fixing, washing with water and drying.

 The obtained photographic results are shown in Table 2.

From the results of Table-2, it can be seen that the sample of the present invention can obtain higher hardness than the sample of the comparative example.

Further, as a result of testing the photographic performance in a fatigue developing solution in the same manner as in Example-1, as shown in Table-2, the samples of the present invention showed small fluctuation and showed favorable results.

Claims (1)

(57) [Claims] 1. A halogenation having at least one silver halide photographic emulsion layer, wherein the photographic emulsion layer or another hydrophilic colloid layer contains a compound represented by the following general formula (I). Silver photographic 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 sulfonyl group or (In the formula, R ₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group, and l 1 represents 1 or 2.) G is (M1 represents 1 or 2) or a sulfonyl group. X represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. R represents an aliphatic group substituted with a group represented by the following general formula (a). General formula (a) In formula (a), Y _a1 and Y _a2 are Alternatively, it represents —SO ₂ — and may be the same or different. R _a1 and R _a2 represent an aliphatic group, an aromatic group or a heterocyclic group and may be the same or different. Further, R _a1 and R _a2 may be substituted and may be bonded to each other to form a ring.