JPH02198440A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain photographic characteristics of an extremely high contrast negative gradation by incorporating a specific compd. into photographic emulsion layers or other hydrophilic colloidal layers. CONSTITUTION:The compd. expressed by formula I is incorporated into the emulsion layers or at least one of the other hydrophilic colloidal layers of the silver halide photographic sensitive material having the silver halide photographic emulsion layers. In formula I, A1, A2 both denote a hydrogen atom or one thereof denotes the hydrogen atom and the other a sulfonyl group, etc.; G denotes a sulfonyl group, sulfoxy group, thiocarbonyl group, etc.; X denotes an aliphat. group, arom. group, or heterocyclic group.; R denotes the aliphat. group substd. by the group expressed by formula II. In formula II, Ya1, Ya2 denote formula III, -SO2, etc.; Ra1, Ra2 denote an aliphat. group, arom. group or heterocyclic group. The photographic characteristics of the extremely hard contrast negative gradation are obtd. in this way even with a developing soln. of low pH.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is a silver halide photographic material that provides extremely high contrast negative images, highly sensitive negative images, good halftone image quality, or directly forms positive photographic images. The present invention relates to a silver halide photographic material containing a novel compound as a nucleating agent for silver halide.

(Prior Art) The addition of a hydrazine compound to a silver halide photographic emulsion or developer is disclosed in U.S. Pat.
No. 227,552 (using hydrazine as an auxiliary developer to obtain a direct positive color image), No. 3,386,83
No. 1 (contains β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), No. 2,41
9.975, and The Theory Off Photographic Ink Process by Mees.
theory of Photographic Proc
ess) 3rd edition (I966), 281 pages, etc.

Among these, in particular, US Pat. No. 2,419.975 discloses that a high-contrast negative image can be obtained by adding a hydrazine compound.

The patent specification states that by adding a hydrazine compound to a silver chlorobromide emulsion and developing it with a developer with a high pH of 12.8, extremely high contrast photographic properties with a gamma (γ) exceeding 10 can be obtained. is listed. However, the pH is 1
A strong alkaline developer close to 3 is unstable and susceptible to air oxidation, and cannot withstand long-term storage or use.

Ultra-high contrast photographic characteristics with gamma exceeding 10 are negative images,
Either a positive image or a halftone image (
It is extremely useful for photographic reproduction of continuous tone images (dot images) or reproduction of line drawings.

Conventionally, for this purpose, the content of silver chloride was set at 50%.
A common method is to use a silver chlorobromide photographic emulsion with a mol%, preferably over 75 mol%, and develop it with a hydroquinone developer with an extremely low effective concentration of sulfite ions (usually 0.1 mol/l or less). It was used in However, with this method, the concentration of sulfite ions in the developer is low, so
The developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, all of these methods require the use of a silver chlorobromide emulsion with a relatively high silver chloride content, and therefore high sensitivity cannot be obtained. Therefore, there has been a strong demand for using a highly sensitive emulsion and a stable developer to obtain ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings.

U.S. Patent Section 4.224,401, 4. Engineering 68.97
No. 7, No. 4,243,739, No. 4゜272.614
No. 4,323,643 discloses a silver halide photographic emulsion that uses a stable developer and provides extremely high contrast negative photographic properties, but how many acylhydrazine compounds were used in these? It has been found that it has some drawbacks.

In other words, these conventional hydrazines are known to generate nitrogen gas during the development process, and these gases collect in the film and form bubbles that damage the photographic image. This is because the leakage into other photographic materials has an adverse effect on other photographic materials.

It has been known to increase the molecular weight of a nucleating agent to make it diffusion resistant as a means of preventing it from leaking into the development processing solution. It turns out there is a problem. That is, when a coating solution containing a nucleating agent is aged, precipitates are formed in the coating solution, deteriorating the filterability, and furthermore, changing the photographic performance.

In addition, when these conventional hydrazines are required in large quantities for sensitization and high contrast, or when particularly high sensitivity is required for the performance of window materials, other sensitization techniques (such as chemical sensitization) may be used. In general, when used in combination with compounds that enhance sensitization such as increasing Sensitization and enhancement blur may occur over time during storage.

Therefore, there has been a desire for a compound that can reduce the generation of bubbles and leakage into the developer, has no problems with stability over time, and can provide extremely high-contrast photographic properties with the addition of a very small amount. .

Also, U.S. Patent No. 4,385,108, U.S. Patent No. 4,269
．． No. 929 and No. 4,243,739 describe that extremely sharp negative gradation photography can be obtained by using hydrazines having substituents that are easily adsorbed to silver halide grains. Among these hydrazine compounds having adsorbent groups, those specifically mentioned in the above-mentioned known examples have the problem of causing desensitization over time during storage. Therefore, it was necessary to select a compound that would not cause such problems.

On the other hand, there are various direct positive photography methods, including a method in which silver halide grains that have been fogged in advance are exposed to light in the presence of a desensitizer, and then developed, and a method in which silver halide grains are exposed to light in the presence of a desensitizer and then developed, The most useful method is to develop the silver oxide emulsion in the presence of a nucleating agent after exposure. The present invention relates to the latter.

Silver halide emulsions that mainly have photosensitive nuclei inside silver halide grains and in which latent images are mainly formed inside the grains are called internal latent image type silver halide emulsions. They can be distinguished from image-forming silver halide grains.

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

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

The nucleating agent used in the above method for obtaining a direct positive image includes US Pat. No. 2,563,785 and US Pat.
8,982, and the hydrazides and hydrazine compounds described in U.S. Pat. No. 3,227.552, U.S. Pat. No. 3,615,615
No. 3,719.494, No. 3,734,738, No. 4゜094.683 and No. 4,115,122
No., British Patent No. 1,283,835, Japanese Patent Application No. 5234
Heterocycle No. 4 described in No. 26 and No. 52-69613
class salt compound, U.S. Pat. No. 4,030°925, 4,
No. 031,127, No. 4.139.387, No. 4.2
No. 45,037, No. 4゜255.511 and No. 4,
276.364, a thiourea-bonded acylphenylhydrazine compound described in British Patent No. 2,012,443, etc., and a peterocyclic thioamide described in U.S. Patent No. 4,080,207 as an adsorption group. compound, a phenylacylhydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in British Patent No. 2,011,397B, and a nucleating substitution described in U.S. Patent No. 3,718,470. Sensitizing dye having a group in its molecular structure, JP-A-59200.230, JP-A No. 59-212,
No. 828, No. 59-212.829, Re5earc
h Disclosure magazine No. 23510 (I953
A hydrazine compound described in (November 2013) is known.

However, all of these compounds have insufficient activity as nucleating agents, and those with high activity have insufficient storage stability, or their activity fluctuates between the time they are added to the emulsion and the time they are coated. It has been found that there are drawbacks such as deterioration of film quality when a larger amount is added.

In order to solve these drawbacks, JP-A-60-179.7
No. 34, No. 61-170,733, Patent Application No. 60-20
No. 6,093, No. 60-19,739, No. 60-11
Adsorption type hydrazine derivatives described in No. 1,936, hydrazine derivatives having a heteroaromatic ring residue in the molecule described in JP-A-62-275247, or JP-A-62-275247.
Hydrazine derivatives having a modifying group as described in No. 2-270948 and JP-A No. 63-29,751 have been proposed, but all of them improve the stability of the developing solution (in other words, they increase the stability of the developing agent). (to prevent deterioration)
The nucleating activity may not be sufficient to meet the demands of lowering H, shortening the development processing time, or reducing dependence on changes in developer composition (e.g. pH, sodium sulfite, etc.). , or leakage into the developing processing solution, resulting in adverse effects.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a halogen-based compound that can obtain photographic characteristics of extremely sharp negative gradations with a gamma exceeding 10 using a stable developer. An object of the present invention is to provide a silver photographic material.

A second object of the present invention is to contain highly active hydrazines that can provide the desired extremely sharp negative gradation photographic characteristics even in a low pH developer with a small amount added without adversely affecting photographic characteristics. An object of the present invention is to provide a negative-working silver halide photographic material.

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

A fourth object of the present invention is to provide a silver halide photographic light-sensitive material that is easy to synthesize, contains a hydrazine, and has good storage stability over time.

A fifth object of the present invention is to provide a silver halide photographic light-sensitive material whose emulsion has good stability over time and whose activity fluctuations are small during the production of the light-sensitive material.

(Structure of the Invention) An aspect of the present invention is that in a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, at least one of the following is added to the photographic emulsion layer or at least one other hydrophilic colloid layer. This was achieved by containing a compound represented by general formula (I).

General formula (I) represents an aryl group, an alkoxy group, or an aryloxy group, and β1 is 1
or 2.

represents. G is +C±, (m+ represents 1 or 2), sulfonyl group, sulfoxy group, P- (wherein R0 represents an alkoxy group or an oxy group), thiocarbonyl group or iminomethylene represents a 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 (al).

Represents the general formula (al P- (in the formula, R113 represents an alkoxy group or an aryloxy group), and may be the same or different. Ro and R3□ are an aliphatic group, an aromatic group, or a heterocyclic group. They represent groups and may be the same or different.

Further, R□ and Ra2 may be substituted or may be bonded to each other to form a ring.

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

In general 2N), A + and A 2 are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl groups (preferably phenylsulfonyl groups or Hammett's sum of substituent constants of -0.5 or more). phenylsulfonyl group substituted so that), +C+. Ro (Ro
is preferably a linear, branched or cyclic alkyl group, alkenyl group, or aryl group having 30 or less carbon atoms (preferably a phenyl group, or a group whose sum of Hammett's substituent constants is -0).
(phenyl group substituted so as to have 5 or more), alkoxy group (e.g. ethoxy group, etc.), oryloxy group (
Preferably monocyclic ones such as phenyl group), etc.
These groups may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an 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 or carboxyl group, alkyl or aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group , sulfonamide group, nitro group, alkylthio group, arylthio group, etc. ), and AI, At
Specifically, the sulfone group represented by
78.928.

As AI and A2, a hydrogen atom is most preferable.

Among the groups represented by G in general formula (I), 10- is preferred.

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 or a naphthyl group.

The heterocycle of It may form a fused ring with an aromatic or heterocycle. Preferably, the heterocycle is a 5- to 6-membered aromatic heterocyclic group, such as a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group,
Those containing a benzthiazolyl group are preferred.

Preferred as X are aromatic groups, nitrogen-containing heterocycles, and groups represented by the general formula (bl).

General formula (bl (wherein, X represents an aromatic group or a nitrogen-containing heterocyclic group, R1 to J each represent a hydrogen atom, a halogen atom, or an alkyl group, and In some cases, it may have a substituent. r and S represent O or 1.) X is more preferably an aromatic group, and particularly preferably an aryl group.

X may be substituted with a substituent. Examples of substituents include alkyl groups, aralkyl groups, alkenyl groups,
Alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, alkylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, etc. In addition to carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, nitro groups, alkylthio groups, arylthio groups, etc., those represented by the following general formula (C) Examples include groups.

General formula (C) RCI-L-YC-N C2 formula (in C1, Yc represents -c--5o2- -pIORc3 (in the formula, Rc3 represents an alkoxy group or an aryloxy group), and L represents Represents a single bond, -08-1 or -N- (in the formula, Rc4 represents a hydrogen atom, an alkyl group, or an aryl group).

RCI and Rcz represent a hydrogen atom, an aliphatic group, or a heterocyclic group, which may be the same or different, and may be bonded to each other to form a ring.

Further, X can contain one or more of general formula (C).

In the general formula (C1), the aliphatic group represented by Rcl is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

The heterocycle of Rcl is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, 0, or S atoms, and these may be monocyclic,
Furthermore, a condensed ring may be formed with another aromatic or heterocycle. Preferably, the heterocycle is a 5- to 6-membered aromatic heterocycle, such as a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, or a benzthiazolyl group. Preferably.

Rel may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
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, These include alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, nitro groups, alkylthio groups, and arylthio groups.

These groups may be linked to each other to form a ring when possible.

The aliphatic group represented by RCZ in the general formula (C1 is
It is a straight chain, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R62 is a monocyclic or bicyclic aryl group, such as a phenyl group.

Rcz may be substituted with a substituent. Examples of the substituent include those listed as substituents for Rcl in the general formula (C1).

Further, RCI and RCZ may be connected to each other to form a ring, if possible.

More preferably, R1 is a hydrogen atom.

Yc in the general formula Tel is particularly preferably -C--SO,-, and L is preferably a single bond or -N-.

The aliphatic group represented by RCl in the general formula (C1 is
It is a straight chain, branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

RCl may be substituted with a substituent. Examples of the substituent include those listed as substituents for RCl in the general formula (C1).

As RCl, a hydrogen atom is more preferable.

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

R may be substituted with a substituent. As substituents,
In addition to the substituents represented by the general formula (al), examples include the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
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, These include alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, nitro groups, alkylthio groups, and arylthio groups.

These groups may be linked to each other to form a ring when possible.

Further, R can include one or more of the general formula (al).

In the general formula Ta+, the aliphatic group represented by R□ and R8□ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by Ro and Ro is a monocyclic or dicyclic group.
It is a ring aryl group, such as a phenyl group or a naphthyl group.

The heterocycle of Ro and R12 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, Ol, or S atoms, and these may be monocyclic or It may also form a fused ring with other aromatic or heterocycles. The heterocycle is preferably 5 to 6
A membered aromatic heterocyclic group, such as a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group,
Those containing a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a benzthiazolyl group are preferred.

Ro and Ro may be substituted with a substituent.

Examples of the substituent include the following.

These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
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, sia] group, sulfo group and carboxyl group , alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, nitro groups, alkylthio groups, arylthio groups, and the like.

In the general formula (al), Y□, Y, and 2 are preferably 10-1 or -302-, and particularly preferably at least one is -C-.

R3 and R3□ in general formula (a) are connected to each other,
It is preferable to form a heterocycle together with the N atom. Further, this ring may have a heteroatom other than the N atom of the general formula (al) as a ring-forming atom, or may form a fused ring structure with other rings.

In general formula (I), either or both of X and R may have a group promoting adsorption to silver halide.

The adsorption-promoting group to silver halide that can be substituted with R1 or X can be represented by Z(-R2-)-t, Z is the adsorption-promoting group to silver halide, and L2 is a divalent linking group. It is. t is 0 or 1.

Preferred examples of the adsorption promoting group to silver halide represented by Z include a thioamide group, a mercapto group, a group having a disulfide 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 C-amino-, and may be a part of a ring structure, or may be an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
, No. 925, No. 4.031, 127, No. 4,080,
No. 207, No. 4,245,037, No. 4,255,5
No. 11, No. 4,266.013, No. 4,276.364, and “Research Disclosure J.
(Research Disclosure) Nodule 1
It can be selected from those disclosed in Vol. 51 Nα15162 (November 1976) and Vol. 176 Nα17626 (December 1978).

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, and dithiocarbamate groups; specific examples of cyclic thioamide groups include 4-thiazoline-2thione, 4-imidacyline-2
-1,000 ions, 2-thiohydantoin, rhodanine, thiobarbic acid, tetrazoline-5-thione, 1,2.4
-triazoline-3-thione, 1,3,4-thiadiazolin-2-thousand, 1,3,4-oxadiazolin-2
-thione, benzimidacillin-2-thione, benzoxazoline-2-thione, and benzothiazoline-2-thione, which may be further substituted.

The mercapto group of Z is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (if the carbon atom to which the -3H group is bonded is a nitrogen atom, a cyclic thioamide group that has a tautomeric relationship with this) and specific examples of this group are the same as those listed above).

The 5- to 6-membered nitrogen-containing heterocyclic group represented by Z includes a 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur, and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine, and the like.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for X. Among those represented by Z, preferred are cyclic thioamide groups (i.e., mercapto-substituted nitrogen-containing heterocycles, such as 2-mercaptothiadiazole 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 (e.g., benzotriazole group, benzimidazole group, benzuzole group, etc.) be. Moreover, Z+L, +, and two or more groups may be substituted, and may be the same or different.

The divalent linking group represented by L2 includes C1N-3,
An atom or atomic group containing at least one type of O.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O--3--NH--
The group N= -C0-302-1 may have a substituent) alone or in combination.

As a specific example, for example -〇〇NH -NHCONH--3O! NH--Co.

Examples include HCOO CHw-1+cnz-)-z, +CHz÷2, =30 NHCONHCH, CH2C0NH CHzCHzSO2NHCHzCHzCONH.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for X.

Further, X or R may contain therein a ballast group commonly used in immobile photographic additives such as couplers.

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

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

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

17° 20° 13° 15° 21° 22゜ 25° 27° 28° 34° =39 29° 30° 31° CI2CH2SH 39° CH.

41゜R 47゜The hydrazine derivative of the present invention can be obtained 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. It was synthesized by

Typical synthesis examples are shown below.

(Synthesis Example 1...Synthesis of Compound 4) p-Tolylhydrazine hydrochloride group (I2,0g), N-methyl-morpholine (I6,7+d), acetonitrile (I50mffi)
) to a mixture of succinimide acetyl chloride (
A solution of I3.3g) in acetonitrile (80-) was added dropwise over 30 minutes.

After cooling with water for 30 minutes, returning to room temperature and stirring for 1 hour,
Volatile components were distilled off under reduced pressure. IN hydrochloric acid was added and the mixture was extracted with 43° ethyl acetate, washed with water, and then dried and concentrated. The desired product was obtained by recrystallizing the residue with ethyl acetate. (Yield: 5.8 g) The chemical structure was confirmed by nmr spectrum, IR spectrum, and elemental analysis.

(Synthesis Example 2...Synthesis of Compound 8) Methanol (
Concentrated hydrochloric acid (4-) was added to 50 ml of the mixture, and the mixture was stirred at room temperature overnight. After the volatile components were completely distilled off under reduced pressure, acetonitrile (80 mf), DMF (20+d), and pyridine (8-) were added, followed by succinimide acetyl chloride (5.5 g). After stirring overnight at room temperature, the volatile components were again distilled off under reduced pressure and purified by silica gel chromatography to obtain the desired product. (Yield 4.7
g). Chemical structure is nmr spectrum, ir spectrum,
Confirmed by elemental analysis.

Other compounds were synthesized in the same manner.

When incorporating 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 (alkali hydroxide or tertiary amine is added as necessary). (You may add it to make salt and dissolve it)
, hydrophilic colloid solution (for example, silver halide emulsion, gelatin aqueous solution, etc.) may be added with VC (at this time, pn may be adjusted by adding acid or alkali as necessary)
.

The compounds of the present invention may be used alone or in combination of two or more. The amount of the compound of the present invention added is preferably I)/×IO~ per mole of silver halide! xl0-2 mono, more preferably uX/θ-5 mol to lx/θ-2 mol,
An appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

The compound represented by the general 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 the general formula (I) of the present invention is preferably used in combination with a negative emulsion to form a negative image with high contrast.

When used to form a negative image with high contrast, the average grain size of the silver halide used is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less. jμ or less is preferable. Although there are basically no restrictions on particle size distribution,
Monodispersity is preferred. Monodisperse herein means that it is composed of a group of particles of which at least 9 particles have a size within 10 μeI) of the average particle size in terms of weight or number of particles.

Silver halide grains in photographic emulsions are cubic, octahedral, and rhombic.
Regular (regu12r) like dihedron, lg-hedron
It may have a regular crystal structure, or it may have an irregular crystal shape such as a spherical or tabular crystal shape, or a composite shape of these crystal shapes.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

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

The silver halide used in the present invention is dino θ-8 per mole of silver.
It is a silver haloiodide prepared in the presence of ~10-5 mol of iridium salt or a complex salt thereof, and in which the silver iodide content on the grain surface is higher than the grain average silver iodide content. When an emulsion containing such a silver haloiodide is used, photographic properties with a high sensitivity layer and high gamma can be obtained.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions. You can.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. A specific example is U.S. Patent No. 1, 1, oto
British Patent No. t/1,0/. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

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

In the present invention, the silver halide emulsion layer is
It is preferable to include two types of monodispersed emulsions with different average particle sizes as disclosed in Tata No. 1 and Japanese Patent Application No. 2320g No. Chemical sensitization is preferred, and sulfur sensitization is the most preferred method of chemical sensitization.Large size monodispersed emulsions do not need to be chemically sensitized, but chemical sensitization may be used. Good.Large size monodisperse particles are −
Generally, chemical sensitization is not performed because black spots are likely to occur, but it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur. Here, "applying shallowly" means carrying out chemical sensitization by shortening the time for chemical sensitization compared to chemical sensitization of small-sized particles, or by reducing the amount of chemical sensitizer added at a lower temperature. Is there any particular limit to the sensitivity difference between dog-sized monodispersed emulsions and small-sized monodispersed emulsions? IJogE
as 0, /~/, 0. More preferably 0.2 to 0.7
However, the higher the dog size monodisperse emulsion, the better.

Here, the sensitivity of each emulsion is obtained when it is coated on a support containing a hydrazine derivative and processed using a developer having a pH of 1O, 3 to 12.3 and containing sulfite ions of 0, is mol/1 or more. It is something.

The average grain size of the small size monodisperse grains is not more than 2a width of the average size of the large size silver halide monodisperse grains, preferably not more than the go coefficient. The average grain size of the silver halide emulsion grains is preferably 0.02μ to 0.0μ
Good luck 0. It is preferable that the average particle size of dog-sized and small-sized monodispersed particles is within this range of /μ to O1jμ.

In the present invention, when two or more emulsions of different sizes are used, the amount of coated silver of the small-sized monodisperse emulsion is preferably ≠O to Owt relative to the total amount of coated silver. θ~10wt.

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

When introduced in separate layers, it is preferred to have the dog size emulsion in the upper layer and the small size emulsion in the lower layer.

The total amount of silver coated is preferably /9/m2 to t27m2.

Sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described in JP-A-33-32030, pages μj to j3, may be added to the light-sensitive material used in the present invention for the purpose of increasing sensitivity. can. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that substantially absorbs visible light and exhibits supersensitization. Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure (
Research Disclosure/Volume 76/7
It is described in item 3 of page 23 (■) of t4t3 (11/7μ, published in February).

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorohanzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. , etc.: mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (particularly hydroxy-substituted (/, 3.3a, 7) tetrazaindenes); A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.), hantaazaindenes, etc.; Among these, preferred are benzotriazoles (e.g., j-methyl-(inzotriazole)) and nitroindazoles (e.g., l'j-nitroindazole for t). It may be included in the liquid.

Development accelerators or nucleating and infectious development accelerators suitable for use in the present invention include JP-A-53-77 Otsu/1, JP-A No. 3773.2, JP-A No. 3-/37/, No. 33, same 0-/≠03jO, same t.

In addition to the compounds disclosed in -it, tys, etc.
Various compounds containing N or S atoms are useful.

The optimum addition amount of these accelerators varies depending on the type of compound, but is 1.0×l0-3 to 0. J9/m2, preferably t, 0x10-3 to 0. It is desirable to use it within the range of /9/m2.

The photographic material of the present invention may contain a desensitizer in the photographic emulsion layer or other hydrophilic colloid layer.

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 polarographic anodic potential and cathodic potential is positive.

A polarographic method for measuring redox potential is described, for example, in US Pat. No. 3,601,307.

The organic desensitizer preferably contains at least one water-soluble group, and specific examples include sulfonic acid groups, carboxylic acid groups, and sulfonic acid groups. , pyridine, triethylamine, pyharidine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.).

Examples of organic desensitizers include general formulas (I[I)~ described on pages J''!~71 of Japanese Patent Application No. 1983/=21?0 Tatar.
Those represented by (V) are preferably used.

The organic desensitizer in the present invention is contained in the silver halide emulsion layer.
, O x 10-8~/, O x 10' mol/m2, especially 1.
It is preferable that 0x10-7~/, 0x1O-5 mol/)712 be present.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers that have a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and dyes that are safe against safelight light when handled as bright-room sensitive materials. A dye having substantial light absorption mainly in the region of 3rOnm-10011m is used to increase the light absorption.

These dyes may be added to the emulsion layer depending on the purpose, or they may be added together with a mordant to the top of the silver halide emulsion layer, that is, to a non-light-sensitive hydrophilic colloid layer far from the silver halide emulsion layer with respect to the support. It is preferable to use it by adding it and fixing it.

Although it varies depending on the molar absorption coefficient of the ultraviolet absorber, it is usually l0
-29/m2 to 7m2 per liter. Preferably j Om9~! 00 mg/m2.

The above ultraviolet absorber can be used in a suitable solvent [e.g. water, alcohol (e.g. methanol, ethanol, propatool, etc.)].
, acetone, methylceronlube, etc., or a mixed solvent thereof] and added to the coating solution.

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

Specific examples of ultraviolet absorbers are given in U.S. Patent J, 133°7
No. 313/G, No. 72, 3.3! , otsu&'/
No., Tokukai Sho'g J-27,! 'G issue, U.S. Patent J,
707, 101, J, 711:17.3.7j, 4t, O Hiroyo, No. 222, 3,700. II! !
No., same J, 4' Tata, 7! :, No. 2, West German Patent Application Publication/, j17. It is described in ♂t3 etc.

Filter dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, citanine dyes and azo dyes. In order to reduce residual color after development, dyes that are water-soluble or decolorized by alkali or sulfite ions are preferred.

Specifically, for example, US Pat.
Virazolone oquinol dye described in U.S. Patent No.
．． Diarylazo dyes described in U.S. Patent No. 3. μ23. ．． No. 207, J, 314t, Hiroshi No. 7, steryl dyes and butadienyl dyes, U.S. Patent No. 2. j, 27. Merocyanine dye described in JtJ, US Patent No. 3゜! J'J, jt No. 97, same No. 3.
tj2,21? No. l/-, No. J, 7/r,! 7.2, the merocyanine dyes and oxonol dyes described in U.S. Patent No. 3. 76°tti and the enamine to myokinol dye described in British patent no. , f'gu, Ni0ri No. 1,1771ri No. 29, Tokukai Shogu ♂-♂! /3θ No. 2-29t'20, No. 4#-//414',! No. 0, U.S. Patent No. 0,! 33.4t7.2, same No.3. /G! .

No. 117, same No. 3. /77.071, same No. 3゜241
7, /, No. 27, same No. 3. jlAO, No. 117, No. 3
．． ! 7! ,, No. 70, No. 3. t 3. The dye described in No. 03 is used.

The dye can be prepared in a suitable solvent [e.g. water, alcohol (e.g. methanol, propatool, etc.), acetone,
methyl cellosolve, etc., or a mixed solvent thereof] and added to the coating solution for a non-photosensitive hydrophilic colloid layer of the present invention.

The specific amount of dye used is generally 10-3/m2 to 1
2/m2, especially 1o-37/m2~o.

A suitable amount can be found within a range of 7 m2.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes (formaldehyde, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), activated vinyl compounds (/, J, z
-triacryloyl-hexahydro-5-triazine,
l,3-vinylsulfonyl-2-proa2norna)
, active halogen compounds (such as ,2,≠-dichloro-t-hydroxy-5-triazine), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization. In particular, the surfactant preferably used in the present invention is Tokko Sho! These are polyalkylene oxides having a molecular weight of 600 or more described in R-9≠72. When used as an antistatic agent, a fluorine-containing surfactant (for details, refer to U.S. Pat.
0/, JRT issue, JP-A-Shoto=g.

♂ Geta issue, same! Particularly preferable is Tar 7guyoyomu (No. 7).

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers 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 any purpose such as improving dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Compounds with acid groups include organic acids such as salicylic acid, acetic acid, ascorbic acid, acrylic acid, ζmaleic acid, 7
Mention may be made of polymers or copolymers having acid monomers such as tarlic acid as repeating units. Regarding these compounds, see Japanese Patent Application No. 77/72.

Otsu No. 1173, Otsu No. 60-/13rJt, and Otsu No. AO-
/9! The description in the tjJ specification can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinking monomers having two or more unsaturated groups such as divinylbenzene as high molecular compounds. It is a water-dispersible latex made of a copolymer.

In order to obtain ultra-high contrast and high-sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developing solution or US Pat. ≠/9. Ri7! It is not necessary to use a high alkaline developer with p:E(/3) described in the above issue, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0. Contains more than /j mol/E, p
)(/ 0, yo~lλ, 3, especially 1)H//, 0-
/λ,O, a sufficiently high contrast negative image can be obtained.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, as it is easy to obtain good halftone dot quality, and dihydroxybenzenes and l-phenyl- A combination of 3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used. The developing agent is usually O, O
S child OS mole 0. Preferably it is used in an amount of r mol/l. Also, dihydroxybenzenes and l-phenyl-3
- When using a combination with pyrazolidones or p-amino-phenols, the former is 0.0! Mol/l-0. j
mol/l, the latter preferably in an amount of o, ot mol/E or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The sulfite is preferably O1 mol/β or more, particularly O9 mol/1 or more.

The developing solution of the present invention contains JP-A Shoj J-,
The compound described in No. 2μ, 3≠7 can be used.

Patent application Sho tO-109 as a dissolution aid added to the developer
, 74'J can be used. In addition, as a pH buffering agent used in developing solutions,
, No. 1133 or patent application Sho A/-, 2
Compounds described in No. 1,701 can be used.

The compound represented by the general formula (I) can be used in high-contrast sensitive materials in combination with a negative emulsion as described above, and can also be used in combination with an internal latent image type silver halide emulsion. The aspects will be described. 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 force layer may have any function, such as a colorant layer, an intermediate layer, a filter layer, a protective layer, an anti-ration layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halogenide grains. It may be a layer.

The content of the compound represented by the general formula rI) in the layer is such that it provides a sufficient maximum density (for example, a silver concentration of 100 or more) when the internal latent image type emulsion is developed with a surface developer. This is desirable. In practice, the appropriate content can 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 Approximately O per mole of silver
A range of 0 ooormg to roomg is practically useful, with a preferred range of from about 0.0 to about 10 oomg per mole of silver.
It is g. When it is contained in a hydrophilic colloid layer adjacent to an emulsion layer, it may be contained in the same amount as above for the amount of silver that can be included in the same area of the internal latent image type emulsion layer. Regarding the definition of internal latent image type silver halogenide emulsion, see JP-A-Sho A/
-/70733 Publication Page 10 Upper Shelf and British Patent No. 2.
It is described in or2.0!7 publication, pages 1r to 20.

Preferred internal latent image emulsions that can be used in the present invention include:
Specification of Japanese Patent Application Sho t/-, No. 2!3716, page λr/line 4 to page 131, line λ, regarding preferred silver halogenide grains, see page 31, line 3 to page 31 of the same specification. It is written on page 32/line 1.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanide dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioquinol dyes, etc. can be used. These sensitizing dyes include, for example, JP-A Shojter 170. No. t3r, same j9-410. tJt issue and the same J-
9-31! ', No. 73, cyanine dyes and merocyanine dyes 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 developer containing a color image-forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 77gg3 (1q7r/, February) ■-D section and 1♂7/7 (/ri7 It is described in patents cited in

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

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and typical examples include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as yoichi pyrazolone and pyrazolotriazoles. The j-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the perspective of the hue and color density of the coloring dye.

As a leaving group for a two-equivalent pyrazolone coupler, US Pat. '310. Nitrogen leaving group as described in No. t/R or U.S. Pat. No. 3J/G.

The arylthio group described in No. 7 is particularly preferred.

Also, European Patent No. 73. It has a pallast group as described in the Tit issue! - Pyrazolone couplers provide high color density.

As pyrazoloazole couplers, US Patent A3,
3'yri, l! 'Pyrazolobenzimidazoles as described in Tata, preferably pyrazolo[yo+'')(/,,2.ri)riazoles as described in US Pat. 20
Pyrazolotetrazoles and Research Disclosure 1g, 23o(t
9. Examples include the pyrazolopyrazoles described in r years (months). Imidazo[:/, , 2-b]pyrazoles described in European Patent No. 1/9,7F/ are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness. , pyrazolo [/.

z-b) [/, 2. l] Triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and US Pat. Hiroshi 7gu.

223, preferably the naphthol couplers described in U.S. Pat. No. 4', 0! Ko, No. 272, same No. ≠.

/4Z4, 39, No. 4L, 2.2g, 233, and Ko No. 1.2, 2oo, two-equivalent naphthol couplers of the oxygen atom separation type are listed as representative examples. It will be done. Further, specific examples of phenolic couplers are disclosed in U.S. Patent No. 2.3t9. Octopus No. 2, same No. 2, 2. l
rO/, No. 171, No. J, 712. /6'' No. 1
．． It is described in rys, r, z6, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,00λ, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, λ,! - has a diacylamino-substituted phenolic coupler and a phenylureido group at the 2-position, and!
These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in US Pat. No. 4t, 3tt.

, 237 and British Patent No. 2. A specific example of a magenta coupler is given in No. 70, European Patent No.
No. 70 and West German Application No. 3. ．． 23'l.

! No. 33 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Pat. ≠j/, 120
No. and Ha, oro.

, No. 2//. Specific examples of polymerized magenta couplers are given in British Patent No. λ, 102. No./73 and U.S. Patent No. G, 3t7. ．． It is described in No. 2g2.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The standard amount of color couplers used is in the range of 90.00 to 1 mole per mole of photosensitive silver halide, preferably Ir1O,0 to 005 mole for yellow couplers and 0 for magenta couplers. .003 to 0
．． 3 moles, and o, oo, 2 to 0.3 moles for cyan couplers.

In the present invention, a developing agent such as hydroxybenzene (for example, hydroquinone M1, aminophenols, 3-pyrazolidones, etc.) may be contained in the emulsion or in the light-sensitive material.

The photographic emulsion used in the present invention is combined with a dye image-providing compound (colorant) for color diffusion transfer to release a diffusible dye in response to development of silver halide, and is subjected to appropriate development processing. It can also be used later to obtain a desired transferred image on an image-receiving layer. Many coloring materials are known for use in color diffusion transfer methods, and although they are initially non-diffusive, they undergo redox reactions with oxidation products of the developing agent (or electron transfer agent). It is preferable to use a type of coloring material (hereinafter abbreviated as a DRR compound) that is cleaved by the dye to release a diffusible dye. Among them, DR having an N-substituted sulfamoyl group
R compounds are preferred. Particularly preferred for use in combination with the nucleating agent of the present invention are US Pat.
4', Or3,3/λ issue and 'I, 336, 3.22
DRR compounds having more 0-hydroxyarylsulfamoyl groups and those described in JP-A Shoyo 3-/
Geta.

It is a DIR compound having a redox core as described in No. 32&'. When used in combination with such an RR compound, the temperature dependence particularly during treatment is significantly small.

Specific examples of DRR compounds include those described in the above patent specifications, as well as magenta dye image forming substances such as l
-Hydroxy-1-tetramethylenesulfamoyl-<
t-(3'-methyl-μIC,!“-Hydroxy-Hiroshi”
-methyl-3"-hexadecyloxyphenylsulfamoyl)-7enylazo]-naphthalene, as a yellow dye image-forming material /-phenyl-3-cyano-t-(
,2″g-tert-pentylphenoxyacetamino)-phenylsulfamoyl]phenylazo)-
Examples include pyrazolone.

Details of the color couplers that can be preferably used in the present invention are described on page 33, line 1g to the last line of page μ0 of the same specification.

After imagewise exposure using the light-sensitive material of the present invention, after or while carrying out a cover treatment with light or a nucleating agent, the pH containing an aromatic primary amine color developing agent is pH//! It is preferable to directly form a positive color image by color development, bleaching and fixing using the following surface developer. The pu of this developer is /l.

More preferably, the range is o-io, o.

The fogging treatment in the present invention is the so-called "light fogging method".
Either of the method of applying a second exposure to the entire surface of the photosensitive layer called "chemical heating method" and the method of developing in the presence of a nucleating agent called "chemical oxidation method" may be used. Development may be carried out in the presence of a nucleating agent and fogging light. Alternatively, a photosensitive material containing a nucleating agent may be exposed in an overlapping manner.

Regarding the light turnip method, the above-mentioned patent application Sho t/-2337/
The nucleating agent that can be used in the present invention is described in the same specification from page 7, line 2 to page 7, line 2 of the same specification. , especially the general formula (N
-/) and [N-1] are preferably used. Specific examples of these include J-x-j of the same specification.
CN-4-/] to CN-l-10] described on page r and [:N-ll-/] to [:
N, -IF-/,2] is preferred.

Regarding the nucleation accelerator that can be used in the present invention, see Section t of the same specification.
♂Page// line to page 71, line 3. In particular, as a specific example, (A-/) to page 69 to page 70 are described.
The use of (A-/J) is preferred.

Regarding the color developing solution used in the development of the photosensitive material of the present invention, it is described in the same specification, page 77, line μ to page 7.2, and in particular, aromatic primary amine color developing solution. As a specific example of the developer, a p-7 unilene diamine compound is preferable, and typical examples thereof include 3-methyl-t-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3- Methyl-7-amino-N-ethyl-
N-(β-hydroxyethyl)aniline, 3-methyl-
Guamino-N-ethyl-N-methoxyethylaniline and its salts such as sulfates and hydrochlorides can be used.

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching treatment may be carried out simultaneously with the fixing treatment in a single bath white fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which fixing is followed by bleach-fixing. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention. The additives used in the bleaching solution or bleach-fixing solution of the present invention include those described in Japanese Patent Application No. Sho A/-, 321, ttλ Specification No. 2.
Various compounds described on pages 2 to 30 can be used. After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed. It is preferable to use softened water as the washing water or stabilizing liquid. Examples of the water softening treatment include a method using an ion exchange resin or a reverse osmosis device as described in Japanese Patent Application No. Sho J/-/3/132. As a specific method for these, it is preferable to carry out the method described in Japanese Patent Application No. 1987-/3/13.2.

Further, as additives used in the water washing and stabilization steps, various compounds described in Japanese Patent Application No. 32, No. 2, pages 30 to 31 can be used.

The smaller the amount of replenisher in each treatment step, the better. The amount of replenisher is 0.00% relative to the amount of prebath brought in per unit area of the photosensitive material. /-30 times is preferable, more preferably 3
~30 times.

Example 1 4X10 per mole of silver in an aqueous gelatin solution kept at 50°C
In the presence of −' molar potassium iridium(III) chloride and ammonia, an aqueous solution of silver nitrate and potassium iodide potassium bromide were simultaneously added over 60 minutes while the pAg
By keeping the average particle size at 7.8, the average particle size is 0.28μ
A cubic monodisperse emulsion having an average silver iodide content of 0.3 mol % was prepared.

This emulsion was desalted by the flocculation method, and then 40 g of inert gelatin per mole of silver was added and kept at 50°C and treated with 5°5'-dichloro-9 as a sensitizing dye.
-ethyl-3-3'-bis(3-sulfopropyl)oxacarbocyanine and 104 moles of Kl per mole of silver.
The mixture was added to the solution, allowed to stand for 15 minutes, and then cooled down. This emulsion was redissolved and methylhydroquinone was added to 0 at 40°C.
．． 02 mol/silver mol, and 1.0 x 10-' mol/Ag mol of the hydrazine derivative of the present invention or comparative example shown in Table 1, and further added 5-methylbenzotriazole, 4-hydroxy-1,3,3a, 7 Tetrazaindene, the following development accelerators (a) and (b), and a dispersion of polyethyl acrylate at 0 and 4 g/rrr, and the following compounds (c), (d), and (e) as a gelatin hardener. A waterproof undercoat layer (0
, 5μ) with a polyethylene terephthalate support (
The silver amount was 3.4 g/Irr.

Js (b) (c) (d) (e) H CHz=CtlSOzCHzCHCHzS(hcH=C
H2CHz=CHSOzCFIzS02cH=cHzC
)Iz = CB5(hC)lzCONHCHzCHz
NHCOCHzSOzCH=CI (zOn top of this as a protective layer, gelatin 1.5g/rrr, polymethyl methacrylate particles (average particle size 2.5μ) 0.3g/n?,
The next surfactant containing layer was applied.

Surfactant CHZCOOCbHl3 CHCOOC6HI3 37■/Po0
aNa CeF I7S OzN CHtCOOKC3H?
2. 5/MCI) Evaluation of high contrast performance These samples were exposed to 3200' tungsten light through an optical wedge, developed with the following developer at 34°C for 30 seconds, fixed, washed with water, and dried.

The photographic sensitivity and gradation obtained are shown in Table 1. When the nucleating agent of the present invention was used, high sensitivity and high contrast were obtained.

[Developer - ■]

[2] Evaluation of photographic properties with exhausted developer Automatic plate-making machine FG660F type (Fuji Photo Film ■
(manufactured by) was filled with the above developer -■, and was heated for 34 hours under the following three conditions.
It was developed at ℃ 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 solution).

CB) Perform development processing using the solution left in the automatic processor filled with developer solution for 4 days. (Development with air fatigue solution)
.

(C) After filling the automatic developing machine with developer, 50.
8cmx61. Exposure is carried out so that 50% of the area is developed in a size of Ocm, 200 sheets are processed in one day, and development processing is carried out using the same solution that is repeated for 5 days. Developer per processed number of sheets -
Replenish 100 cc of 1.

(Development using high-volume processing fatigue solution). The photographic properties obtained are shown below.
Shown in 1. In terms of processing running stability, CB) and (C
It is desirable that the photographic properties obtained in (A) and (A) be the same. As can be seen from the results in Table 1, when the nucleating agent of the present invention is used, there is little variation in photographic sensitivity even when the developer is exhausted.

[Comparative compound A]

* The sensitivity is expressed as the difference from the blank sensitivity (JogE) as the standard. Therefore, even if cf-1,o
This means that the feeling is 1.0 lower in logE than the blank, that is, the feeling is 10 times lower.

Umbrella wheel Gradation (G): Point of density 0.3 and 3.0 on the characteristic curve
is the slope of the straight line connecting the points. A large value) indicates that the word is hard.

＊＊＊ΔS! l-A: Difference between sensitivity (si) when developed with air fatigue solution and sensitivity (SA) when developed with fresh solution*** Δ5c-A: Sensitivity when developed with mass processing fatigue solution ( Sensitivity (Sa) when developed with S,) and fresh solution
Difference Example-2 5.0X per mole of silver in gelatin aqueous solution kept at 50℃
After simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of 10-6 moles of (NH4,)3RhCβ6, soluble salts were removed, gelatin was added, and chemical ripening was performed using methods well known in the art. 2-methyl-4hydroxy-1,3,3a,7-titraazaindene was added as a stabilizer without any addition. This emulsion was a cubic monodisperse emulsion with an average grain size of 0.15 microns.

To this emulsion, a hydrazine compound was added as shown in Table 2, a polyethyl acrylate latex was added in a solid content of 30 wt% based on gelatin, and a mixture of the three types of compounds used in Example 1 was added as a hardening agent. In addition, it was coated on a polyester support to give an Ag content of 3.8 g/n (gelatin was 1.8 g/n). On top of this was gelatin 1.5 g/rd as a protective layer and a matting agent. As, polymethyl methacrylate particles (average particle size 2.5μ) 0.3g/
M, and a protective layer containing the following surfactant, stabilizer, and ultraviolet absorbing dye as coating aids were coated and dried.

Surfactant CH2COOCbH13 CHCOOCbHI3 SO,Na CeF I? S OZN CHtCOOK37■/d Cs H'r 2,5■/d Stabilizer thioctic acid 2,1■/rtr This sample was used with Dainippon Screen ■ Seishitsu Printer p
-607, exposed through an optical wedge, developed at 38° C. for 20 seconds, fixed, washed with water, and dried.

The photographic properties obtained are shown in Table 2.

From the results in Table 2, it can be seen that higher contrast can be obtained with the sample of the present invention than with the sample of the comparative example.

In addition, as in Example 1, the photographic performance was tested using a fatigued developer, and as shown in Table 2, the samples of the present invention had the following properties:
Fluctuations were small, showing favorable results.

4゜The column “Detailed description of the invention” in the specification to be amended .

1゜ Display of incidents Heisei 1 Special Application No. 11377 1) Third Yuma/ /, chemical structural formula 2゜ name of invention Silver halide photographic material 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Scope of Claims] It has at least one silver halide photographic emulsion layer, and the photographic emulsion layer or other hydrophilic colloid layer has the following general formula (I).
A silver halide photographic material comprising a compound represented by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 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 ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_0 is an alkyl group, alkenyl group, aryl group, alkoxy group,
or represents an aryloxy group, l_1 is 1 or 2
represents. ). G has ▲a mathematical formula, a chemical formula, a table, etc.▼(m_1 represents 1 or 2), a sulfonyl group, a sulfoxy group, ▲a mathematical formula, a chemical formula, a table, etc.▼(in the formula, R_1 is an alkoxy group or an aryloxy group) ), represents a thiocarbonyl group or an iminomethylene 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) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (a), Y_a_1 and Y_a_2 are ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_a_3 represents an alkoxy group or an aryloxy group.) They may be the same or different. R_a_1 and R_a_2 represent an aliphatic group, an aromatic group or a heterocyclic group, and may be the same or different. Further, R_a_1 and R_a_2 may be substituted or may be combined with each other to form a ring.