JP2732002B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for forming an ultra-high contrast negative image using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process.

[0002]

BACKGROUND OF THE INVENTION The addition of hydrazine compounds to silver halide photographic emulsions and developers is disclosed in U.S. Pat.
No. 727 (a developing solution combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (silver halide) It contains β-mono-phenylhydrazine of an aliphatic carboxylic acid as a stabilizer for the light-sensitive material), No. 2,419,975, and Mees.
Author, The Theory of Photographic Process, 3rd Edition (19
66), page 281.

[0003] Of these, in particular, US Pat.
No. 9,975 discloses that a hard negative image can be obtained by adding a hydrazine compound. The patent specification adds a hydrazine compound to a silver chlorobromide emulsion,
When developed with a developer having a high pH such as 12.8,
It is described that extremely hard photographic characteristics having a gamma (γ) of more than 10 can be obtained. However, a strong alkaline developer having a pH close to 13 is liable to be oxidized by air and is unstable, and cannot withstand long-term storage or use. There have been attempts to develop a silver halide photosensitive material containing a hydrazine compound with a developer having a lower pH to form a high contrast image.

JP-A-1-179939 and JP-A-1-179940 disclose a photographic material containing a nucleation developing accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group. And a processing method of developing with a developer having a pH of 11.0 or less. However, when a compound having an adsorptive group is added to a silver halide emulsion, the photosensitivity is impaired when the amount exceeds a certain limit,
Since it has the harm of suppressing development or hindering the action of other useful adsorption additives, the amount used is limited, and sufficient high contrast cannot be exhibited.

US Pat. Nos. 4,998,604 and 4,994
No. 365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is apparent from these examples, the high contrast is not sufficient, and it is difficult to obtain the high contrast and the necessary Dmax under practical development conditions.

Further, a nucleation hard contrast material using a hydrazine derivative has a large change in sensitivity and gradation due to fatigue of a developing solution, and attempts have been made to improve processing stability. In the prior art, it was not possible to obtain a light-sensitive material having sufficient processing stability and sufficient processing stability even when processed with a developer having a pH of less than 11.

[0007]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide photographic light-sensitive material for plate making which has excellent rapid processing and high processing stability.
A second object of the present invention is to provide a silver halide photographic material for plate making which can be developed at a lower pH.

[0008]

These objects of the present invention have been attained by a silver halide photographic material characterized by containing a compound represented by the following general formula (1). General formula (1)

[0009]

Embedded image

In the formula, L ¹ is a single bond, -O- group, -S- group, -N
R ⁵ -group, -CO- group, -SO ₂ -group, -P (O) (G ² R ⁵ )-group, or
L ² represents —SO ₂ NR ⁵ — group, —NR ⁵ SO ₂ N
R ⁵ -group, -CONR ⁵ -group, -NR ⁵ CONR ⁵ -group, -G ² P (O) (G ² R ⁵ ) NR ^5-
Represents a group. G ¹ is -CO- group, -SO ₂ -group, -SO- group, -COCO
-Group, thiocarbonyl group, iminomethylene group or -P (O)
(G ² R ⁵ ) — represents a group, and G ² represents a single bond, —O—, or —NR ⁵ —. R ¹ represents an aliphatic group, an aromatic group, R ^2,
R ³ is a divalent aliphatic group or an aromatic group, R ⁴
Represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, a substituted or unsubstituted amino group,
R ⁵ represents a hydrogen atom, an aliphatic group or an aromatic group.
m represents 0 or 1. R ¹ is substituted with at least one group represented by the following general formula (2) or (3).

[0011]

Embedded image

In these formulas, R ¹¹ represents an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group or an aryl group. X ⁻ represents a counter anion or a counter anion moiety when forming an inner salt.

The compound represented by formula (1) will be described in more detail. In the general formula (1), the aliphatic group represented by R ¹ preferably has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The aromatic group represented by the general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group. The aliphatic group or aromatic group represented by R ¹ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido group. , Urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, Examples include a phosphoric amide group, a diacylamide group, and an imide group. Preferred substituents include an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), and a substituted amino group (Preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 3 carbon atoms)
0), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Things). These groups may be further substituted. Particularly preferred as R ¹ is an alkyl group having 1 to 10 carbon atoms.

In the general formula (1), the aliphatic groups represented by R ² and R ³ preferably have 1 to 30 carbon atoms, and particularly have 1 to 20 carbon atoms, such as linear, branched or cyclic. Is an alkyl group. The aromatic groups represented by R ² and R ³ in the general formula (1) are a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group. Preferred as R ² and R ³ are aryl groups, and particularly preferred are those containing a benzene ring. The aliphatic group or the aromatic group of R ² and R ³ may be substituted, and typical substituents include those listed as the substituent of R ¹ .

In the general formula (1), L ¹ is a single bond, -O-
Group, -S- group, -NR ⁵ -group, -CO- group, -SO ₂ -group, -P (O) (G ²
R ⁵ ) -group or a combination thereof, preferably -S
O ₂ NR ⁵ - group, -NR ⁵ SO ₂ NR ⁵ - group, -CONR ⁵ - group, -NR ⁵ CONR ⁵ -
Represents a group, -G ² P (O) (G ² R ⁵ ) NR ⁵ -group, particularly preferably -C
ONR ^5- represents a group. Among the groups represented by L ² in the general formula (1), a particularly preferred group is a —SO ₂ NR ⁵ — group. General formula
In (1), m is preferably 1 and may be 0.

In formula (1), the alkyl group represented by R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, a benzene ring Including). G ¹ is
In the case of a —CO— group, preferred among the groups represented by R ⁴ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenyl group) Sulfonylmethyl group, phenoxymethyl group, methoxymethyl group, pyridiniomethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 35-dichlorophenyl group, o-methanesulfonamidophenyl group) A 4-methanesulfonylphenyl group,
2-hydroxymethylphenyl group, etc.), and particularly preferably an alkyl group and a hydrogen atom substituted with an electron-withdrawing group. R ⁴ may be substituted, and as the substituent, the substituents listed for R ¹ can be applied. General formula
G ^{1 in} (1) is most preferably a —CO— group. Further, R ⁴ disrupts the portion of the G ¹ -R ⁴ from the remainder molecule may be such as to generate a cyclization reaction to form a cyclic structure containing a -G ¹ -R ⁴ moiety of atoms Examples thereof include those described in JP-A-63-29751.
R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. Further, when the compound represented by the general formula (1) contains two or more R ⁵ and G ^2, which may or may not be the same.

R ¹ is substituted with at least one group represented by the following general formula (2) or (3).

[0018]

Embedded image

Then, three R ^{11 s} in the general formula (2),
The two R ¹¹ in the general formula (3) may be the same or different, and may combine with each other to form a ring.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ or R ¹¹ incorporates a ballast group or a polymer commonly used in immobile photographic additives such as couplers. It may be something. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Examples of the polymer include those described in JP-A-1-100530. R ¹ , R ² , R ³ , R ⁴ or R ¹¹ in the general formula (1) may have a group in which a group which enhances the adsorption to the surface of the silver halide grain is incorporated. Such adsorbing groups include a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group,
U.S. Pat. No. 4,385,108 including triazole groups
No. 4,459,347, JP-A-59-1955.2.
No. 33, No. 59-200, No. 231 and No. 59-201,
No. 045, No. 59-201, No. 046, No. 59-20
Nos. 1,047, 59-201,048, 59-2
Nos. 01,049, 61-170,733, 61-
Nos. 270,744, 62-948, 63-23
No. 4,244, No. 63-234, No. 245, No. 63-2
34,246. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

The hydrazine compounds of the present invention are described, for example, in JP-A-61-213,847 and JP-A-62-260,153.
No. 4,684,604, Japanese Patent Application No. 63-9 / 1988.
No. 8,803, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,377,634, 4,332,878, and JP-A-49-129,536.
Nos. 56-153,336 and 56-153,34
No. 2, U.S. Pat. Nos. 4,988,604 and 4,99
No. 4,365, for example.

In the present invention, the amount of the compound represented by the general formula (1) is
The optimum value may be determined depending on the type of the compound, etc.
Usually, the range is preferably from 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably from 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol, per mol of silver halide.

To obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer,
It is not necessary to use a high alkali developer of 11 or more, and a stable developer can be used. That is, the silver halide light-sensitive material of the present invention contains at least 0.15 mol / l of sulfite ion as a preservative, and has a pH of 11.0 to 9.
With the developing solution of 0, a negative image having a sufficiently high contrast can be obtained. Preferably, a stable processing system can be constructed by using a developer having a pH of 10.7 to 9.2. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1
-Phenyl-3-pyrazolidone, 4,4-dimethyl-1
-Phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol) and the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developing solution containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, the dihydroxybenzenes in the developer are 0.05%.
0.5 mol / l, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / l or less.

As described in US Pat. No. 4,269,929, by adding amines to a developer, the development speed can be increased and the development time can be shortened. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates and phosphates, bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). ), An antifoggant and the like. If necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, a silver stain preventing agent for a film. (For example, 2-mercaptobenzimidazolesulfonic acids).
As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process according to the invention is usually 18
Between 50 ° C and 50 ° C. Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine to when it comes out is set to 90 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained. In the developer of the present invention, compounds described in JP-A-56-24347 can be used as silver stain inhibitors. Compounds described in JP-A-61-267759 can be used as a dissolution aid to be added to the developer. Further pH used for developer
As the buffer, a compound described in JP-A-60-93,433 or a compound described in JP-A-62-186259 can be used.

There are no particular restrictions on the various additives and development processing methods used in the light-sensitive material of the present invention. For example, those described in the following sections can be preferably used. Item The relevant place 1) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) ) And compounds II-1 to II-22, and compounds described in JP-A-1-179939. 2) Silver halide emulsion and JP-A-2-97937, page 20, lower right column, line 12 to the same process, the upper column, page 21, lower left column, line 14, JP-A-2-12236, page 7, upper right column The selenium sensitization method described from line 19 to line 12, page 12, lower left column, and Japanese Patent Application No. 3-189532. 3) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to right lower column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Column 20, line 20. Further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, Japanese Patent Application Nos. 3-189532 and 3-4111064. 4) Surfactant JP-A No. 2-12236, page 9, upper right column, line 7 to right lower column, line 7, and JP-A 2-18542, page 2, lower left column, line 13 to page 4, right Line 18 in the bottom column. 5) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, furthermore, JP-A 1-237538 6) Polymer latex described in JP-A-2-103536, page 18, lower left column, lines 12 to 20. 7) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 8) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 to plasticizer, page 19, upper right column, line 15; 9) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17; 10) Dyes Dyes on page 17, lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-94638 and JP-A-3-185773. 11) Binder Line 1 to line 20 in the lower right column on page 3 of JP-A-2-18542. 12) Black spot inhibitor A compound described in US Pat. No. 4,956,257 and JP-A-1-18832. 13) Redox compounds Compounds represented by formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50) described in JP-A-3-174143, pages 3 to 20 are disclosed. Compounds represented by formulas (R-1), (R-2) and (R-3), compounds 1 to 75, and further described in Japanese Patent Application Nos. 3-69466 and 3-15648. 14) Monomethine compounds JP-A-2-87532 discloses compounds of the general formula (II) (especially compounds II-1 to II-26). 15) Dihydroxybenne A compound described in JP-A-3-39948, page 11, upper left column to page 12, lower left column, and EP 452772A.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

[0034]

EXAMPLES Example 1 (Emulsion preparation) Emulsion A: 0.14 M aqueous silver nitrate solution and 0.04 M bromide containing (NH ₄ ) ₃ RhCl ₆ corresponding to 1 × 10 ⁻⁷ mol per mol of silver Combining a halogen salt solution containing potassium and 0.09 M sodium chloride with sodium chloride;
To a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione was added by a double jet method at 38 ° C. for 12 minutes with stirring, and the average particle size was 0.15.
Nucleation was carried out by obtaining silver chlorobromide grains having a particle size of 70 μm and a silver chloride content of 70 mol%. Subsequently, similarly, a 0.87 M aqueous silver nitrate solution, 0.26 M potassium bromide, 0.6
An aqueous halogen salt solution containing 5 M sodium chloride was added by a double jet method over 20 minutes. Then one
A conversion was carried out by adding a KI solution of × 10 ^-3 mol, followed by washing with water by a flocculation method according to a conventional method, adding 40 g of gelatin, adjusting to pH 6.5 and pAg 7.5, and further adding 5 mg of sodium thiosulfate per mol of silver. And mg of gold chloride were added thereto, and the mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl-
150 mg of 1,3,3a, 7-tetrazaindene were added. The resulting grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

(Preparation of Coated Samples) The compounds of the present invention were added to these emulsions as shown in Table 1. The following compounds were used as comparative compounds of the hydrazine derivative of the present invention.

[0036]

Embedded image

Next, a nucleation accelerator of the following structural formula was added.

[0038]

Embedded image

[0039]

[Table 1]

Further, a sensitizing dye represented by the following structural formula (S ₁ ) was added in an amount of 3.4 × 10 ^-4 mol per mol of silver, and 1-phenyl-5-
2 × 10 ⁻⁴ mol of mercaptotetradol, 5 × 10 ⁻⁴ mol of short-wave cyanine dye represented by the following structural formula (a), water-soluble latex represented by (b) (200 mg /
m ² ), a dispersion of polyethyl acrylate (200 mg /
m ² ) and 1,3-divinylsulfonyl-2-propanol (200 mg / m ² ) as a hardener.

[0041]

Embedded image

Gelatin 1.0 g / m 2 as a protective layer^Two,particle
Irregular SiO with a size of about 3.5μ _TwoMatting agent 40mg /
m^Two, Methanol silica 0.1 g / m^Two, Polyacrylamide
100mg / m^Two, Hydroquinone 200mg / m^Two, Silico
Oil represented by the following structural formula
Surfactants and sodium dodecylbenzenesulfonate
The layer containing the emulsion was coated simultaneously with the emulsion layer.

[0043]

Embedded image

The back layer and the back layer protective layer were applied according to the following formulation.

[Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Gelatin hardener

[0046]

Embedded image

Dye, mixture of dyes [a], [b] and [c]

[0048]

Embedded image

[Back protective layer] Gelatin 0.8 mg / m ² Polymethyl methacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² Dihexyl-α-sulfosacnate sodium salt 15 mg / m ² Dodecylbenzenesulfonic acid sodium salt 15 mg / m ² sodium acetate 40 mg / m ²

(Evaluation of photographic characteristics)
After being exposed through an optical wedge with tungsten light of 00 ° K, the film was developed with the following developer 1 at 34 ° C for 25 seconds, fixed, washed with water, and dried. GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used as the fixing solution.

Developer I Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-Methylbenzo Triazole 0.4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Sodium toluenesulfonate 8.0 Sodium carbonate 11.0 1 ml by adding water Adjust to pH 10.3

Further, a processing fatigue developing solution after processing 15 sheets per liter of a 100% blackened FUJI RIS Ortho Film RO-100 large size (50.8 cm × 61 cm) with the developing solution of the above formula, The same treatment was carried out using an air oxidation fatigue developer in which the developer having the above-mentioned formulation was placed in a beaker and left for 3 days.

The reciprocal of the exposure amount giving a density of 1.0 was defined as the sensitivity, and Table 2 shows the relative sensitivity of the sample A to the new solution treatment. Table 2 also shows the gradient of a straight line connecting the points of density 0.1 and 3.0 on the characteristic curve as gradation.

[0054]

[Table 2]

By using the hydrazine derivative of the present invention, it is possible to obtain a light-sensitive material which is hardly contrasted and has little change in sensitivity and gradation due to a change in the composition of the developing solution even when processed with a developing solution having a pH of less than 11.

Example 2 The coated samples shown in Table 1 were developed with the following developer 2, and the photographic characteristics were evaluated in the same manner as in Example 1.

Developer 2 Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-Methylbenzo Triazole 0.4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Sodium toluenesulfonate 8.0 Sodium carbonate 11.0 N-dimethyl-n- Hexanolamine 15.0 1 liter with water

Table 3 shows the obtained photographic characteristics.

[0059]

[Table 3]

As shown in Table 3, by adding an amine compound to the developing solution, the pH of the developing solution can be further lowered to obtain high-contrast photographic characteristics.

Example 3 Using an emulsion prepared as described below, using a sensitizing dye
As the following structural formula (S _Two) Of the present invention
Adding a hydrazine derivative as shown in Table 4, developing
Performed in the same manner as in Example 1 except that the time was set to 45 seconds.
Was.

[0062]

[Table 4]

(Emulsion Adjustment) A cubic monodispersed silver iodobromide emulsion having a grain size of 0.25 μm (coefficient of variation: 0.15, silver iodide: 1.0 mol%, iodine distribution uniform) was obtained by the control double jet method. Prepared. The silver iodobromide emulsion contains K ₃
IrCl ₆ was added to contain 4 × 10 ⁻⁷ mol / Ag mol. The emulsion was desalted by flocculation and kept at 50 DEG C., followed by 10 ^{@ -3} mol of potassium iodide solution per mol of silver and 4-hydroxy-6 as a stabilizer.
-Methyl-1,3,3a, 7-tetrazaindene was converted to silver 1
5 × 10 ^-4 mol was added per mol.

[0064]

Embedded image

Table 5 shows the obtained photographic characteristics.

[0066]

[Table 5]

As shown in Table 5, the sample of the present invention has p
It can be seen that even when processed with a developing solution of less than H11, a high-contrast image is given and the change in photographic characteristics due to fatigue of the developing solution is small.

Example 4 (Emulsion preparation) 1 mol of silver was added to an aqueous gelatin solution maintained at 30 ° C.
5.0 × 10^-6Mole (NH_Four)_ThreeRhCl ₆Silver nitrate in the presence of
After simultaneously mixing the aqueous solution and the aqueous sodium chloride solution,
The soluble salts were removed by methods well known in the art.
Gelatin is added and used as a stabilizer without chemical ripening.
Methyl-4-hydroxy-1,3,3a, 7-tetraa
Zindene was added. This emulsion has an average grain size
This was a monodisperse emulsion having a cubic crystal form of 0.08 μm.

(Preparation of Coated Samples) The compounds of the present invention were added to these emulsions as shown in Table 6. Next, a nucleation accelerator represented by the following structural formula was added.

[0070]

Embedded image

Further, a polyethyl acrylate latex was added at a solid content of 30% by weight based on gelatin, and 1,3-vinylsulfonyl-2-propanol was added as a hardening agent.
Coating was performed on a polyethylene support so that the amount of Ag was 3.8 g / m ² . Gelatin was 1.8 g / m ² . As a protective layer, a layer of gelatin 1.5 g / m ² and a particle size of 2.5 μm of polymethyl methacrylate 0.3 g / m ² was applied thereon.

[0072]

[Table 6]

(Evaluation of Photographic Properties) These samples were exposed through an optical wedge with a light room printer P-607 manufactured by Dainippon Screen Co., Ltd.
Using the treatment fatigue fluid and the air oxidation fatigue fluid, 38 ° C 4
It was developed for 0 second, fixed, washed with water and dried. Table 7 shows the obtained photographic characteristics.

[0074]

[Table 7]

As shown in Table 7, the sample of the present invention has p
It can be seen that even when processed with a developing solution of less than H11, a high-contrast image is given and the change in photographic characteristics due to fatigue of the developing solution is small.

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising a compound represented by the following general formula (1). General formula (1) In the formula, L ¹ is a single bond, -O- group, -S- group, -NR ⁵ -group, -CO-
Group, -SO ₂ -group, -P (O) (G ² R ⁵ )-group or a combination thereof, and L ² represents -SO ₂ NR ⁵ -group, -NR ⁵ SO ₂ NR ⁵ -group, -CONR
⁵ - group, -NR ⁵ CONR ⁵ - ^{group, -G 2 P (O) (} G 2 R 5) NR 5 - represents a group. G ¹ is -CO- group, -SO ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or ^{-P (O) (G 2 R} 5) - represents a group, G ² Represents a single bond, -O- group, or -NR ⁵ -group.
R ¹ represents an aliphatic group or an aromatic group; R ² and R ³ represent a divalent aliphatic group or an aromatic group; R ⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, Represents an aryloxy group, a substituted or unsubstituted amino group, and R ⁵ represents a hydrogen atom, an aliphatic group or an aromatic group. m is 0
Or represents 1. R ¹ is at least one of the following general formulas
(2) or substituted with a group represented by the general formula (3). Embedded image In these formulas, R ¹¹ represents an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, or an aryl group. X ⁻ represents a counter anion or a counter anion moiety when forming an inner salt.