JPH04194923A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent variation of sensitivity and drop of contrast due to the lapse of time and increase of black spots occurring on unexposed parts by processing in the presence of at least one of specified compounds. CONSTITUTION:At least one of silver halide emulsion layers formed on a support and/or its adjacent layer contains a hydrazine derivative, and this silver halide photographic sensitive material is processed in the presence of at least one of the compounds represented by formula I in which each of R1 - R4 is independently H, alkyl, or aryl, and each may combine with each other to form a 5- - 7-membered ring; X is -O-, -S-, or the like; and R5 is halogen, thus permitting rise of sensitivity and drop of contrast due to the lapse of time, increase of black spots, and the like to be prevented even in the case of using a developing solution low in pH and storage stability before exposure to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method using a silver halide photographic material on a support, and more particularly to an image forming method that provides high contrast.

[Background of the invention]

The photolithography process involves converting a continuous tone original into a halftone image. In this process, contagious development has been used as a photographic technique capable of reproducing ultra-high contrast images.

The lithium-type silver halide photographic light-sensitive material used for infectious development has, for example, an average grain size of about 0.2 μm, a narrow grain distribution, a well-shaped grain, and a high silver chloride content (at least 50 mol). 2) Consisting of a silver chlorobromide emulsion. By processing this lithium-type silver halide photographic light-sensitive material with an alkaline nitroquinone developer with a low concentration of sulfite ions, a so-called lithium-type developer, high contrast,
You can obtain images with high sharpness and high resolution.

However, these lithium-type developers are susceptible to air oxidation and have extremely poor storage stability, making it difficult to maintain constant development quality during continuous use.

There is a known method for quickly obtaining high-contrast images without using a Lithium-type developer.

For example, as seen in the specification of JP-A-56-106244, a hydrazine derivative is contained in a silver halide photographic light-sensitive material. In contrast to these methods, high-contrast images can be obtained by processing with a developing solution that has good stability and can be processed quickly.

These techniques require processing with a developer having a pH of 11.0 or higher in order to fully exhibit the high contrast properties of hydrazine derivatives. When a high pH developer with a pH of 11.0 or more comes into contact with air, the developing agent is likely to oxidize. It may be more stable than Lith developer, or it may not be possible to obtain ultra-high contrast images due to oxidation of the developing agent.

In order to compensate for this drawback, Japanese Patent Application Laid-open No. 63-29751 and European Patent Nos. 333,435 and 345,025
No. 4,992,302 discloses a silver halide photographic material containing a contrast agent that increases contrast even in a relatively low-pH developer.

However, in the case of an image forming method in which silver rokenide photographic light-sensitive materials containing high contrast agents such as these are processed with a developer having a pH of less than 11.0, sensitization and softening of contrast over time, and unexposed areas after development processing occur. Currently, satisfactory performance cannot be obtained due to the problem of deterioration of the sand-like fog, so-called black spots, that occur on the parts.

[Purpose of the invention]

A first object of the present invention is to provide a method for forming an ultra-high contrast image that prevents sensitivity fluctuations and softening over time, as well as an increase in black spots that occur in unexposed areas.

A second object of the present invention is to provide a method for forming ultra-high contrast images that prevents sensitivity fluctuations and softening over time and increase in black spots that occur in unexposed areas even when processed with a developer having a pH of less than 11. There is a particular thing.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic photosensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the /% silver halide emulsion layer and/or its adjacent layer. This is achieved by an image forming method characterized in that the material is treated in the presence of at least one compound represented by the following general formula CN).

General formula [N] In the formula, R,, 'R2, R3 and R2 represent a hydrogen atom, an alkyl group, or an aryl group, and may be different from each other and may be the same, and may be bonded to a mega group to form a 5-7 It may also form a membered ring. X represents -0-1-3-, /N -R,
R3 and R represent halogen atoms.

Further, in a preferred embodiment of the present invention, the processing liquid p I+ is less than 11.0, and at least one kind selected from amine compounds and quaternary onium salts is contained in the silver halide emulsion layer and/or its adjacent layer. It contains a nucleation-promoting compound and/or a compound of the general formula [N].

The present invention will be explained in detail below.

In the general formula [N], R1, R2, R3 and R4 may be different or the same, and may be a hydrogen atom, an alkyl group,
Preferably, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, metquinethyl group, annoethyl group, octyl group, etc.), substituted or unsubstituted aryl groups (e.g., evaphenyl group, p- chlorophenyl group, etc.), and are bonded to each other to form a 5- to 7-membered ring (for example,
nclopenkune ring, nclohexane ring, etc.).

and R6 represent a halogen atom (chlorine, bromine, iodine, fluorine).

The compound of the present invention [N] is described as a preservative for seratin in JP-A-1-237647, etc., but it is surprising that when combined with a hydrazine derivative, ultra-high contrast images can be obtained with less fluctuation in photographic performance over time. It was the right thing to do.

Representative compounds of the present invention are described below.

C0.

Shi1131 CQ.

C(I! CQ.

r CQ Next, the synthesis method of the present invention will be described.

The synthesis of N-haloamine used in the present invention is carried out using rJourn
al of Pharmaceutical 5cie
65, pp. 1743-1746 and as taught in U.S. Patent Application No. 2,629,740. These teachings require first synthesizing the 2-oxazolidinone from an amino alcohol and diethyl carbanate and then halogenating the nitrogen.

In addition, the N-haloamine used in the present invention includes r Jou
rnal of Pharmaceutical 5c
iencesJ Vol. 76, pp. 245-247 and rJ
our own of the American Che
mical 5ocietyJ Vol. 77, 6689-6
It can be made as taught on page 690. These teachings first synthesize 2-imidazolidinone from an ethylenediamine derivative and then synthesize the nitrogen no.
They are requesting that they be converted into lokens.

Since the present invention is characterized in that processing is carried out in the presence of the compound of the general formula [N], the compound of the general formula CN) may be added during the production of the silver halide photosensitive material, or during development,
Although it may be added during processing such as fixing and washing, it is preferably added to a photosensitive material containing a hydrophilic colloid layer. More preferably, each layer constituting the photosensitive material including the wood-philic colloid layer, such as a silver halide emulsion layer, a subbing layer, an intermediate layer,
Ho I I! It can be applied to anti-harrayon layers and filter layers.

When added to the silver halide emulsion layer, it may be added at any time from the preparation of silver halide grains to coating, but it is preferable to add it after the completion of desalting during the preparation of silver halide grains. More preferably, the period is from after the completion of desalting during the preparation of silver lokenide grains to the end of chemical ripening.

When added to the subbing layer, intermediate layer, protective layer, anti-halation/con layer, or filter layer, it is preferable to add it at the time of preparing the mixture.

Further, in the manufacturing process, when each of these layers is prepared by mixing two or more liquids, it can be added to the combined liquid.

The amount of the compound of the present invention [N] added is preferably from 1X10-' to 10-2 mol per 1 mol of silver genide.

The compound of the present invention [N] is dissolved in water or an organic solvent such as methanol, isopropanol, acetone, or ethylene glycol that does not adversely affect photographic performance, and added as a solution to the hydrophilic colloid layer. It may be coated on a protective layer.

Next, the structure of the hydrazine derivative used in the present invention is preferably the following general formula (H).

General formula (H) A-N-N-G-R 1] A, A2 In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G is ○
0÷C')7 group, a sulfonyl group, a sulfoky7 group, a -P- group, or an iminomethylene group, n represents an integer of 1 or 2, A, A2 are both hydrogen atoms, or - One hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, and R is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloquine group, an amine group, a carbamoyl group, or an oxycarbonyl group. group or ORs group, R
3 represents an alkyl group or a saturated heterocyclic group.

Furthermore, the following general formula CADI CB) is preferable.

General formula (13) % Formula % In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n-1, R1 and R2 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroquine group, an alkoxy group, an alkenylox/group, an alkynylox/group, an arylox/group, Alternatively, it represents a heterocyclic oxy group, and R1 and R2 may form a ring together with the nitrogen atom. When n=2, R+ and R2
is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroquine group, an alkokene group, an alkenyloxine group, an alkynyloxine group, an aryloki/group, or a heterokyne group, respectively. represents. When n=2, at least one of R1 and R2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroquine group, an alkokyne group, an alkenyloxy group, an alkynyloxo group, an aryloxo group, or a heterocyclic okyne group. shall represent a group. R3 represents an alkynyl group or a saturated heterocyclic group.

The compounds represented by the general formula [A) or CB) include compounds in which at least one H of -N HN H- in the formula is substituted with a substituent.

More specifically, A represents an aryl group (e.g., phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (e.g., thiophene, furan, benzothiophene, pyran, etc.) .

R and R2 are each a hydrogen atom, an alkyl group (for example, methyl, ethyl, methoxynoethyl, /anoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.),
Alkenyl groups (e.g., allyl, butenyl, pentenyl, pentagenyl, etc.), alkynyl groups (e.g., glopargyl, butynyl, pentynyl, etc.), aryl groups (e.g., phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups ( Examples include unsaturated heterocyclic groups such as pyridine, thiophene, and furan, and saturated heterocyclic groups such as tetrahydrofuran and sulfolane), hydroquine groups, alkokene groups (e.g., methoxy, ethquine, benzyloxy, cyanomethoxy, etc.), and alkenyl groups. ox/group (e.g., alkoxy group niluoki/etc.), alkynyl oxe/group (e.g., propargyluoquine, putinyluoquine, etc.),
It represents an aryloxy group (e.g., phenoxy, naphthylogin, etc.) or a heterocyclic okyne group (e.g., pyridyloxi/, pyrimidyloxine, etc.), and when n-j, R1 and R2 together with the nitrogen atom represent a ring (e.g. , piperidine, piperazine, morpoline, etc.).

When n=2, at least one of R1 and R2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy7 group, an alkynyloxy7 group, an arylox/group, or a heterocyclic group. It represents an okine group.

Specific examples of the alkynyl group and saturated heterocyclic group represented by R3 include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of substituents that can be introduced include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkini groups, alkylthio groups, aryldio groups, sulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups,
Sulfamoyl group, anlu group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group, hydroxy group, carboxy group, sulfo group, di]-ro group, n-ano group, etc. Can be mentioned. Among these substituents, a sulfonamide group, an alkylamino group, an alkylidene amino group, etc. are preferred.

In each general formula, A preferably contains at least one diffusion-resistant group or silver halide adsorption-promoting group.

The diffusion-resistant group is preferably a pallast group, which is widely used in immobile photographic additives such as couplers.

A ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, and examples include an alkyl group, an alkokene group, a phenyl group, an alkylphenyl group, a fenoquine group,
You can choose from seven alkylphenox.

Examples of the silver halide adsorption promoting group include the groups described in US Pat. No. 4,385.108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

In general formulas (A) and [B], R1 of -NHNH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, l-luenesulfonyl, etc.), an anlu group (for example, acetyl, trifluoroacetyl, The compounds represented by the general formulas [A] and CB] may be substituted with a substituent such as an oxalyl group (e.g., ethoxalyl, pyruvoyl, etc.). Also included.

More preferred compounds in the present invention are compounds of general formula (A) where n=2 and compounds of general formula [B].

In the compound of general formula [A] where n=2, R1 and R2
is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, or an alkoxy group, and at least one of R1 and R2 is an alkenyl group, an alkynyl group, or a saturated heterocyclic group. More preferred are compounds representing a cyclic group, a hydroxy group, or an alkoxy group.

Representative compounds represented by the above general formula (A:l, CB) include those shown below. However, it goes without saying that the specific compounds of general formulas (A) and CB) that can be used in the present invention are not limited to these compounds.

Specific compound example *-NHNHCOCONHCH2CI = CH2 and R
3 *-NHNHCOCONI (CH2-CI = CH2
=23- +(-22 =26- H-39 H-40)U2' IOI H-103 H-104 H-105 H-1,06 H-1,09 I-r-116 H-118 H-120 H-122 H-123 H-124 ■1 ■ I-1-13'2 H-1'34 -45= H-136 =46- ■ CH3 H-141 C82C11□5H T-1-142 H-143 H-145 H-150 =49- H-153 H-154 C1]3 H- 155 H-156 υ H3 H-168 □ H3 H-169 CH2CH25H H-170 H-171 H-172 I-1-181 H-182 H-183 H-184 Next, examples of methods for synthesizing compounds according to the present invention Let's talk about.

For example, compound H-1 can be synthesized according to the following synthesis method.

CB□=(:H-CH2N++2 C2H,0COCOCff C2H50
It can also be synthesized using COCONHCH2-CH=CH2 or the following method.

15! I- These synthetic methods can also be referred to, for example, the synthetic methods described in JP-A-55-52050 and US Pat. No. 4,686.167.

Compound 1-3 can be synthesized according to the following synthesis method.

Compound I]-5 can be synthesized according to the following synthesis method.

160- Alternatively, it can be synthesized by the following method.

Compound H-35 can be synthesized according to the following synthesis method.

C21J5 Compound H-49 can be synthesized according to the following synthesis method.

Also, another method for synthesizing compound H-I H-5 and compound H
Examples of each synthesis method for -57 are shown below.

Synthesis of compound H-1 The synthesis scheme is as follows.

Ethoquinoxalylchloride 9411981 and then 14 g of triethylamine were added dropwise to a suspension of 15 g of p-nitrophenylhydrane and 150 ml of acetonitrile under ice-water cooling. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. Next, after removing insoluble matter by filtration, the filtrate was concentrated and the residue was dissolved in 400 ml (l) of chloroform. After washing with dilute alkaline water, the layers were separated, and the chloroform layer was concentrated to obtain 29.7 g of a crude product. This was purified by stirring and washing in 20 mff [Improper Tool] to obtain 16.9 g of compound (I). Acetic acid 1
16 g of compound CI) and 5 g of Pd/C catalyst were added to 6Omc and stirred under a hydrogen stream at normal pressure and room temperature. After the reaction was completed, the catalyst residue was removed and the filtrate was concentrated to obtain a composition.

This was purified by column chromatography to obtain 5.6 g of compound (II).

Compound (U) 8.1g and acetonitrile 80m0
．． A suspension of ethyl isothio/I-1 was heated under reflux.
・Drop 9.5g. After further heating under reflux for 2 hours, the mixture was concentrated to obtain 11 g of a composition. This was purified by recrystallization with acetonitrile to obtain 4.5 g of compound (III) =
65-l.

5.0 g of compound (m) was dissolved in 40 mQ of allylamine and heated under reflux for 2 hours. Concentrate after completion to obtain 4.9g of composition.
I got it. This was purified with chloroform two times to obtain 14.3 g of compound H-1.

Melting point: 2069°C8 M++1=322 was detected by FAB-MS.

Synthesis of compound H-5 The synthesis scheme is as follows.

Compound (1) was synthesized according to the method described in US Pat. No. 4,686.167. Compound (T)3]. 3 g of ethanol, 300 mff of ethanol, and 6 g of arylamine lo were heated and reacted at reflux temperature overnight. The reaction solution was concentrated, 600 mQ of benzene was added to the residue, and the mixture was cooled to 5°C and the precipitated crystals were collected by filtration to obtain 30 g of compound (TI).

30 g of compound (H) are dissolved in 540 ml of T)IF (tetrahydrofuran) and 150 ml of concentrated hydrochloric acid are added. Then 5 nC0,2150,8 g of T HF 5
A 40 m Q solution was added at room temperature and reacted overnight at 40-50°C. After the reaction, the precipitated crystals were collected by filtration, and methanol 1
The suspension was suspended in NH and OH under stirring to adjust the pH to 7.5 to 8 and stirred for 1 hour. Then, half the methanol was concentrated and 0℃
After cooling, the crystals were collected by filtration, and 9.8 g of compound (m
I got it.

After dissolving 15 g of compound (1) in 600 ml of pyridine, 1 L g of phenyl chloroformate was added dropwise to the solution while cooling from the outside at an internal temperature of 15° C. or lower. After the dropwise addition, the mixture was reacted overnight at room temperature. After the reaction, pyridine was concentrated and the residue was dissolved in acetone 2.
The mixture was washed with stirring using 00v2 and collected by filtration to obtain 17 g of compound (TV).

Dissolve 16.2 g of compound (TV) in 160 mQ of pyridine, and dissolve 16.8 g of compound (V) in 1.6 mQ of pyridine.
A 0 m Q solution was added, heated, and reacted at reflux temperature for 3 hours. After the reaction, pyridine was distilled off and 30% of n-hexane was added to the residue.
0 mQ was added, stirred and washed, and the crystals were collected by filtration. The crude crystals were heated and dissolved in 60 m+2 of DMF (dimethyl 7-olumamide), 180 mρ of acetone was added, and the mixture was cooled to OoC and the precipitated crystals were taken out to obtain 8 g of Compound H-513.

Melting point: 198.5-199.5°C M+=565 was detected with FAA B-1it S.

Synthesis of Compound H-57 1i9- 27 g of Compound (I), 250 mcL of ethanol, and 25 g of Compound (II) were heated and reacted at reflux temperature overnight. After the reaction, the reaction solution was cooled, and the crystals were collected by filtration and washed with ethanol. 31 g of the obtained crude crystals were recrystallized from 30° methanol to obtain 20.8 g of compound (m).

19 g of compound (I) was suspended in 400 mQ of THF, and 115 m (l) of concentrated hydrochloric acid was added.
, 4g of THF 300mQ solution was added at room temperature.
The reaction was carried out at 50°C overnight.

After the reaction, the precipitated crystals were collected by filtration, dissolved in 420v2 of methanol, suspended in 1680mQ of THF, and stirred with N.
The pH was adjusted to 8.5 with H and OH and stirred for 15 minutes. Thereafter, the precipitated crystals were collected by filtration to obtain 5 g of compound (TV) Il.

After dissolving lOg of compound (IV) in pyridine IQ, =
70- 5.2 g of phenyl chloroformate was added dropwise while cooling with ice from the outside at an internal temperature of 15°C or less. After dropping, react overnight at room temperature.

After the reaction, pyridine was concentrated to 700 to 800 mQ, 400 ml of acetone was added to the residue, stirred, and the precipitated crystals were collected by filtration.

The crude crystals were suspended in 200 mff of acetone and refluxed,
Next, 260 mQ of DMF was added dropwise to dissolve and insoluble matter was removed, and the mixture was cooled to 0°C. The precipitated crystals were collected by filtration and compound (V) 8
．． 5g was obtained.

Compound (V) log was suspended in 200ml of pyridine,
Compound (VI) 8.1g piri 77100m0. The solution was added and reacted at reflux temperature for 3 hours. After the reaction, 2Q acetone was added to the reaction solution to crystallize it, which was collected by filtration. The crude crystals were suspended in 35 mff of acetic acid and refluxed, and 85 m of methanol was added.
Immediately after dissolving 4 drops, the mixture was cooled to 0°C, and the precipitated crystals were collected by filtration to obtain 576 g of Compound H.

Melting point 230-231°C 7l-172= Compound (T) m in pyridine 50m+2 solution of
-6.6 g of nitrobenzenesulfonyl chloride was added externally while cooling in an ice-water bath. After reacting at room temperature for 10 hours, the solvent was distilled off, water was added, and the solid was collected by filtration.

This was subjected to column chromatography (chloroform/methanol-3
/2) to obtain 5.9 g of compound (II).

Compound (H) 5.5g, wet5%Pd/C1,O
A mixed solution of 150 mff of MEDH was hydrogenated and reduced at normal pressure.

After the reaction, Pd/C was filtered off, the solvent was distilled off, and the compound (I
II) was obtained. This was dissolved in 50 mff of pyridine, and a solution of 4.0 g of compound (IV) in 1 OmQ of pyridine was added dropwise to the solution while externally cooling in an ice-water bath. After stirring at room temperature for 5 hours, the solvent was distilled off, water was added, and the solid was collected by filtration. This was subjected to column chromatography (methylene chloride/methanol-571
) and then recrystallized from ethyl acetate-n-hexane to obtain 11.0 g of Compound H-61. Melting point 165-17
The structure of the 2°co compound was confirmed by MS and NMR.
child .

Compound H-62 can be synthesized by the following method.

Compound H-116 can be synthesized by the following method.

Compound H-133 can be synthesized by the following method.

Compound I(-140 can be synthesized by the following method.

−76= Compound 1'1-71 can be synthesized by the following method.

Compound H-71 Compound H-149 can be synthesized by the following method.

Compound H-149 In the present invention, the following general formula [■] is used as an amine compound and quaternary onium salt compound as a nucleation promoting compound to be used in combination with the hydrazine compound represented by the general formula [A] and CB).
- [■] Compounds are mentioned. Among these, preferred compounds are (V)-■, (v)-n, [■]-■, (V
l)-1, (Vl)-■, (■:]-III).

General Formula (T) [General Formula [19 In the formula, R, , R2, and R3 represent a hydrogen atom or a substituent. R+, R2, and R3 may be linked to each other to form a ring. Examples of the substituents represented by R, R2, R include alkyl groups (e.g., methyl, ethyl, propyl, butyl, hexyl, nclohexyl, etc.)
, alkenyl groups (e.g. allyl, butenyl, etc.), alkynyl groups (e.g. glopargyl, butynyl, etc.),
Aryl groups (for example, phenyl, naphthyl, etc.), heterocyclic groups (for example, piperidinyl, piperazinyl, morpholinyl, -78 = piperinyl, piperinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.) Base) etc. can be mentioned.

R, , R2, and R may be linked to each other to form a ring (for example, a ring such as piperine, morpholine, piperazino, quinuclizone, pyridino, etc.).

The groups represented by R, R2, and R include substituents (for example, hydroquine, alkoxy/, aryluoquine, carboquine,
(groups such as sulfo, alkyl, aryl, etc.) may be substituted.

As R,, R2, R, a hydrogen atom or an argyl group is preferable.

Specific examples represented by general formula (1) are listed below.

I-] I-2CH, NHCH□C+, 20ilI-7(C2
H5) 3N ■-8■-9 Jtl ■-13 ■-14 ■-15 JH ■-17 1-18l-19 lI ■-21 8l- I-22l-23 ■-26 General formula [■] Rz Q RI I RI Xo [In the general formula CmE, Q represents an N or P atom.

Rl+R2 and Rl+Rl represent a hydrogen atom or a substitutable group. XO represents an anion.

R,, R2, R3, and R may be linked to each other to form a ring. Examples of substitutable groups represented by Rl, R2, R3, and R4 include alkyl, alkenyl, alkynyl, aryl, heterocycle, and amine. Specifically, R of general formula [1゛], , R2, and R3. Examples of the ring that can be formed by R+, R2, R3, and Rl include the same rings as those described for the ring that can be formed by R+, R2, and R3 in the general formula [E]. XO
Examples of the anion represented by this include inorganic and organic anions such as halide ions, sulfate ions, nitrate ions, acetate ions, and paratoluenesulfonic acid ions. ] Specific examples of the compound represented by the general formula (Tl, ) are listed below.

C16831N(CHI)l BrQ(
C, Hl), N CQ○I -4 (CH3)3NCH2CH20HCQ.

(CJs)+N CH2ClI2 N(CIHI)
8 50%0(C2H6)3N-(CH2)8-N
(C: Hi) 3210 ■-12 ■ CH2C00CH3C120 ■-14 ■-16 ■-17 2Br.

■-18 CQ0 ■-19 ■-20 ■-21 ■-22 (CH3)3N (CH2)2S 5 (CH2)2
N(CH3)3■-23 (CH3) , N(CH2), 5(CH,) 2S(C
H2)2S(CH2) 2N(CH,) ]11-2/
1 ■～25 ■-26 ■-27 ■-28 (C+89:h P-C16H332BrO■-29 General formula (III) [General formula [■]] In the formula, R+ and R2 represent an alkyl group, and R1 and R2 are Even if they are connected to form a ring: Yes.

R3 represents an alkyl group, an aryl group, a heterocyclic group, and A
represents an alkylene group.

Y is -CONR, -+-0CONR, -, -NRICO
NRl-.

-NR,Coo-, -COO-, -0CO-, -CO
-, -0COO-.

-NR, Co-, -3o2NR, -1-NR,5O2-
, -NR,5O2NR,-,'-SO□-, -S-,-
It represents a 0-, -NR,-, -N- group, and R4 represents a hydrogen atom or an alkyl group.

The alkyl group represented by R,, R2 has the general formula (N
Examples include the same alkyl groups as R + , R2, and R3 explained above, and the rings to be formed also include the same alkyl groups.

The alkyl group and aryl group represented by R3 also have the general formula ([)
Examples include the same alkyl groups and aryl groups represented by R, , R2, and R.

As the heterocyclic group represented by R3, R of the general formula CI)
Examples of 1, R2, and Rs include those similar to heterocyclic groups and groups represented by the following general formula (III-a).

-1--I In the formula, a represents 0 or ■, m represents 1, 2 or 3,
n does not represent O or 1.

Q represents an atomic group necessary to form a 5- or 6-membered heterocycle composed of at least one type of carbon atom, nitrogen atom, oxygen atom, and sulfur atom.

Further, this heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle formed by Q include substituted or unsubstituted indazoles, pensimidazoles, penztriazoles, pensuoxazoles, pensteazoles, indazoles, thiazoles, oxazoles, i-lyazoles, Tetrasols, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, quinolines, etc. are available.

M is a hydrogen atom, an alkali metal atom (e.g., a sulfur atom, a potassium atom, etc.), an ammonium group (e.g., a trimethylammonium group, a dimethylbenzylammonium group, etc.), and under alkaline conditions, M = H or an alkali metal atom. It represents a diluent group (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.).

In addition, these heterocycles include 21.4 groups, halogen atoms (e.g. chlorine atom, bromine atom, etc.), mercapto groups, cyano groups, substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, propyl group, etc.). , butyl group, cyanoethyl group, methoxy/edyl group, methylthioethyl group, etc.), aryl group (e.g. phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3.4-
dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, 4-methylhensyl group, phenethyl group, etc.),
Alcoquine group (e.g. methoxy/ethoxy group, ethquine group, etc.),
Acetyloxy group (example: phenoxy/group, 4-methoxy/
phenylthio group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, metquinethylthio group), arylthio group (e.g. phenylthio group), sulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluene) sulfonyl group, etc.), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.) ), carbonamide group (e.g. ace[・amide group, pensamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, pencenesulfonamide group, p-1' luenesulfonamide group, etc.)
, aralkyl group (e.g. acetyloxy group, benzoyloxy group, etc.), sulfonyloquine group (e.g. methanesulfonyloxy group, etc.), ureido group (e.g. unsubstituted ureido group, methylureido group, ethylureido group) , phenylureido group, etc.), thiochlei 1-group (e.g., unsubstituted thioureido group, methylthioureido group, etc.),
Anru group (e.g. acetyl group, benzoyl group, etc.), heterocyclic group (e.g. l-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group,
■-pyrazolyl group, 1-imidazolyl group, 2-ti-rahydrofuryl group, te-rahitoc+-F-enyl group, etc.), oquinecarbonyl group (e.g. mel-oxycarbonyl group, phenoxycarbonyl group, etc.), oquine carbonylamino group (e.g., methquine carbonylamino group, phenokine carbonylamino group, 2-ethylhexyloxy/carbonylamino group, etc.), amine group (e.g., unsubstituted amino group, dimethylamino group, Mei・ki/ethylamino group,
anilino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt, hydroxy group, etc.

Examples of the alkylene group represented by A include methylene,
Examples include ethylene, trimethylene, and tetramethylene, and examples of substituents for A include aryl groups, alkokene groups, hydroxy groups, and halogen atoms.

The alkyl group represented by R3 is preferably a lower alkyl group having 1 to 5 carbon atoms or an aralkyl group (eg, benzyl group). ] Below are specific examples of compounds represented by the general formula [■] 1l-1 Tf>2 1l-5 I[1-6 r14°=94- IIT-3 ■-13 ■-14 ■-15 ll-17 ■-18 1l-19 '-96- ll-20 ll-21 ■-23 ■-25 ■-26 ■-27 ll-28 ■-29 rθ ll-30 ■-31 ■-32 ■-33 9(] - lll-34 ■-35 ■-36 ■-37 rl.

■-38 ■-39 I] lll-40 ■-41 ■] ■-42 ■-44 General formula (IV) [In general formula (IV), R, , R2 are hydrogen atoms, alkyl groups, alkenyl groups, It represents an alkynyl group, an aryl group, or a heterocyclic group, and R, , R2, and E may form a ring.

E is a group containing at least one group represented by (-CH2CH3O)-n. n represents an integer of 2 or more.

Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group and R1゜R2,E represented by R11R2
As the ring formed by R, , R2, of general formula [I],
It may be the same as that explained in R3. ] Specific examples of the compound represented by the general formula CCV are listed below.

IV-] IV-2 IV-3 IV-4 IV-5 IV-6 IV-7 +1-8 +1-9 IV-10 TV-I+ ■-12 ■-13 ■-14 ■-15 IV-16 ■- 17 Vi8 IV-19 ■-20 IV 21 C5H+ INH(CH2CH20
),,-CH2CH2NHC5H,,IV-22C,8
,5NH-(CH,CH,O)1. cH2cH2Nl(
C, H, 5■-23 rv-24CCH2=CH-CH2NH)■(CH7C
H20) 14CH2CH2+v-25CcH=c-CH
,NH)2(c++2c++2o),,cl(2c+-
+2 ■-26 ■-27 ■-28 ■-29 ■-30 IV-31 ■-32 ■-33 ■-34 ■-35 ■-36 ■-37 ■-38 ■-39 CH.

■-40 IV-41 General formula (V)-1 Represents a kyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. However, at least one of R, R2, and R3 represents an alkenyl group or an alkynyl group, or at least one of R, R2+ represents an aryl group or a heterocyclic group. R, , R2, L, and R3 may form a ring. L represents a linking group.

R,, R2, R, and the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group include the same groups as those listed for R,, R2, and R3 in general formula [■]. It will be done. Examples of the ring formed by R, , R2, L, and R3 include heterocycles such as piperidine, morpholine, and pyrrolidine.

Examples of the linking group represented by the formula (III) include 1A-Y- as shown in the general formula (III). ] Specific examples of the compound represented by the general formula (V)-I are listed below.

-1-I -I-2 -r-3 V -1-4 -I-5 -I-6 -I-7 -I-8 ■-■-10 -I-11 -I-12 =113- - I-13 ■-■-14 -I-15 -11=1- V-I-18 V-I-19 -I-20 ■-■-22 -I-23 v-■-24 -I-25 v -■-26 -I-27 General formula (1-n [General formula [■]] -■ In the formula, R, , R2, R represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group .R3 represents a hydrogen atom or a substitutable group.

L represents a linking group, and n represents an integer of 0 or l.

R,, R2, R3, and R may be connected to form a ring.

The alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R, , R2, and R include the same groups as explained for R, , R2, and R3 in general formula [I]. Can be mentioned.

Among the groups represented by R3, substitutable groups include, for example, alkyl, alkenyl, alkynyl, aryl, heterocycle, and the same groups as mentioned above.

L represents a linking group, for example -co-, -coo-.

Represents a group such as -CONR6-, -5O2-, -5o2NR5-.

R5 represents a hydrogen atom or a substitutable group.

Examples of the ring formed by RI+R2, Rl, L and Rt include heterocycles such as piperidine and morpholine. ] Specific examples of the compound represented by the general formula [:V)-II are listed below.

■−■−4 −118. - VI [-6 V-11-8 V-11-10 -n-12 V-IT-13 -H-14 V-II-15 V-11-16 V-11-17 V-]>18 -n-19 V-II-20 V -ll-21 V-It-22 V-I[-23 V-I[-24 v-n-26 ■-■-27 V-11-28 -n-29 V-11-30 General formula (V)-IIl, 1', represents a substituent. R2 represents alkyl, alkenyl, alkynyl, aryl, and heterocycle. L represents a linking group.

,・'-1., Ni represents a nitrogen-containing heterocycle. nl:io or l\, -
represents an integer of m-'.

／゛−′・、 R, may form a ring together with li.

'., -2.' As the alkyl, alkenyl, alkynyl, aryl, and heterocycle represented by R2, Rl of the general formula [I]
+R2+R, and the same groups as explained above may be mentioned.

Among the groups represented by R1, substituents include, for example, the above R
Groups similar to those explained in 2 can be mentioned.

Examples of the heterocycle include heterocycles such as quinuclidine, piperidine, and pyrazolidine. Examples of the linking group represented by this include those similar to those represented by Y in the general formula [■]. ] Specific examples represented by the general formula [v]-■ are given below.

-111I -ml-5 -H1-6 V-111-7 VI [1-8 V-111-9 -m-11 V-Ill-12 I 2H5 V-111-17 ■ CH2-CH=CH2 v-Ill-21 -m-25 V-nl-26 -m-27 vll+-28 V-111-29 v-m-34 General formula (Vl)-I p.

[In the general formula (Vl)-1, R, , R2 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R6R+ represents a hydrogen atom or a substituent.

A group containing at least one group. R represents a hydrogen atom or an alkyl group, X represents an OlS or NH group,
Y represents a hydrogen atom or an OH group, and n represents an integer of 2 or more.

R,, R2, R3, and R may be connected to form a ring. Examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by R, R2 include the same as those explained for Rl, R2, and Rh in general formula CI). It will be done.

Examples of substituents among the groups represented by R3 include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, aryl groups, sulfonyl groups, oxycarbonyl groups, and carbamoyl groups.

Among the substituents represented by R3, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and heterocyclic groups include:
Examples include the same groups as explained for R, , R2, and R3 in the general formula [■].

Examples of the acyl group include acetyl, benzoyl, etc.; examples of the sulfonyl group include methanesulfonyl, toluenesulfonyl, etc.; examples of the oxycarbonyl group include etquin carbonyl, phenoxy7carbonyl, etc.; So, methylcarbamoyl,
Examples include phenylcarbamoyl.

Examples of the ring formed by Rl, R2, R3, and Rl include rings such as piperidine and morpholinone.

Among the groups represented by R, the alkyl group is methyl, edyl, etc., and the methyl group is preferred. ] Below is the general formula [Vl)-
Specific examples of the compound represented by I will be given below.

Vl-1-1 1-I-3 1l-4 l113- Vl-l-5 1-I-6 Vl-1-7 T-I-8 Vl-1-9 VI-I-10 -1:14- VT-T -11 VT-I-12 Vl-T~13 Vl-I-14 VT-■15 Vl-I-16 Vl-Ti7 Vl-I-18 Vl-I-19 VT-I-20 Vl-I -21 VT-I-22 ■-I-23 Vll-I-24 Vl-I-25 Vl-1-26 Vl-1-27 VT-I-28 VT-1-29 Vl-1-30 Ul+ Vl- I-31 ■-1-32 vr-T-33 Vl-I-34 VT-I-35 vr-I-36 ■-f-37 Vl-T-38 Vl-I-39 Vl-1-40 ■～ l-41 Vl-1-42 UI'I ■-■-43 Vl-T-44 ll11- General formula 1: VI)-11 [General formula 1: VI]-It In the formula, R,, R2 are hydrogen atoms , represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R, , R2, and T may form a ring. T is I
Alternatively, it is a group containing at least one group represented by CH2-CH-CH2-0. R represents a hydrogen atom or an alkyl group, Xi represents a tO, S or NH group, Y represents a hydrogen atom or an OH group, and n represents an integer of 2 or more.

However, when R is a hydrogen atom, X represents an S or NH group. Among the groups represented by R, and R2, the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group include Ro of the general formula [■].

Examples include the same groups as those explained for R2 and R3.

Examples of the ring formed by R,, R2, and T include heterocycles such as piperine, morpholine, quinuclidine, and pyrazolidine. The alkyl group represented by R is methyl,
A group such as ethyl, preferably a methyl group. ] Specific examples of the compound represented by the general formula [Vl)-It are listed below.

Vl-II-1 VT-11-1 Vl-11-3 VI-11-4 Vl-11-5 1-H-6 CHI C8I II C5H,, NH (CH2-CH-0), 0-CI+2-
CHNHC,l(,,1-n-7 Vl-I[-8 Vl-n-9 Vl-II-10 Vl-11-11 Vl-II-12 Vl-11-13 VT-II-14 r+4- ■ CH3 VT-I[15 b15- VT-11-16 VT-I[-17 Vl-11-18 Vl-1119 Vl-11-20 146-Vl-11-21 Vl-It-22 Vl-11-23 C5H ,□NH(CH3CH-CH20)+2HH VI-H-26 'JI-H-27 Vl-II-29 ■〜■-30 VT-II-31 VJ-11-32 CH3 C8H,7NH(CH2-CH-0 )+t(CH2CH
-CH20) 20HH Vl-11-33 r+4- Vl-IT-34 J11 VI-11-35 l119- VT-■-36 r1]6 Shi113 VI-11-37 Vl-11-38 VI-11-39 Vl -II-40 H ■-It-41 Vlt-11-42 Vl-H-43 C, H17NH (CH2CH2SH), 6HVl-11
-44 VT-11-45 ■-11-46 vr-H-47 vr-11-48 Vl-71-49 C6H,3NH (CH2CH2S), □-CH2CH
2NHC6H13Vl-H-50 Vl-I[-52 Vl-11-53 CH-C-CH2NH(CH2CH2S)2. -CH2
CH2NHCH2-CmiCHVT-H-54 H30HI Vl-11-55 Vl-11-56 Vl-IT-,57 Vl-IT-58 Vl-II-59 Vl-II-60 vr-n-61 Vl-It- 62 CsH++NH(CH2CH2CH20)+J■-11
-63 Vl-11-64 Vl-11-65 VI-II-66 Vl-11-67 Vl-II-68 General formula (vB-m [General formula [:VI:]-11I in the formula, R,, R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and R,, R2, and G may form a ring.

G is at least 1 group represented by f:cH2cH20Th
and hydrophobic substituent constant π value -0,5 to -10
or at least one substituent having a π value of less than -1.0. n represents an integer of 2 or more. Among the groups represented by R, and R2, the six groups of alkyl, alkenyl, alkynyl, allul, and heterocycle include the same groups as explained for R1, R2°R3 in general formula (1).

Examples of the ring formed by R, , R2, and G include rings such as piperidine, quinuclidine, and morpholine.

The hydrophobic substituent constant π is described in Structure-Activity Relationships of Drugs (Nankodo) P79-P103 (1978).

Examples of substituents with a π value of -05 to -1,0 include -CONH2, -CONHOH, -CO
NHCH.

-NH2, -NIiCONH2, -NHC3NH2, -
NH302CH3, -NO(CH3)3. −〇”.

0CONH2,503°, 5O2N+(2,5OC
Examples include groups such as H3, 5O2CH3, and CooO. ] Specific examples of the compound represented by the general formula [:V'1)-IIT are listed below.

Vl-1n-1 VT-IIT-2 Vl-111-3 VT-111-4 Vl-111-5 1-I-6 CH2=CHCH2NH-(CH2CH20)6cH2
cOOKVl-111-7 VI-I[1-8 Vl-l-9 Vl-I[1-10 Vl-111-11 VI -Ill-12 "C)13 Vl -llll-1,3 ■ H3 Vl-IIT -14 Vl-Ill-15 Vl-111-16 ■-111-17 VT-1'1l-18 Vl-Tll-19 VI-II[-20 Na Vl-111-21 ■-m-22 Vl-111- 23 Vl-I[1-24 ■-1[1-28 VI-I[[-29 Vl-m-30 Na Vl-I[+-31 Na ■-m-32 VT-117-33 Vl-111 -34 Vl-III-35 VI-111-37 The silver halide photographic material to which the present invention is applied and which can be said to have high contrast contains at least one of the hydrazine compounds represented by the above general formulas [A] and [B]. The amount of the compound of the general formula CA ), C B ] contained in the photographic light-sensitive material is 5% per mole of silver halide contained in the photographic light-sensitive material.
It is preferable that X 10-' mol-5 X to-' mol.

In particular, it is preferable to range from 5 x 10-6 mol to IXIO-2 mol.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer. That is, at least one silver halide emulsion layer may be provided on one side of the support, or at least one silver halide emulsion layer may be provided on both sides of the support.

This silver halide emulsion can be coated directly on the support, or it can be coated via another layer, such as a hydrophilic colloid layer that does not contain the silver halide emulsion, and further coated with the halogen emulsion. A wood-philic colloid layer may be coated on the silver emulsion layer as a protective layer. In addition, the silver halide emulsion layer is
Silver halide emulsion layers having different sensitivities, for example high sensitivity and low sensitivity, may be coated separately. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, if necessary, an intermediate layer made of a hydrophilic colloid may be provided. Also, an intermediate layer, a protective layer, an anti-halation 732 layer, a banking layer, etc. may be provided between the silver halide emulsion layer and the protective layer. A non-photosensitive hydrophilic colloid layer may also be provided.

The compound represented by the general formula CA], l:B), (f) to ['VT] is present in the silver halide emulsion layer or adjacent to the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention. Contained in the hydrophilic colloid layer.

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. The silver halide is silver chloroiodobromide or silver iodobromide containing 4 mol % or less of silver iodide, preferably 3 mol % or less of silver iodide. The average diameter of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, particularly in the range of 0.10 to 0.40 μm.
Preferably, the diameter is μm.

Although the grain size distribution of the silver halide grains used in the present invention is arbitrary, it is preferably adjusted to have a monodispersity value of 1 to 30, more preferably 5 to 20, as defined below.

Here, the monodispersity is defined as the value obtained by dividing the standard deviation of particle diameter by the average particle diameter times 100. For convenience, the grain size of silver halide grains is expressed by the edge length in the case of cubic grains, and is expressed by the edge length for other grains (octahedral, tetradecahedral, etc.).
is calculated by the square root of the projected area.

When carrying out the present invention, for example, silver halide grains having a multilayer structure of at least two layers can be used, for example, silver iodobromide in the core and bromide in the shell. It is also possible to use silver iodobromide grains, which are silver. At this time, iodine can be contained in any layer within 5 mol%.

The silver halide grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt, Metal ions can be added using at least one selected from salts (including famous salts) and iron salts (complex salts including) to contain these metal elements inside the particles and/or on the surface of the particles, Further, by placing the particles in a suitable reducing atmosphere, reduction sensitization can be imparted to the inside of the particles and/or to the particle surfaces.

Furthermore, silver halides can be sensitized with various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfur sensitizers (sorta thiosulfate, allylthiocarbamide, thiourea, allyl isothyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea etc.), reduction sensitizers (I, lyethylenetetramine, silver chloride,
tin, etc.), such as potassium chlorooleite, potassium aurithionanate, potassium chlorooleate, 2
- Various noble metal sensitizers represented by aurosulfobenzothiazole methyl chloride, ammonium chloroparade 1-, potassium chlorobratate, sodium chlorovaladite, etc. can be used alone or in combination of two or more. It can be used as

When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The silver halide grains used in the present invention can be preferably applied to grains whose surface sensitivity is higher than that of their internal sensitivity, so-called silver halide grains that give a strong image. Performance can be improved.

Further, the silver halide emulsion used in the present invention includes mercapto compounds (1-phenyl-5-mercap[·te]razole, 2-mercaptobenzthiazole), benztriazoles (5-brombenzotriazole-5- Stabilization or fog suppression can be performed using methylbenzotriazole), benzimidazoles (6-nidropentzimidazole), indazoles (5-nitroindazole), and the like.

The photosensitive silver halide emulsion layer or its adjacent layer contains a Research Disclosure for the purpose of increasing sensitivity, increasing contrast, or promoting development.
17463, xxr, B-D can be added.

The silver halide emulsion used in the present invention includes a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added.

When the compound of the general formula according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at an amount of 1Og/m2 or less.

Supports that can be used in the practice of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

For developing the silver halide photographic material of the present invention, the following developing agents may be used, for example.

Typical HO-(CH=CH)n-OH type developing agents include hydroquinone, and others include catechol and pyrogallol.

Typical HO-(CH=CH)n NH2 type developers include ortho and para aminophenol or aminopyrazolone, N-methyl-p-aminophenol, N-β-hydrogynethyl- Examples include p-aminophenol, p-hydroquinphenylaminoacetic acid, and 2-aminonaphthol.

Examples of the heterocyclic developer include l-phenyl-3-pyrazolidone, ■-phenyl-4,4-dimethyl-3-birasoliton, ■-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-7enyl-4-methyl −
3- such as 4-hydroquinemethyl-3-virasoliton
Examples include pyrazolidones and the like.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of the Photographic P
rocess.

Fourth Edition, pp. 291-334 and Journal of the American Chemistry Society.
erican Chemical 5ociety
) Vol. 73, p. 3.100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, or it is preferable to use two or more types in combination.

Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired.

Furthermore, hydroquineluamine and hydrazide compounds may be used as preservatives.

In addition, pH adjustment and buffer functions can be provided using caustic alkali, carbonate alkali, or amine, which are used in general black and white developing solutions.

The developer used in the present invention is characterized in that it can be used if it has a pH of less than 11. In addition, the developer contains bromopotash, an inorganic development inhibitor, 5-methylbenztriazole,
Organic development inhibitors such as 5-methylbenztriazole, 5-2l-loindazole, adenine, guanine, ]-]phenyl-5-mercaptothi]rasol, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, Development accelerators such as pencil alcohol and polyalkylene oxide; surfactants such as sodium alkylarylsulfonate, natural saponins, sugars or alkyl esters of the above compounds; hardeners such as glutaraldehyde, formalin, and glyoxal; It is optional to add an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention may contain alkanolamines such as jetanolamine and triethanolamine, and glycols such as diethylene glycol and triethylene glycol as organic solvents. Furthermore, alkylamino alcohols such as diethylamine-1,2-propanediol and butyramitubrobanol can be particularly preferably used.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

(Preparation of Silver Halide Photographic Emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. At the time of this mixing, 21rCff
6 was added at 8X 10-' moles per mole of silver.

The resulting emulsion was composed of cubic monodisperse grains (coefficient of variation 9%) with an average grain size of 0.20 μm. Modified seratin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added to this emulsion, and Example 1 of Japanese Patent Application No. 1-180787 was added.
Washed with water and desalted in the same manner. Subsequently, a potassium iodide aqueous solution of 0.1 mol % per mol of silver was added to this emulsion to convert the grain surface, and then the compound [N] of the present invention was added as shown in Table 1 to form an emulsion. A
I got it. I)Ag at 40°C after desalting was 8.0.

(Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (Japanese Patent Application Laid-Open No. 2-12145
A silver halide emulsion layer having the following formulation (1) was coated on one undercoat layer of a 100 μm thick polyethylene terephthalate film coated with a polyethylene terephthalate film having a seratin content of 2.0.
g/m2, silver amount is 3.2 g/m2, and on top of that, an emulsion protective layer of the following formulation (2) is applied with a seratin amount of 1.2 g/m2. og/m2, and on the other undercoat layer on the opposite side, apply a backing layer according to the following recipe (3) so that the amount of gelatin is 2', 4g/m2, Furthermore, a no-knocking protective layer of the following formulation (4) was applied on top of it so that the amount of gelatin was 1 g/m2, and Sample No. 1 was prepared.
-18 was obtained.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0 g/m2 Silver halide emulsion A Silver amount 3.2 g/m2 Sensitizing dye: Stabilizer: 4-methyl-6-hydroxy-1,3,3a,
7-Chitrazaindene 30mg/
m2 hornworm prevention agent: Adenine lomg/m21-7enyl-5-mercaptotetrazole 5mg/m2 Surfactant Zabonin O, 1g/m2:
S-18mg/m2 Human lan derivative according to the present invention Amount not shown in Table 1 Latex polymer: Polyethylene glycol Molecular weight 4000 0.1g/m
2 prescription (2) [Emulsion protective layer composition] Ceratin 0.9 g/m2 Surfactant S-2 03Na Surfactant: S-3 Mantle agent Monodisperse with average particle size 3.5 Izm/Rica 3 mg
/n+2 Hardener: 1.3-vinylsulfonyl-2=propatol 40mg/m2 formulation (3) (backing layer composition) Gelatin 2-4 g /
m 2 surfactant: saponin 0.1g/
m2: S -16mg/m2 coroital silica loomg/m2
Prescription (4) [Backing protective layer composition] Gelatin Ig/m2 Matting agent: Monodispersed polymethyl methacrylate with an average particle size of 5.0 μm 50 mg/m2 Surfactant: S-210
mg/m2 Hardener: Glyoxal 25
mg/m2: H-135mg/m2 The obtained sample was closely attached with a stamp wedge and heated at 3200
After exposure to tungsten light for 5 seconds, processing was carried out under the following conditions using an automatic developing machine for rapid processing into which a developer l and a fixer having the composition shown below were introduced.

In addition, the obtained sample was heated at 23°C, 150% R11 for 24 hours.
After storage for a period of time, it is sealed and packaged for 55 minutes as a thermal treatment for aging.
It was left at °C for 3 days. This thermo-treated sample was exposed, developed, and fixed in the same manner.

Developer formulation 1 Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Trisodium phosphate (12 hydrate) 75g Boric acid
-Hydroquinone
225g Sodium hydroxide 8g Sodium bromide 3g 5-Methylbenzotriazole 0.25g 2-Mercaptobenzthiazole 0.1g 2-Mercaptobenzothiasol-5-sulfonic acid 0.2g N.Methyl p.Aminophenol l/2 Sulfur salt 0.25
gn・butyl・ethanolamine 15.0g
Phenitylpicolinium bromide F 2 , 5 g
Add water and adjust pH with 10° sodium hydroxide 10.4 Fixer formulation (fl composition A) Ammonium diosulfate (725% W/V aqueous solution) 240
mff sodium sulfite 17g
Sodium citrate dihydrate 6.5g Boric acid 6.0g Sodium citrate dihydrate 2. Og (composition) Pure water (ion exchange water) 17mQ sulfuric acid (50% W/V aqueous solution) 4.7g
Aluminum sulfate 26.5g (A
12O, equivalent content: 8.1% W/V (7) Aqueous solution) When using a fixer, 500 m0. The above-mentioned composition A1 was dissolved in the same order as above, finished to IQ, and used. The pH of this fixer was adjusted to 48 using acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 3
Fixing at 8°C for 15 seconds Washing at 35°C for 15 seconds Drying at 30°C for 10 seconds 50°C for 10 seconds The comparative compounds of the hydrazine derivative according to the present invention added to the silver halide emulsion layer in formulation (1) include the following (a) ) was added.

(a) RH The obtained developed sample was measured using a digital densitometer P.
Measured with DA-65, expressed as relative sensitivity with the sensitivity of sample No. 1 at a concentration of 2.5 as 100, and further at a concentration of 0.1.
A comma is displayed with a tangent of and 2.5. A gamma value of less than 6 is unusable, and a comma value of 6 or more and less than 10 still provides insufficient high contrast performance.

A gamma value of 10 or higher results in an ultra-high contrast image, making it fully practical.

In addition, black blemishes in unexposed areas were also evaluated using a 40x magnifying glass. The highest rank is ``5'' where there are no black spots at all.
”, and the ranking is “4” depending on the degree of occurrence of Black Bottle.
”, “3”, “2”, and “1”. At ranks "1" and "2", black spots are also at a practically unfavorable level.

-181= From the results in Table 1, it can be seen that the samples of the present invention do not become sensitized over time, have few black spots, and have high contrast.

Example 2 The same procedure as in Example 1 was conducted except that the nucleation accelerator according to the present invention was added to the silver halide emulsion layer in the amount shown in Table 2. The results are shown in Table-2.

As a comparative compound of the nucleation accelerator added to the silver halide emulsion layer, the following compound (b) disclosed in JP-A-62-187340 was added.

(b) From the results in Table 2, it can be seen that the samples of the present invention did not become sensitized over time, had fewer black spots, and had high contrast compared to the comparison.

Example 3 The same procedure as Example 2 was carried out except that the following developer solution 2 was used. The results are shown in Table-3.

Developer formulation 2 Ethylenediaminetetraacetic acid sodium salt 1g Lithium sulfite 60g Boric acid
40g Hi-I Loginone
35g sodium hydroxide
8g sodium bromide
3g5-medylbenzotriazole 0
．． 2g2-Mercaptobenzthiazole 0.1
g2-mercaptobenzthiazole-5-sulfonic acid
0.2gj-phenyl-4,
4-dimethyl-3-pyrazolidone
Add 0.2g water
pH adjusted with lQ hydroxide, 1O
From the results in Table 15, it can be seen that the samples of the present invention do not undergo sensitization over time, have few black spots, and have high contrast.

〔Effect of the invention〕

According to the present invention, it is possible to provide an image forming method using a silver halide photographic light-sensitive material that has excellent shelf life without sensitization, softening of tone, increase in black spots, etc. over time even when a low pH developer is used. did it.

Claims (1)

Scope of Claims (1) A silver halide photographic material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer and/or its adjacent layer. An image forming method, characterized in that processing is carried out in the presence of at least one compound represented by the following general formula [N]. General formula [N] ▲ Numerical formulas, chemical formulas, tables, etc. A 5- to 7-membered ring may be formed. X represents -O-, -S-, ▲There are numerical formulas, chemical formulas, tables, etc.▼, and R_3 and R_4 represent halogen atoms. (2) The image forming method according to claim 1, wherein the image forming method is processed with a developer having a pH of less than 11.0. (3) At least one nucleation-promoting compound selected from amine compounds, hydrazine compounds, and quaternary onium salts is contained in the silver halide emulsion layer and/or its adjacent layer. Item 2. Image forming method according to item 2.