JPH0192738A - Silver halide photographic sensitive material and process for forming superhigh contrast negative image therefrom - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material effective for reproduction of dot picture images and line originals, having high sensitivity and hard contrast and causing scarcely generation of black spots by using at least one kind of hydrazine derivs. and at least one kind of specified compds. in combination for a photosensitive material. CONSTITUTION:A silver halide photographic sensitive material having at least one silver halide emulsion layer on a base, and contg. at least one kind of hydrazine derivs. and at least one compd. expressed by formula II: C-L-D in the emulsion layer, is prepd. and the photosensitive material is image-exposed. The exposed material is developed with a developing soln. contg. >=0.15mol/liter sulfite ions and having 10.5-12.3 pH. C and D in the formula II may be same or different, expressing a 5- or 6-membered N-cong. hetero-cyclic ring residue. L is an unconjugated divalent joint group, with the proviso that C, D, or L has at least one acidic group. By this constitution, a silver halide photographic sensitive material having extremely high hard contrast, causing scarcely generation of black spots is provided, and a negative picture image having extremely hard contrast is formed therefrom.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material useful in the field of graphic arcs and a method of forming ultra-high contrast negative images using the same.

(Prior art) In the field of graphic arcs, in order to improve the reproduction of continuous tone images using halftone images or the reproduction of line images, the true characteristics of carbide tA (especially with a gamma of 10 or more) have been shown. An imaging system is required.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is extremely low (usually O01). Therefore, the Lith developer has the serious disadvantage that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method for obtaining high contrast photographic properties using a stable developer, US Pat.
No. 168.977, No. 4,166.742, No. 4
There is a method using a hydrazine derivative described in, for example, No. 311,781, No. 4,272,606, No. 4,211.857, No. 4,243,739.

According to this method, photographic properties with ultra-high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. It improves dramatically in comparison.

However, in the system using this hydrazine derivative,
It has been found that there is a problem in this field in that failures called black-bottoms are likely to occur.

Here, black areas are non-image areas (for example, between halftone dots)
(black pellicle) refers to the black spots that appear on the surface of the developer, and is caused by the developer becoming fatigued over time and the sulfite ions commonly used as preservatives decreasing, or the pH of the solution decreasing.
This phenomenon occurs noticeably when the temperature becomes high, and it impairs photographic quality.

Various methods have been known in the past to improve such black spots, but the improvement of black spots is often accompanied by a decrease in sensitivity and gamma. Until now, there was no known means of improving Kurobot without inhibiting it. As research into preventing black spots has progressed, it has been discovered that certain sensitizing dyes can prevent the occurrence of black spots without deteriorating sensitivity or gamma. It has been found that since it has a maximum absorption, if it remains in the film after the processing of development, fixing, and washing with water, residual color becomes a problem.

(Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic material with high sensitivity and ultra-high contrast using a stable developer, and a method for forming ultra-high contrast negative images using the same. It is in.

A second object of the present invention is to provide an ultra-high contrast silver halide photographic material with less occurrence of black spots and a method of forming an ultra-high contrast negative image using the same.

A third object of the present invention is to provide an ultra-high contrast silver halide photographic material with improved residual color and a method of forming an ultra-high contrast negative image using the same.

(Structure of the Invention) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and in the emulsion layer or other layer, at least one hydrazine derivative and a silver halide compound represented by the general formula (■). A silver halide photographic light-sensitive material is characterized in that it contains at least one of the following compounds, and after imagewise exposure of this light-sensitive material, it contains 0.15 mol/l or more of sulfite ions and has a pH of 10.5 to This was achieved by a method of forming an ultra-high contrast negative image using a developing solution of No. 12.3.

General formula (II) -LD In the formula, C and D may be the same or different and represent a five- or six-membered nitrogen-containing heterocyclic group, and L represents a non-conjugated divalent linking group, provided that C, D or L has at least one M group.

The compound of general formula (If) of the present invention exhibits the effect of significantly improving black spots without inhibiting the effects of exacerbation and ultra-high contrast caused by hydrazine derivatives.

In addition, we have softened the halftone gradation and improved the reversibility, etc.
It turned out that it had an unexpected effect.

The -i formula (II) ψ compound is preferably added to the same layer as the hydrazine derivative, but may be added to separate layers.

Next, the hydrazine derivative used in the present invention is preferably one represented by the following general formula (1).

General formula <r> Re R1 In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxy group. represents a carbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfaniyl group, or a heterocyclic group, and Re and R+ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

However, B, R1 and the nitrogen atom to which they are bonded may form a hydrazine partial structure -N-C.

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

-i In formula (1), the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms, and the alkyl group may be an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

For example, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group,
Examples include a tetrahydrofuryl group and a morpholino group.

The aromatic group represented by the general formula CA is a monocyclic or bicyclic ring group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic ring group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Among the isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc., those containing a benzene ring are preferred.

Particularly preferred as A is an aryl group.

The aryl group or unsaturated heterocyclic group of A may have a substituent. Typical substituents include a linear, branched or cyclic alkyl group (preferably one with 1 to 20 carbon atoms) , aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), alkoxy group (
(preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), Sulfonamide group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

A in general formula (1) may have a ballast group, which is commonly used in immobile photographic additives such as couplers, incorporated therein; It is a relatively inert group, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like.

A in general formula (1) may have a group incorporated therein that enhances adsorption to the silver halide grain surface.
Examples of such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and U.S. Pat. No. 4,385,108, U.S. Pat.
No., JP-A-59-195.233, JP-A No. 59-200,
No. 231, No. 59-201,045, No. 59-201
．． No. 046, No. 59-201.047, No. 59-20
No. 1.048, No. 59-201,049, Patent Application No. 1983
-36,788, 60-11459, 60-1
Examples include groups described in No. 9739 and the like.

B specifically represents a formyl group, an acyl group (acetyl group,
propionyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, 4-chlorobenzoyl group, pyruvoyl group, methoxalyl group, methyloxamoyl group, etc.)
, alkylsulfonyl groups (methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl groups (
benzenesulfonyl group, etc.), alkylsulfinyl group (
methanesulfinyl group, etc.), arylsulfinyl group (
benzenesulfinyl group, etc.), carbamoyl group (methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (dimethylsulfamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (
phenoxycarbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl group (
methoxysulfonyl group, ethoxysulfonyl group, etc.), thioacyl group (methylthiocarbonyl group, etc.), thiocarbamoyl group (methylthiocarbamoyl group, etc.), or heterocyclic group (pyridine ring, etc.).

Particularly preferable B is a formyl group or an acyl group.

-a B in formula (1) is R, and the nitrogen atom to which these are bonded together with the partial structure of hydrazone -N=(,"
may be formed.

R1 In the above, R2 represents an alkyl group, an aryl group, or a heterocyclic group, and R5 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Ra and Rr are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfnyl group (preferably a phenylsulfonyl group, or a sum of Hammett's substituent constants -
0.5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a 2111 substituted so that the sum of Hammett's substituent constants is -0.5 or more) Benzoyl group, or straight chain, branched or cyclic unsubstituted and substituted aliphatic acyl group (
Examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )) Re and Rr are most preferably hydrogen atoms.

Specific examples of the compounds represented by -m2〇〇 are shown below, however, the present invention is not limited to the following compounds.

! -2tHs! -6 S CHyoCH* CHt SH ■-10 ■-11 1-1'2 ■-15 SH ■-16 SH ■-18 ! -21 ■-22 C Fuji Hs ■-23 COOHO ■-24 ■-25 ■-26 ■-27 1-2'8 ■-29 ■-32 Hs ■-33 ■-34 General formula used in the present invention ( The method for synthesizing the compound represented by 1) is described in JP-A-53-20.921, JP-A No. 53-20,
No. 922, No. 53-66.732, No. 53-20,3
No. 18, U.S. Patent No. 4,459.347, U.S. Patent No. 4,47
No. 8,928, etc.

Next, the compound represented by the general formula (I[) used in the present invention will be explained.

General formula (n) -LD In the formula, C and D may be the same or different and represent a five- or six-membered nitrogen-containing heterocyclic group, and L represents a non-conjugated divalent linking group, provided that C, D, or L has at least one acid group.

As the five-membered or six-membered nitrogen-containing heterocyclic group of C and D,
Examples include heterocycles consisting of a combination of nitrogen, oxygen, sulfur, selenium, tellurium, and carbon. These may further be fused with an aromatic ring or a heterocycle.

The heterocycles of C and D are preferably heterocyclic nuclei possessed by cyanine dyes or merocyanine dyes, such as thiazole nuclei, thiazoline nuclei, thiazolidine nuclei, benzothiazole nuclei, benzothiazoline nuclei, naphthothiazole nuclei, naphthothiazoline nuclei, Oxazole nucleus, oxazoline nucleus,
Oxazolidine nucleus, benzoxazole nucleus, benzoxazoline nucleus, naphthoxazole nucleus, naphthoxazoline nucleus, imidazole nucleus, imidacilline nucleus, imigzolidine nucleus, benzimidazole nucleus, benzimidacillin nucleus,
Naphthoimidazole nucleus, naphthoimidapurine nucleus, selenazole nucleus, selenazoline nucleus, selenazolidine nucleus, benzoselenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, naphthoselenazoline nucleus, pyridine nucleus, dihydropyridine nucleus, quinoline nucleus, dihydroquinoline In addition to the acidic nuclei of merocyanine dyes, such as the nucleus, pyrrolidine nucleus, indoline nucleus, tetrazole nucleus, tetrazoline nucleus, triazole nucleus, triazoline nucleus, and benzotriazole nucleus,
For example, rhodanine core, 2-thioxazoline-2,4-
Dione nucleus, 2-thioselenazoline-2,4 dione nucleus,
2-thiohydantoin nucleus, barbyl nucleation, or 2-
Examples include thiobarbir nucleation. Where possible, these may also be in the form of quaternary ammonium salts, which then have charge-balancing counterions.

These heterocyclic nuclei may have substituents.

Examples of substituents include alkyl groups (preferably those having 1 to 18 carbon atoms, such as methyl, ethyl, hexyl, isobutyl, etc.), alkenyl groups (preferably those having 2 to 18 carbon atoms) (for example, vinyl group, aryl group, butynyl group), alkynyl group (preferably one with 2 to 18 carbon atoms, such as ethynyl group, propargyl group, butynyl group, etc.), aralkyl group (preferably one with 7 to 18 carbon atoms), 20 groups, such as benzyl group)
, aromatic group (preferably one with 6 to 20 carbon atoms, such as phenyl group, naphthyl group, etc.), hydroxy group, aliphatic oxy group (alkoxy group, alkenyloxy group,
Alkynyloxy group, etc.; preferably one having 1 to 18 carbon atoms, such as methoxy group, ethoxy group, oryloxy group, propargyloxy group, butynyloxy group; aromatic oxy group (preferably 6 to 20 carbon atoms); (e.g., phenyloxy group), halogen atoms (e.g., fluorine, chlorine, bromine, iodine, etc.), amino groups,
Substituted amino group (preferably one with 1 to 18 carbon atoms,
For example, methylamino group, dimethylamino group, hexylamino group, phenylamino group, etc.) Aliphatic thio group (preferably one having 1 to 18 carbon atoms, such as methylthio group,
hexylthio group, etc.), aromatic thio group (preferably one with 6 to 20 carbon atoms, such as phenylthio group),
Acyloxy group (preferably one with 1 to 18 carbon atoms, such as an acetoxy group or a benzoxy group), sulfonyloxy group (preferably one with 1 to 18 carbon atoms, such as a methanesulfonyloxy group or a toluenesulfonyloxy group) etc.), acylamino group (preferably 1 carbon number)
1 to 18 carbon atoms, such as an acetylamino group or a benzoylamino group), a sulfonylamino group (preferably one having 1 to 18 carbon atoms, such as a methanesulfonylamino group or a benzenesulfonylamino group), or a carboxyl group. , aliphatic oxycarbonyl group (preferably carbon number 1
to 18 carbon atoms, such as a methoxycarbonyl group or a butyloxycarbonyl group), an aromatic oxycarbonyl group (preferably one having 7 to 20 carbon atoms, such as a phenoxycarbonyl group), an acyl group (preferably a carbon 1 to 20 carbon atoms, such as formyl group, acetyl group, benzoyl group, etc.), carbamoyl group, N-9-substituted carbamoyl group (preferably 2 to 20 carbon atoms, such as N-methylcarbamoyl group, N-isobutylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfamoyl group, N-fftA sulfamoyl group (preferably one having 1 to 18 carbon atoms, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group) moyl group, N-butynylsulfamoyl group, N-phenylsulfamoyl group, etc.), sulfo group, cyano group, ureido group, substituted ureido group (preferably one having 2 to 20 carbon atoms, e.g.
-methylureido group, 3-allylureido group, 3-phenylureido group, etc.), substituted urethane groups (preferably those having 2 to 20 carbon atoms, such as methoxycarbonylamino group, cyclohexyloxycarbonylamino group, phenoxy carbonylamino group, etc.), carbonate ester group (
Preferably, a group having 2 to 20 carbon atoms, such as an ethoxycarbonyloxy group, an oxycarbonyloxy group, a phenoxycarbonyloxy group, a nitro group, or a substituted or unsubstituted imino group (preferably one having 18 or less carbon atoms) Examples include N-methylimino group, N-phenylimino group, etc.).

Furthermore, the above-mentioned substituents may be further substituted with these substituents. Regarding preferable examples of the heterocyclic nucleus of C and D, examples of the benzothiazole nucleus include benzothiazole, 4-chlorobenzothiazole, 5 -chlorobenzothiazole, 6
-chlorobenzothiazole, 7-chloror:1hensothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6
-Bromobenzothiazole, 5-iodobenzothiazole/5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5-propoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxy Carbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5-trifluoromethylbenzothiazole, 5.6-dimethylbenzothiazole, 5-hydroxy-6-methyl Benzothiazole, etc., as naphthothiazole core, for example, naphtho(2
, 1-d) thiazole, naphtho(1,2-d)thiazole, naphtho(2,3-d)thiazole, 5-methoxynaphtho(1,2-d)thiazole, 7-nitoxynaphtho(
2,1-d) Thiazole, 5-methoxynaphtho(2,3
-d) thiazole, etc., and examples of the benzoselenazole core include benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-ethoxybenzoselenazole, 5- Hydroxybenzoselenazole, 5-chloro-6-methylbenzoselenazole, etc., as the naphthoselenazole core, for example, naphtho(1,2-d)selenazole, naphtho(2,1-d)selenazole, etc.
Examples of the thiazole nucleus include thiazole nucleus, 4-methylthiazole nucleus, 4-phenylthiazole nucleus, and 4.5-
Examples of the thiazoline nucleus include dimethylthiazole nucleus, 4,5-diphenylthiazole nucleus, and the like, and examples of the thiazoline nucleus include thiazoline nucleus and 4-methylthiazoline nucleus. Furthermore, examples of the benzoxazole nucleus include benzoxazole nucleus, 5-chlorobenzoxazole nucleus, 5-methylbenzoxazole nucleus, 5-bromobenzoxazole nucleus, 5-fluorobenzoxazole nucleus, 5-phenylbenzoxazole nucleus, 5-methoxy Benzoxazole nucleus, 5-ethoxybenzoxazole nucleus, 5-trifluoromethylbenzoxazole nucleus, 5-hydroxybenzoxazole nucleus, 5-carboxybenzoxazole nucleus, 6-methylbenzoxazole nucleus, 6-chlorobenzoxazole nucleus , 6-medoxybenzoxazole nucleus, 6-hydroxybenzoxazole nucleus, 5,6-dimethylbenzoxazole nucleus, etc. Naphthoxazole nucleus includes, for example, naphtho(2,1-d)oxazole nucleus, naphtho(1, 2-d) Oxazole nucleus, naphtho (
2,3-d) Oxazole nucleus, 5-methoxynaphtho(1
, 2-d) oxazole nucleus, etc.

Furthermore, as the oxazole nucleus, for example, oxazole nucleus,
4-methyloxazole nucleus, 4-ethyloxazole nucleus, 4-phenyloxazole nucleus, 4-benzyloxazole nucleus, 4-methoxyoxazole nucleus, 4.5-dimethyloxazole nucleus, 5-phenyloxazole nucleus or 4
-Methoxyoxazole nucleus, etc., and examples of pyridine nucleus include 2-pyridine nucleus, 4-pyridine nucleus, 5-methyl-
2-pyridine nucleus, 3-methyl-4-pyridine nucleus, etc.
Or as a quinoline nucleus, for example, 2-quinoline nucleus, 4-
Quinoline nucleus, 3-methyl-2-quinoline nucleus, 5-ethyl-2-quinoline nucleus, 6-methyl-2-quinoline nucleus, 8-
Fluoro-4-quinoline nucleus, 8-chloro-2-quinoline nucleus, 8-fluoro-2-quinoline nucleus, 6-medoxy 2
-quinoline nucleus, 6-nitoxy-4-quinoline nucleus, 8-chloro-4-quinoline nucleus, 8-methyl-4-quinoline nucleus,
Examples include 8-methoxy-4-quinoline nucleus.

Furthermore, selenazoline nuclei (e.g., 4-methylselenazoline, 4-nitroselenazoline, 4-phenylselenazoline, etc.), 3,3-dialkylindoline nuclei (e.g., 3,3-dimethylindoline, 3,3-diethylindoline, etc.), 3.3-dimethyl-5-cyanoindoline,
3,3-dimethyl-6-nitroindoline, 3,3-dimethyl-5-nitroindoline, 3,3-dimethyl-5
-methoxyindoline, 3,3-dimethyl-5-methylindoline, 3,3-dimethyl-5-chloroindoline, etc.), selenazolidine core (e.g. selenazolidine, 4
-methylselenazolidine, 4-phenylselenazolidine, etc.), benzoselenazoline core (e.g., benzoselenazoline, 5-chlorobenzoselenazoline, 5-nitrobenzoselenazoline, 5-methoxybenzoselenazoline,
5-hydroxybenzoselenazoline, 6-nitrobenzoselenazoline, 5-chloro-6-nitrobenzoselenazoline, etc.), naphthoselenazoline core (for example, naphtho(
2,1-d) selenazoline, naphtho(1,2-d) selenazoline, etc.), naphthothiazoline cores (e.g., naphtho(2,1-d) thiazoline, naphtho(1,2-d) thiazoline, naphtho(2, 3-dl thiazoline, 5-methoxynaphtho(1,2-d) thiazoline, 7-nidoxynaphtho(2,1-d) thiazoline, 8-methoxynaphtho(2
,1-d) thiazoline, 5-methoxynaphtho(2,3-
d) thiazoline, etc.), thiazolidine core (e.g. thiazolidine, 4-methylthiazolidine, 4-nitrothiazolidine, etc.), oxazoline core (e.g. oxazoline,
4-methyloxazoline, 4-nitrooxazoline, 5
-Methyloxazoline, 4-phenyloxazoline, 4
5-diphenyloxazoline, 4-ethyloxazoline, etc.), benzoxazoline core (benzoxazoline, 5-chlorobenzoxazoline, 5-methylbenzoxazoline, 5-bromobenzoxazoline, 5-fluorobenzoxazoline, 5-phenylbenzoxapurine) , 5-methoxybenzoxazoline, 5-nitrobenzoxazoline, 5-trifluoromethylbenzoxazoline, 5-hydroxybenzoxazoline, 5-carboxybenzoxazoline, 6-methylbenzoxazoline, 6-chlorobenzoxazoline, 6-nitrobenzoxazoline , 6-ethoxybenzoxazoline,
6-hydroxybenzoxazoline, 5,6-dimethylbenzoxazoline, 5-ethoxybenzoxazoline, etc.), naphthoxazoline core (e.g., naphtho(2,
1-d) oxazoline, natu(1,2-d) oxazoline, naphtho(2,3-d) oxazoline, 5-nitronaphtho(2,1-d) oxazoline, etc.), oxazolidine nuclei (e.g. 4,4-dimethyl oxazolidine, etc.)
, imidacilline core (e.g., 1-alkylimidacilline, l-alkyl-4-phenylimidacilline, 1-oriri-imidazoline, etc.), benzimidacilline core (e.g., 1-alkylbenzimidacillin, 1 -alkyl-5
-chlorobenzimidacillin, 1-alkyl-5,6-
Cyclolobenzimidazoline, 1-alkyl-5-methoxybenzimidacillin, 1-alkyl-5-cyanobenzimidacillin, 1-alkyl-5-fluorobenzimidacillin, 1-alkyl-5-trifluoromethyl Benzimidacillin, l-allyl-5,6-cyanobenzimidacillin, 1-allyl-5-chlorobenzimidacillin, 1-ori-rubenzimidazoline, 1-ori-ru-5-chlorobenz imidacillin, 1-aryl-
5,6-cyanobenzimidacillin, 1-okori-ru 5
-methoxybenzimidacillin, 1-aryl-5-cyanobenzimidacillin, etc.), naphthimidacillin core (e.g., 1-alkylnaphtho(1,2-d) imidacilline, 1-arylnaphtho(1,2 -d) imidacillin, etc.), the alkyl mentioned above is especially one with 1 to 8 carbon atoms,
For example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, and hydroxyalkyl groups (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.) are desirable. The aforementioned aryl group is phenyl,
Halogen (e.g. chloro) substituted phenyl, alkyl (
for example methyl) substituted phenyl, alkoxy (e.g. methoxy) substituted phenyl, etc.), pyrrolidine nucleus (
(e.g. 2-pyrrolidine), dihydropyridine nucleus (e.g. 1,4-dihydropyridine, 5-methyl-1゜2-
dihydropyridine, 3-methyl-1,4-dihydropyridine, etc.), dihydroquinoline core (e.g., 1,4-dihydroquinoline, 3-methyl-1,2-dihydroquinoline, 5-ethyl-1,2-dihydroquinoline, 6 -Methyl-1,2-dihydroquinoline, 6-nitro-1,2-
Dihydroquinoline, 8-fluoro-1,2-dihydroquinoline, 6-medoxy 1,2-dihydroquinoline, 6
-Hydroxy-1,2-dihydroquinoline, 8-chloro-1,2-dihydroquinoline, 6-nitoxy-1,4-
Dihydroquinoline, 6-nitro-1,4-dihydroquinoline, 8-chloro-1,4-dihydroquinoline, 8-fluoro-1,4-dihydroquinoline, 8-methyl-1,
4-dihydroquinoline, 8-methoxy-1,4-dihydroquinoline, dihydroisoquinoline, 6-nitro-1°2-isoquinoline, 6-nitro-2,3-dihydroisoquinoline, etc.).

Preferred heterocycles for C and D include benzothiazole nucleus, benzoxazole nucleus, naphthothiazole nucleus, naphthoxazole nucleus, thiazole nucleus, oxazole nucleus, benzothiazoline nucleus, benzoxazoline nucleus, thiazoline nucleus, oxazoline nucleus, benzimidazole nucleus, benz Examples include imidacilline nucleus, pyrrolidine nucleus, and pyridine nucleus.

Furthermore, when the heterocycles C and D are acidic nuclei of merocyanine dyes, rhodanine nuclei, 2-thioxazoline-2,4-dione nuclei, 2-thioselenazoline-
2,4-dione nucleus, barbyl nucleation or thiobarbyl nucleation [e.g. l-alkyl group (e.g. 1-methyl,
1-ethyl, 1-propyl, 1-butyl, etc.), 1.3
- dialkyl group (e.g. 1,3-dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl, 1,3 dicyclehexyl, 1,3-di(β-methoxyethyl), etc.), 1,3-diaryl group (e.g. 1,
3-diphenyl, 1,3-di(p-chlorophenyl),
, 1.3-di(p-ethoxycarbonylphenyl), etc.), l-sulfoalkyl groups (e.g. 1-(2-sulfoethyl), 1-(3-sulfopropyl), 1-(4-sulfobutyl), etc.), 1,3-disulfoalkyl group (e.g. 1,3-di(2-sulfoethyl), 1,3-di(3-
sulfopropyl), 1,3-di (such as 4-sulfocyclohexyl), 1,3-di (sulfoaryl group (such as 1,3-di (4-sulfophenyl)), or 1-sulfoaryl group (such as 1,3-di (4-sulfophenyl)), Examples include barbyl nucleus or thiobarbyl nucleus containing 1-(4-sulfophenyl), etc.), or thiohydantoin nucleus.

Among these acidic nuclei, rhodanine nuclei or thiohydantoin nuclei are preferred, and rhodanine nuclei are more preferred.

L is a nonconjugated divalent linking group. Here, non-conjugate means
This means that the heterocycles C and D are not bonded through a conjugated system of π electrons (for example, cyanine dyes and merocyanine dyes). The divalent linking group represented by L includes C, N, S
, O, or an atomic group.

Specifically, L includes, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -3-
, -NH-, -N-, -Co-.

or -5OW-<these groups may have a substituent) alone or in combination of two or more. More specifically, as L, for example, (11 alkylene group (preferably one having 1 to 12 carbon atoms, such as methylene group, ethylene group, trimethylene group, tetramethylene group, etc.), (2) alkynylene group (
Preferably, those having 2 to 12 carbon atoms, such as vinylene group and butenylene group, +31 alkynylene group (preferably those having 2 to 12 carbon atoms, such as ethynylene group,
(51-0-1+61-3-1 (7
)-NH-1(81-N-1(91-Co-1Ql-3
O, -, etc., and as a combination of these, for example, αn-
n-c-1Qa-NH-C-1α31- N HSO
t-1Q41-0-CNH-1α'9-NHCNH-5
αl-NH30t NH-2 and (an appropriate combination of (11 to +41 and +51 to O1 (for example, -(alkylene)-CNH-1 -(arylene)-3Ow NH-1 -(arylene)-NHCNH-, etc.) can give.

Examples of the acid groups possessed by C, D and L include those that can dissociate into anions during development. Some examples have already been mentioned as substituents for C, but to explain in more detail, for example, sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, sulfinic acid groups, sulfamino groups, phosphinic acid groups, sulfuric acid monomers, etc. Examples include an ester group, a sulfonamide group, a sulfamoyl group, a hydroxyimino group, a hydroxyaminocarbonyl group, a sulfinamide group, a sulfinamoyl group, and a hydroxyaminosulfonyl group.

Preferred acid groups include sulfonic acid groups, carboxylic acid groups,
It is a phosphonic acid group, a sulfinic acid group, a sulfamino group, or a sulfuric acid monoester group, more preferably a sulfonic acid group, a carboxylic acid group, or a phosphonic acid group, and most preferably a sulfonic acid group.

These acid groups may be in the form of acid anions, in which case they may have suitable cations as charge-balancing counterions, such as, for example, ammonium salts (e.g. triethylammonium or pyridinium). ) and alkali metal ions (such as sodium ions and potassium ions).

Preferred examples of the substituent having an acid group are listed below.

For example, an alkyl group substituted with a sulfo group (a sulfo group may be bonded via an alkoxy group, an aryl group, etc.) such as a 2-sulfoethyl group, 3-unphobrobyl group, 3-sulfobutyl group, 4- Sulfoptyl group, 2-(3
-sulfopropoxy)ethyl group, 2-(2-(3-sulfopropoxy)ethoxy)ethyl group, 2-hydroxy-
3-sulfopropyl group, p-sulfophenethyl group, p-
an alkyl group substituted with a carboxy group (such as a sulfophenylpropyl group) (the carboxy group may be bonded via an alkoxy group, an aryl group, etc.);

Examples include carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, etc.), sulfate alkyl group (such as 3-sulfate propyl group, 4-sulfate butyl group, etc.). Although it may be bonded to any position of C, D, or L, bonding to the nitrogen atom of the heterocyclic nucleus of C or D is particularly preferable.

When the heterocyclic nucleus of C or D forms a quaternary ammonium, any anion (e.g., bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion , perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, etc.).

However, it preferably takes the form of a betaine with an acid group (for example, a sulfoalkyl group) possessed by C, D or L, or a relatively cationic counter ion due to the presence of two or more acid groups. In particular, it is more preferable to have two or more acid groups and a cation as a counter ion.

Among the compounds of general formula (II), the following general formula (I[[)
(rV) is preferred.

General formula (I [I) In the formula, Zffl and Z3t are the heterocyclic nucleus C of the general formula (■)
and a group of nonmetallic atoms to form D, (, s′
, 1. t and L''' may be the same or different and have the same meaning as the linking group in general formula (II).p.

q is 0 or l.

General formula (IV) In the formula, Z”+ Z”l L”l L”l L”
l r and S are each zxl of general formula (III)
, zst, L31°Lat, LSI,
M L″, which is synonymous with p and q, is a cation for charge balance and is as described in general formula (II).

Specific examples of the compound represented by general formula (II) are listed below, but the invention is not limited thereto.

11-1゜ (cHt)s (cHt)s soi soi ■−2゜ CH.

50s H303H ■-3゜CHt CHt 50s CHz CH
t 50s ■-4゜CHt ■-5゜S Os S
Os■-6゜S Os S Os ■-7゜CI(! COO1(CHz C0OH(CHz C
Hz O)t (CHi CHz O)
)z (CHt)s (CHx)sS O
z S O3■-8゜(CHz)z (CHz)tCH2CH
CHCHs so= so= ■-9゜CHz C0OHCHt C00H I [-10゜n-11゜ll-12゜SCh H-N (Cx Hs) SCh H
-N (C to H4)3Ir-13°C0OHC00H U-14°ll-15°ll-16° The compounds of the present invention can generally be synthesized with reference to the following literature.

(1) A. Heissberger and E.
C.Taylorg “The Chess+1 try
of Heterocyclic Cosipoun
dsNJohn Wiley & 5ons (2
)A.

Katritzky and C.W.Ree4“Comp
rehensiveHeterocyclic Che
s+1stry, The 5structure.

Reactions, 5 synthesis and [
Ise of I (eterocyclic Compo
unds″ Pergason Press +
1984.

That is, after synthesizing the heterocyclic bis form 4, Δ is treated with various quaternizing agents (e.g., propane sultone, butane sultone, bromoacetic acid, β-bromopropion) without a solvent or in a solvent such as anisole, carbon tetrachloride, or chloroform. Breath can be synthesized by reacting with acids, etc.). It can be synthesized by reacting breath with various bases (such as pyridine, triethylamine, NaOH, etc.).

S Ox S 0s (CHz)n (CHi)nI S Ox H・(Base)z S Ox Hf
1 In the present invention, hydrazine derivatives and general formula (I
When the compound represented by I) is contained in a photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloids N (e.g., protective layer, intermediate layer, filter layer, Specifically, if the compound used is water-soluble, it may be contained in an aqueous solution, or if it is poorly water-soluble, it may be mixed with water such as alcohols, esters, ketones, etc. It can be added to a hydrophilic colloid solution as a solution of an organic solvent that can be used.When added to a silver halide emulsion layer, it can be added at any time from the start of chemical ripening to before coating, but after the completion of chemical ripening. It is preferable to add it between then and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The content of the hydrazine derivative of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of antifogging compound, etc. It is desirable to select the optimal amount depending on the situation, and testing methods for its selection are known to those skilled in the art (usually and preferably from 10-h mol to 1X10-' mol per mol of silver halide, In particular, it is used in a range of 10@-5 to 4.times.10@-1 moles.

In the present invention, the compound represented by the general formula (II) can be added in the same manner as the above-mentioned hydrazine derivative, and the compound may be added in an amount of 1×10-' mol to 1X10-'' mol per 1 mol of silver halide. Preferably especially lXl0
-' to 2.0 x 10-' moles are preferred.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc., but the content of silver iodide should be 10 mol% or less, especially It is preferably 0.1 to 5 mol%.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
There is basically no limit to the zero particle size distribution, which is preferably 5 μm or less, but it is preferably monodisperse. Monodisperse herein refers to a particle group that is small in weight or number of particles (95% of which is within ±40% of the average particle size).

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) crystals, or a composite form of these crystal forms.

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

Two or more silver halide emulsions formed separately may be used in combination.

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.

Silver halides particularly suitable for use in the present invention are those prepared in the presence of 10 to 10 moles of iridium salt or complex salt per mole of silver, and whose silver iodide content on the grain surface is lower than the grain average iodine content. It is silver haloiodide with a higher content than silver oxide. When an emulsion containing such a silver haloiodide is used, photographic characteristics with a higher frequency range and higher gamma can be obtained.

In the above, it is desirable to add the iridium salt in the above amount before the completion of physical ripening in the silver halide emulsion manufacturing process, particularly during grain formation.

The iridium salts used here are water-soluble iridium salts or iridium complex salts, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (I[[), potassium hexachloroiridate (mV), hexachloroiridate (I[[)], and potassium hexachloroiridate (mV). ) acid ammonium, etc.

The silver halide emulsion in the light-sensitive material used in the present invention is
One type may be used alone, or two or more types (for example, those with different average particle sizes, those with different halogen compositions, those with different crystal habits, and those with different chemical sensitization conditions) may be used in combination.

Further, the silver halide emulsion layer may be a single layer, or may be a heavy Ji! In the case of zero layers (which may be two layers, three layers, etc.), different silver halide emulsions may be used, or the same one may be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of imidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized (although it may be chemically sensitized). Chemical sensitization methods and noble metal sensitization methods are known, and any of these methods may be used alone or in combination for chemical sensitization.

Among the noble metal enhancement methods, the gold sensitization method is a typical one, and uses a gold compound and a total complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium.
No. 0, British Patent No. 618.061, etc.

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. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, No. 278.947, No. 2,410,689, No. 2,
No. 728,668, No. 3,501,313, No. 3.6
56. It is described in No. 952.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include U.S. Pat. No. 2,487,850,
2,518.698, 2゜983.609, 2,9
83.610 and 2°694.637.

The light-sensitive materials used in the present invention include sensitizing dyes (e.g., cyanine dyes, merocyanine dyes, etc.) can also be added. This allows spectral sensitization to be performed on the longer wavelength side than the inherent sensitivity region of silver halide.

Useful enhancing dyes, supersensitizing dye combinations, and supersensitizing substances are listed in Research Disclosure (Res.
176 @ 1
7643 (published in December 1978), page 23, item 5, ■. .

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, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; A number of compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.; Among these, preferred are benzotriazoles (e.g., 5-methyl-benzotriazole) and nitroindazoles (e.g., 5-nitroindazole); these compounds may also be included in the treatment liquid. .

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.
For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives (2,3
- dihydroxydioxane, etc.), activated vinyl compounds (
1,3゜5-Triacryloyl, -hexahydro-5-
) riazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-
6-hydroxy-5-1-riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.)
, 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.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as alkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters; Ampholytic surfactants such as amino acids, aminoalkyl-containing sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazo Cationic surfactants such as heterocyclic quaternary ammonium salts such as lithium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 1,600 or more and described in Japanese Patent Publication No. 58-9412.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant.

The photographic light-sensitive material of the present invention contains hydroquinone derivatives (so-called DIR-
hydroquinone).

Specific examples thereof include U.S. Pat. No. 3,379.529, U.S. Pat. No. 3,620.746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Japanese Unexamined Patent Publication No. 49-1
29,536, JP 54-67.419, JP 56-153.336, JP 56-153,342
No., Patent Application No. 59-278,853, No. 59-9043
Examples include compounds described in No. 5, No. 59-90436, and No. 59-138808.

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 light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid. , methacrylic acid, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (methacrylate, styrene sulfonic acid, etc.) can be used as a monomer component.

In the light-sensitive material of the present invention, a compound such as an acid polymer or a reductone may be included in the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer for the purpose of preventing black spots.

A preferred acid polymer is an acid polymer latex copolymerized with acrylic acid or methacrylic acid monomers.

Preferred reductones are ascorbic acid and its derivatives.

The developing agent used in the developer used in the present invention is not particularly limited, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydrobutylone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-3-virapritone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethy7L/-3-pyrazolidone, -Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3- Pyrazolidone, 1-p-
Examples include tolyl-4,4-dimethyl-3-pyrazolidone.

Examples of p-aminophenol developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl>-p-aminophenol, and N-(4-hydroxyphenyl)glycine). ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/l to 0.8 mol/l, and a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is also preferred. When using the former, set it to 0.
05 mol/l~0゜5 mol/! , the latter 0.06 mol/
It is preferable to use it in an amount of 1 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. Sulfite is 0.4 mole/! The above is particularly preferably 0.5 mol/l or more, and the upper limit is preferably 2.5 mol/l.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
The pH of the developer, including the H adjuster and buffer, is 10.5.
It is set between 12.3 and 12.3.

Additives used in addition to the above components include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dinchylformamide, and methyl Organic solvents such as cellosolve, hexylene glycol, ethanol, and methanol; antifoggants such as indazole compounds such as 1-phenyl-5-mercaptotetrazole and 5-nitroindazole; and penttriazole compounds such as 5-methylbenztriazole; It may also contain a black pepper inhibitor, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-10
It may also contain the amino compounds described in No. 6244.

The developing solution of the present invention contains a silver stain preventive agent.
, No. 347 can be used. Patent application 1986-109, 1974 as a solubilizing agent added to the developer.
The compound described in No. 3 can be used, and the compound described in JP-A No. 60-93, 4 can be used as a pHff1 buffer for use in the developer.
Compounds described in No. 33 or Japanese Patent Application No. 61-28708
Compounds described in this issue can be used.

As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain water-soluble aluminum (e.g. aluminum sulfate, light bread, etc.) as a hardening agent, where the amount of water-soluble aluminum salt is usually 0.4 to 2.0.
g-Ag/l. Furthermore, a trivalent iron compound can also be used as an oxidizing agent in the form of a complex with ethylenediaminetetraacetic acid.

The processing temperature is usually selected between 18°C and 50°C, more preferably between 25°C and 43°C.

(Examples) Next, the present invention will be described in more detail based on Examples.

Example 1 Silver nitrate aqueous solution and potassium bromide potassium iodide aqueous solution,
A monodispersed cubic silver iodobromide emulsion A (1.2 mol% iodide, 98 mol silver bromide) was prepared by mixing in the presence of ammonia by a double jet method while maintaining lllAg at 769. %)made. Apart from this, 6
A silver bromide aqueous solution and a potassium bromide aqueous solution were mixed in the presence of ammonia by a double jet method while maintaining pAg at 7°9 to prepare a monodisperse cubic silver bromide emulsion B with an average grain size of 0.35 μm. . Emulsion A was further sulfur sensitized with sodium thiosulfate.

In addition, for both emulsions A and B, the sensitizing dye r5,5'-dichloro-3,3'-di(3-sulfopropyl)-9-ethyl-oxacarbocyanine sodium salt. LtNs)3
bUs.

6 per mole of silver for emulsions A and B, respectively.
Addition of X10-'mol and 4.5X10-'mol caused spectral deterioration.

Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,
3,3a,? - Tetrazaindene was added.

These emulsions A and B were mixed in a silver halide weight ratio of 6:4, and the above-mentioned aggravating dye (indicated as A in the table) was further added as shown in Table 1. or a compound represented by the general formula (II) of the present invention was added.

Furthermore, 0.5810-'' mol of a hydrazine derivative represented by the following formula was added per mol of silver.

Further, an alkylbenzene sulfonate as a surfactant and a vinyl sulfone hardener as a hardening agent were added to adjust the pH of the emulsion to 5.8, and the film thickness was 10.
on a 0 micron polyethylene terephthalate support.
Each of the emulsions prepared above was coated to give a coated silver of 13.3 g/ft, and a protective layer of gelatin was coated on top of the emulsion to give a coated silver of 1 g/ft.
1 to (22) were created.

Each of these samples was exposed to tungsten light at 3200° for 5 seconds through an optical wedge for sensitometry, developed for 30 seconds at 38°C with a developer having the following composition, fixed, washed with water, and dried. (For the development process, an automatic processor FC-660F manufactured by Fuji Photo Film Co., Ltd. was used.) Basic formulation of developer Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 13. 0g potassium triphosphate 74.0g potassium sulfite
90.0g ethylenediaminetetraacetic acid tetrasodium salt 1.0g potassium bromide 4.0g 5-methylbenzotriazole 0.6g 3-diethylamino-1,
Table 1 shows the photographic characteristics of each sample obtained by adding 15.0 g of 2-propanediol water.

Relative sensitivity is expressed as a relative value of the exposure i111ogE value giving a density of 1.5. To evaluate the level of black spots, observe the size and number of black spots that have occurred in the unexposed areas of the sample using a 25x looper. For residual color, a sample was separately developed at 38°C for 20 seconds, and the color of the unexposed area was visually evaluated.

As can be seen from the results in Table 1, when the compound of the present invention is used, the black spot level is significantly improved.

The spectral sensitizing dye 5,5'-dichloro-3,3'-di(3
-Sulfopropyl)-9-ethyl-oxa, carbocyanine (λmax 550 nm) can be added in an increased amount to improve the black spot level, but the residual color worsens. On the other hand, the compound of the present invention used instead of additionally adding the above-mentioned spectral sensitizing dye had good residual color.

Furthermore, the compound of the present invention used here has an absorption maximum substantially in the visible region, and does not have the function of spectral sensitization in long wavelengths. It was not at a level that would pose a problem.

Table 1 (l) Example 2 Silver iodobromide emulsion A' (iodide 1i11 mol%, bromide!!99 In place of Emulsion B, a monodispersed cubic silver bromide emulsion B' having an average grain size of 0.3 μm and not subjected to chemical sensitization was used.

As a sensitizing dye, 5°5' was used instead of the sensitizing dye of Example 1.
-diphenyl-3,3'-di(3-sulfobutyl)-9
-Ethyl-oxacarbocyanine sodium salt (λma
x 550 nm) was added to emulsions A' and B' in an amount of 3.5 x 10-' mole per mole of 8 emulsions for spectrally sensitization.

Other than that, as in Samples 5 to 19 of Example 1, the compound of the present invention was further added and tested, and as in Example 1,
When Sanapuru of the present invention was used, the level of black spots was significantly improved. Further, even after processing at 38° C. for 20 seconds, residual color remained good.

Example 3 Silver nitrate aqueous solution and potassium bromide potassium iodide aqueous solution were mixed by double jet method in the presence of ammonia while keeping pAg at 7.9 to iodobromide monodisperse cubes with an average particle size of 0.2 microns. Silver emulsion C (silver iodide 2 mol%, silver bromide 98 mol%) was prepared.

Next, the exacerbating dye r5,5'-dichloro-3,3'-di(
3-Sulfopropyl)-9-ethyl-oxacarbocyanine sodium salt,! per 11 moles, 5.0X1
0-'mol was added for spectrally sensitization.

Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,
3,38,7-chitrazaindene was added.

Compound 11-6 of the present invention at 5.0XIO per mole of silver
-' mol was added, and then the following nucleating agent and nucleation accelerator were added, 0.2 x 10-' mol/Ag mol 3.9 x lO-' mol/Ag mol 3, OX 10-' mol/ Ag mole and 5-methylbenzotriazole 18/rd
.

4, 5*/rrr polyethyl acrylate 0.8 g/ld was added, 1,3-vinylsulfonyl-2-propertool was added as hardener, 3.0 g/r on the polyester support.
It was applied so that it became Agff1 of A. The coating amount of gelatin was 1.8*/rrr.

On top of this, as a protective layer, ascorbin 926 / d, polymethyl methacrylate (particle size 2.5μ) 70 / d
As a surfactant, C?H? Gelatin 1.5g/n? was applied.

It was exposed and developed in the same manner as in Example-1.

There were no black spots and little residual color.

(Effects of the Invention) The photosensitive material of the present invention has a remarkable high sensitivity and is effective for reproducing halftone images and line drawings by using a combination of at least one hydrazine derivative and at least one compound represented by (II). You can obtain characteristics with high contrast and less black spots.

Further, according to the present invention, the halftone gradation can be made softer.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Display of the incident Showa JJ year patent application No.-24'ri6
Relationship with Kota No. 36 Amendment Person Case Patent Applicant Embassy Office 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of “Detailed Description of the Invention” in the specification, “Invention” in the description of the contents of the amendment The description in the section "Detailed explanation of" has been amended as follows.

1) Page 3, line 3 "Parts" "photograph" and correct it.

2) Page J', line 2 "Hydrazine" "Hydrazone" and correct it.

3) Structural formula of page 1/-/r " ” and correct it.

4) Second! page 10th line "Aryl group" "Allyl group" and correct it.

5) Put the λth on the 7th line of the page. "Oxycarbonyloxy group Jt- "Butoxycarbonyloxy group" and correct it.

6) Page 3r, line 10 "dicyclohexyl" "Dicyclohexyl" and correct it.

7) Substitute the structural formula of page 11-70 for Part V. [ and correct it.

8) Number 7! Page l! row "Sanapur" "S/pull" and correct it.

Claims (2)

[Claims] (1) It has at least one silver halide emulsion layer on a support, and contains a hydrazine derivative and a compound represented by general formula (II) in the emulsion layer or other layers. A silver halide photographic light-sensitive material. General formula (II) C-L-D In the formula, C and D may be the same or different and represent a five- or six-membered nitrogen-containing heterocyclic group, and L represents a non-conjugated divalent linking group. . However, C, D or L has at least one acid group. (2) It has at least one silver halide emulsion layer on the support, and contains a hydrazine derivative and at least one compound represented by the following general formula (II) in the emulsion layer or other layers. After imagewise exposure of a silver halide photographic light-sensitive material consisting of A method for forming a high contrast negative image. General formula (II) C-L-D In the formula, C and D may be the same or different and represent a five- or six-membered nitrogen-containing heterocyclic group, and L represents a non-conjugated divalent linking group. However, C, D or L has at least one acid group.