JPH02214850A - Negative type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and contrast in an image and to reduce pressure sensitization by incorporating a hydrazine derivative and a specified compound in a silver halide emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The silver halide emulsion layer or another hydrophilic colloidal layer contains the hydrazine derivative or the compound represented by formula I in which R1 is sulfoalkyl, carboxyalkyl, sulfoaralkyl, or carboxyaralkyl; R2 is optionally substituted alkyl or aryl group; R3 is -(CH2)n1CONH(CH2)m1OH or -(CH2)n2O(CH2)m2OH; and W is H, halogen, phenyl, or the like, thus permitting sensitivity and contrast in an image to be enhanced, and pressure desensitization to be reduced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material that provides a high contrast photographic image, and more particularly relates to a silver halide photographic light-sensitive material that provides a high-contrast photographic image. This paper relates to improvements in contrast enhancement technology.

(Prior art) In the field of graphic arts, characters, line images,
Alternatively, an image forming system exhibiting high contrast photographic characteristics is used to form a half-tone photographic image.

For example, high silver chloride content (at least 50 mol%)
A photosensitive material consisting of a well-organized silver chlorobromide emulsion (as described above) with an average grain size of approximately 0.3 μm is processed using a developer containing hydroquinone as a developing agent and having a low concentration of sulfite ions (referred to as a Lith developer). By processing, images with high contrast can be formed. This is known as an image forming system using lithographic development.

However, since the lithium developer has an extremely low concentration of sulfite ions, it is susceptible to air oxidation, and therefore has the disadvantage that it is extremely difficult to maintain stability as a developer.

In addition, systems that stably form high-contrast images by processing with a developer with a high sulfite ion concentration are disclosed in U.S. Pat. .742, 4.311,781
No. 4.272606, No. 4.211.857
No. 4゜243.739, etc.

This method uses a silver halide photographic material containing a hydrazine derivative. According to this method, it is permissible to add sulfite at a progeny concentration to the developer, so that stable processing can be performed with enhanced preservation.

On the other hand, light sources used to expose photographic light-sensitive materials include tungsten light, mercury lamp, halogen lamp, argon laser, helium neon laser, semiconductor laser, L
ED and the like have been put into practical use, and photosensitive materials have been developed that have optimal spectral sensitivity by selecting spectral sensitizing dyes based on the spectral energy distribution of these light sources.

In particular, derivatives of panchromatic sensitized silver halide emulsions and hydrazine are used as photosensitive materials to obtain images with high sensitivity and high contrast to light sources such as helium neon lasers and LEDs. A photosensitive material containing the above-mentioned compound is provided.

However, silver halide photosensitive materials containing this hydrazine derivative and sensitized with panchromatic sensitizing dyes have the characteristics of high sensitivity and being able to obtain images with high contrast; The disadvantage is that concentration increases tend to occur due to (hereinafter referred to as pressure sensitization)
It had

In other words, when photosensitive materials are subjected to contact friction, or when the emulsion-coated surface of the photosensitive material is subjected to contact friction with a different substance, the development process causes defects in non-image areas depending on the pattern and strength of the contact friction. It has been desired to develop a photosensitive material that does not cause such problems because fixed images tend to occur.

Furthermore, when a hydrazine derivative and a panchromatic sensitizing dye are contained in a light-sensitive material, there is a drawback that the sensitivity fluctuates greatly under conditions such as long-term storage or high temperature conditions.

[Purpose of the invention]

Therefore, an object of the present invention is to form an image with high sensitivity and high contrast in a silver halide photosensitive material containing a hydrazine derivative and color sensitized with a panchromatic sensitizing dye, and to provide a silver halide photosensitive material containing a hydrazine derivative and having less pressure sensitization. An object of the present invention is to provide a silver-oxide photosensitive material.

Another object of the present invention is to provide a silver halide photosensitive material with excellent storage stability.

The object of the present invention is to provide a silver halide photographic light-sensitive material containing a silver halide emulsion color-sensitized with a panchromatic sensitizing dye, in which a hydrazine derivative is contained in the silver halide emulsion layer or other hydrophilic colloid layer. This was achieved by including a compound represented by general formula (I).

General formula (I) where R is a sulfoalkyl group, a carboxyalkyl group,
Represents a sulfoaralkyl group or a carboxyaralkyl group.

R2 represents a substituted or unsubstituted alkyl group or aryl group.

R3 is -(CH2), cONII(CH2)IIIOH
, or (CHz)-zO(CI+2)ffi2011
m I , In 2 , n 1 and R2 each represent an integer of 1 to 7.

However, m, +n, and m2+n2 are each 8 or less.

W represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, or a phenyl group.

Examples of the sulfoalkyl group represented by R1 in general formula (I) include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfopropyl group, and 3-sulfopropyl group.
-Sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-acetoxy-3-sulfopropyl group, 2-hydroxy-3-(3'-sulfopropoxy)propyl group, etc. represented by R1 Examples of the carboxyaralkyl group include a carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, and 2-(2-carboxyethoxy)ethyl group.

In addition, as the sulfoaralkyl group represented by R5, p
-sulfobenzyl group, p-sulfophenethyl group, etc. Examples of the carboxyaralkyl group include p-carboxybenzyl group.

The substituted or unsubstituted alkyl group represented by R2 includes methyl group, ethyl group, propyl group, butyl group, 2-
Examples include hydroxyethyl group, 3-hydroxypropyl group, benzyl group, phenylpropyl Lp-)lylprobyl group, carbamoylethyl group, cyanoethyl group, paramethoxyphenethyl group, and the like.

Examples of the substituted or unsubstituted aryl group represented by R2 include phenyl group, p-methoxyphenyl group, 2-
Examples include pyridyl group and 4-pyridyl group.

Specific examples of the compound represented by general formula (I) are shown below. However, the invention is not limited to these specific examples.

(CF12) 5sO3Na lh (CHg) a30aK H3 I-7 ■ (CHHz)3COOH 2H5 ■-11 ■ CH.

(1)-13 General formula (II) The compound represented by general formula (I) is preferably used in a silver halide emulsion in an amount of 10<-6> to 10<-1> mol per 1 mol of silver. Particularly preferably 1×10-5 to 5×1
It is in the range of 0-3 moles.

Next, examples of the panchromatic sensitizing dye used in the present invention include compounds represented by the general formula (formula).

(Xo).

In the formula, R1 and R2 may be the same or different, and each represents an alkyl group (preferably carbon number/~♂,
For example, methyl group, ethyl group, propyl group, methyl group, methyl group, heptyl group, etc.), substituted alkyl group (substituents such as carboxy group, sulfo group, cyano group, etc.)
・Rogen i atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, alkoxycarbonyl group (carbon number less than ♂, e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), Alkoxy group (2 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, p-)
(lyloxy group, etc.), aceroxy group (3 or less carbon atoms,
For example, acetyloxy group, propionyloxy group, etc.)
, acyl group (carbon number and below, e.g. acetyl group, propionyl group, hensoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, pyrrolidinocarbamoyl group, etc.), Sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group), aryl group (e.g. phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, Alkyl group (with the number of carbon atoms or less) substituted with α-naphthyl group, etc. However, one or more of these substituents may be substituted in combination with an alkyl group. ). R represents a hydrogen atom, a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), a phenyl group, or a benzyl group.

Zl and Z2 may be the same or different,
Each represents a group of nonmetallic atoms necessary to complete a J-membered or 3-membered nitrogen-containing heterocycle, such as a thiazole nucleus [e.g. benzothiazole, dark 0 rubenzothiazole, ! −
Chlorbenzothiacil, ni-Chlorbenzothia sheets 7-Chlorbenzothia sheets Goomethylbenzothiazole,! -To methylbenzothia sheets 6-methylbenzothiazole, s-bromobenzothiazole, otsuromobenzothiazole,! -iodobenzothiazole,
! -Phenylbenzothiazole, termethoxybenzothiazole, methoxybenzothiazole! - Ethoxybenzothiazole, Ocarboxybenzothiazole, Terethquin Carbonylbenzothiazole,! -Phenethylbenzothiazole, terfluorobenzothiazole-
To, 3 trifluoromethylbenzothiazole,! O-dimethylbenzothiazole! -Hydroxy O-methylbenzothiasheet to tetrahydrobenzothiazole, gouphenylbenzothiasonohenaphtho [co, /-d] thiazole, naphtho [/.

code d] thiazole, naphtho [co, 3-d:] to chia sheet ma-methoxynaphtho [/, -2-d] thiazole, 2-ethoxynaph) [J, /-d) thia G zole, and -methoxynaphtho ( Ni2./-d) thiazole, J-methoxynaphtho[x,3-d]thiazole, etc.], zelenazole core [e.g. penzozelenazole, ochlorbenzozelenazole, ! Methoxy (nzozelenazole, !-methylbenzozelenazole, termethoxybenzothiazole, naphtho[, z, /=d) zelenazole, naphtho[i, r-dl zelenazole, etc.], oxacyl nucleus [to benzoxa sheets! -Chlorbenzoxazole! -Methylbenzoxazole,! -3-fluorobenzoxazole to promobenzoxazole,
Terenylbenzoxazole, ohmethoxybenzoxazole, autotrifluorobenzoxazole,!
-Hydroxybenzoxazole,! -To Carpoxybenzoxazole B-Methylbenzoxazole, 6
Chlorbenzoxazole, 6-methylbenzothiazole, O-hydroquine benzoxacyl,! , O-dimethylbenzoxazole, ri.

- Dimethylbenzene oxasol! -ethoxybenzoxazole, naphtho[J,/-d]oxazole, naphtho[/, J-d)oxazole, naphtho[x, 3
-d) oxazole, etc.], quinoline nuclei [e.g. 2-quinoline, 3-methyl-coquinoline, terethyl-coquinoline, di-methyl-2-quinoline, ? -Fluoro-approved-quinoline, Otsu-methoxycoquinoline, Otsu-hydroxoquinoline,! - Chlorokoquinoline],
3.3-Dialkylindolenine nucleus [e.g., 33-dimethylindolenine, 33-diethylindolenine, 3
, 3-dimethyl-j-cyanoindolenine, 3,3-dimethyl-termethoxyindolenine, 3,3-dimethyl-termethylindolenine, 313-dimethyl-j-chlorindolenine, etc.], imidazole nucleus [e.g. /
-Methylbenzimidazole, /-ethylbenzimidazole, /-methyl-! -Chlorbenzimidacyl, /
-Ethyl-J-chlorobenzimidacyl, /-methyl-O, -dichlorobenzimidazole, /-ethyl=!
, ≦-cyanobenzimidazole, /-alkyl-methoxybenzimidazole, /-methyl-tercyanobenzimidazole, /-ethyl-j-cyanobenzimidazole, /-methyl-! -To fluorobenzimidazole /-ethyl-J-fluorobenzimitasole, /-phenyl ruta, O-dichlorobenzimidazole, /-allyl-j16-dichlorobenzimidazole, /-allyl ruta chlorbenzimidazole Nope /-
Phenylbenzimidazole, /-phenyl-J-chlorobenzimidazole, /-methyl-j-trifluoromethylbenzimidazole, /-ethyl-j-)lifluoromethylbenzimidazole, /-ethylnaphtho[/
2.2-d] imidazole etc.], pyridine nucleus [e.g. pyridine,! -methyl-copyridine, 3-methyl-goupyridine, etc.].

However, at least one of Zl and Z2 is a thiazole nucleus, a selenazole nucleus, or a quinoline nucleus.

X represents an acid anion.

S m, n, and p each represent and/or . When the dye has a betaine structure, p is /.

Specific examples are shown below, but the scope of the present invention is not limited to these only.

■-/) ■-2) 2H5 2H5 r ■-3) (2H5 L:2H5 ■ G ■-g) ■-? ) ■-3) ■-9) n-J) ■-7) ■ //) ■ /3) ■ /2) ■ /? ) 1-/9) ■ /the law of nature) 11-/1) (CH2)4 SO3 2H5 ■-/go) ■ 2θ) ■ 2/) ■ 2+2) 2F.

■ ■ 2g) ■-+2o) ■ ■-3θ) ■ 3/) 2H5 r ■, 26) ]1-. 27) y-, z, r) ■ [-3<7) ■ These dyes may be used alone or in combination of two or more.

Next, as the hydrazine derivative used in the present invention, a compound represented by general formula (III) is used.

General formula (III) R+ N N GI R2AIA! In the formula, R1 represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carboxyl group, or an oxycarnebonyl group, and G represents a carbonyl group. , a sulfonyl group, a sulfoxy group, a P-group, or an iminomethylene group, and A and A2 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 aryl group. Represents a sulfonyl group or a substituted or unsubstituted acyl group.

In the general formula (I[l), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. In addition, this alkyl group includes an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group,
It may have a substituent such as a carbonamide group.

The aromatic group represented by R1 in the general formula (I[[) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be monocyclic or bicyclic.
may be combined with a group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R8 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably a carbon number of 1 to 20), a substituted amino group (preferably an alkyl group having 1 to 20 carbon atoms) (amino group substituted with
), ureido groups (preferably 33-, and ureido groups having 1 to 30 carbon atoms), and the like.

-IIIQ The alkyl group represented by R2 in formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, substituted with a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group, etc. It may have a group.

The aryl group represented by R2 is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

A monocyclic group is preferable as the aryoloxy group, and examples of the substituent include a halogen atom.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
An alkylamino group or an arylamino group is preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like. The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 10 carbon atoms, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, etc.). ), aralkyl group (e.g., 0-hydroxyhensen group, etc.)
, aryl group (e.g., phenyl group, 3.5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4
(methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
dimethylamino group, etc.) are preferred.

When G1 is a sulfoxy group, R2 is preferably a cyanohensyl group, a methylthiobenzyl group, a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group, and a phenyl group are preferred, and a phenoxy group is particularly preferred.

When G is an N-3f substituted or unsubstituted iminomethylene group, R2 is preferably a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R2, in addition to the substituents listed for R1, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

G in general formula (I') is most preferably a carbonyl group.

In addition, the R2 GI R2 portion is split from the remaining molecules,
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the -G-R2 moiety, and specifically, one that can be represented by general formula (a).

General formula (a) R, -Z.

In the formula, Z nucleophilically attacks G, and GIR3Z
It is a group that can split the + moiety from the remaining molecule, and R3 is R
With one hydrogen atom gap from 2, Zl makes a nucleophilic attack on G1, and a cyclic structure can be generated with GI, R3, and Z.

More specifically, Z easily undergoes a nucleophilic reaction with 01 when the hydrazine compound of general formula (I) generates the following reaction intermediate by oxidation etc. R+ N-N GI R3ZI R, -N=N A group capable of splitting a group from 01, specifically OH, SH or NHRa (R4 is a hydrogen atom, an alkyl group, an aryl group, -COR5, or -8
O□R5, where R9 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), or a functional group that directly reacts with 01, such as COOR, (where OH, S H, N HRa-COOH is ON-R even if it is temporarily protected to generate these groups by hydrolysis with an alkali or the like.

good) or CRb CRb (R6, R1
(represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group) can react with G by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group such as

Furthermore, the ring formed by GI, R3, and Zl is preferably a 5- or 6-membered ring. Among those represented by general formula (a), preferred are those represented by general formulas (b) and (tZ).

General formula (b) (-CRb 'R, 2su1; C-=, 1 B 2, +.Rb 3Rb '<0-''''''11-R in the formula
, 4 is a hydrogen atom, an alkyl group, (preferably has 1 to 1 carbon atoms)
12) alkenyl group (preferably 2 to 12 carbon atoms)
) represents an aryl group (preferably one having 6 to 12 carbon atoms), and may be the same or different. B is an atom necessary to complete a 5-membered ring or 6-membered ring that may have a substituent, m, n is O or 1, (n0m)
is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Zl has the same meaning as in general formula (a).

General formula (C) Rc3 +N←“Fang CRc’ Rc2h Z.

In the formula, Rc1 to RC2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom,
It can be the same or different.

RC3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents 0 or 1, and q represents 1-4.

RC' to RC' and RC3 may be bonded to each other to form a ring as long as Z can make an intramolecular nucleophilic attack on G1.

Rc' and RC'' are preferably a hydrogen atom, a halogen atom, or an alkyl group, and RC3 is preferably an alkyl group or an alkyl group.

q preferably represents 1 to 3; when q is 1, p represents 1 or 2; when q is 2, p represents 0 or 1; when q is 3, p represents O or 1; or CR when 3
c′ RC” may be the same or different.

zI has the same meaning as in general formula (a).

A1 and A2 are hydrogen atoms, alkylsulfonyl groups and arylsulfonyl groups having 20 or less carbon atoms (preferably phenylsulfonyl groups or Hammett's sum of substituent constants is -0)
, 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) group, or linear, branched, or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups) .)) Hydrogen atoms are most preferred as AI and A2.

R1 or R2 in the general formula (I) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, a furkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

R or R2 in the general formula (I[[) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
U.S. Patent No. 43.85,108, U.S. Pat.
No. 59.347, JP-A No. 59-195,233, No. 5
9-200゜231, 59-201.045, 59201.046, 59-201,047, 59-201.048, 59-201.049,
JP-A-61-170,733, JP-A No. 61270.744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

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

■ ■ ■ ■ ■ ■ CI (2CH, CH25)l ■ H ■ ■ ■ H ■ ■ ■ ■ ■ ■ 2H5 ■ ■ 31〉 ■ ■ ■ II-37) Item H The hydrazine derivatives used in the present invention include the above-mentioned hydrazine derivatives. In addition to Nomotsuno, RESEARCHDISCLO3IIRE
Iten23516 (November 1983 issue, P,
346) and the references cited therein, as well as U.S. Pat.
No. 080.207, No. 4,269,929, No. 4.2
No. 76.364, No. 4,278,748, No. 4. ．． 3
85.108, 4,459,347, 4,56
0. ．． No. 638, No. 4.478928, U.S. Patent No. 2,
011,391B, JP 60-179734, JP 61-170,733, JP 61-270,744, JP 62-948, EP217. ．． No. 310, Japanese Patent Application No. 61-175.234, No. 61-251,482,
No. 61-268.249, No. 61-276-283, No. 62-67.508, No. 62-67゜529,
62-67.510, 62-58.513, 62-130.819, 62-143,469,
Those described in No. 62-166.117 can be used.

When a hydrazine derivative is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer.
It may be contained in a non-photosensitive hydrophilic colloid layer adjacent to other emulsion layers.

When adding hydrazine derivatives to these layers,
If these compounds are water-soluble, they should be added as an aqueous solution, or if they are poorly water-soluble, they should be added after being dissolved in a water-miscible organic solvent such as alcohols, esters, ketones, or glycols. Can be done.

Hydrazine derivative is 10-6 per mole of silver halide.
The content is preferably in the range of 10-1 mol, particularly 10-5 to 10-2 mol of IX.

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 70 mol% or more, especially 90 mol% or more is silver bromide. A silver halide consisting of is preferred.

The content of silver iodide is 10 mol% or less, especially 0.1 to 5 mol%
It is preferable that

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.
It is preferably 5μ or less. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles is composed of particles having a size 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.

Further, the silver halide emulsion layer may be a single layer or a multilayer (two layers, three layers, etc.). In the case of multiple layers, different silver halide emulsions may be used, or the same silver halide emulsions may be used.

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 prepared in the presence of 10 to 10 moles of iridium salt or complex salt thereof per mole of iridium, and have a silver iodide content on the surface of the grains. It is a silver haloiodide having a higher silver iodide content than the grain average silver iodide content. When an emulsion containing such silver haloiodide is used, photographic characteristics with even higher sensitivity and high comma 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 salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (IL), potassium hexachloroiridate (■), ammonium hexachloroiridate (I), etc. There is.

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; hydroquine ethyl cellulose,
Cellulose derivatives such as carboxin methylcellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

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

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodans, etc. can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, Nran compounds, etc. can be used.

For the purpose of promoting high sensitivity and high contrast, the photographic light-sensitive material of the present invention includes Japanese Patent Application Publication Nos.
Compounds described in No. 7939 can be added. These may be used alone or in combination of two or more.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobanzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro( mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly t-hydroxy-substituted (/, 3, 3a, y )
Tetrazaindenes, -<tetrazaindenes, etc.;
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like. Among these, preferred are benzotriazoles (e.g. !-methyl°benzotriazole)
and nitroindazoles (eg, !-nitroindazole). However, these compounds may be included in the treatment solution.

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

For example, chromium salts (such as chromium alum), aldehydes (formaldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (t, 3.S-) acryloyl-hexahydro S-triazine , / 3-vinylsulfonyl 2-pro-t-nol, etc.), active halogen compounds (, +4-dichloro-2-hydroxy-3-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. These can be used singly or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylcono- Nonionic surfactants such as phosphoric acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl sulfonates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfones Such as acid salts, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, null succinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfur m-ester groups, and ester phosphate groups; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines amphoteric surfactants such as amine oquinides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic 9th class ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic Cationic surfactants such as phosphonium or sulfonium salts can be used.

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 photosensitive material of the present invention includes, for the purpose of improving dimensional stability, etc.
Dispersions of water-soluble or sparingly soluble synthetic polymers can be included. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (
Meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination;
Or these and acrylic acid, methacrylic acid, α β-
A polymer containing a combination of unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

Supports for the photosensitive material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose,
Although polystyrene, polyethylene terephthalate, etc. can be used, a polyethylene terephthalate film is most preferred.

These supports may be corona treated by a known method, and if necessary, may be underbowed by a known method.

However, a waterproof layer containing a polyvinylidene chloride polymer may be provided in order to improve so-called dimensional stability, in which dimensions change with changes in temperature and humidity.

As development accelerators or nucleating and infectious development accelerators suitable for use in the present invention, JP-A-3-27 Otsu/Otsu, Ibid.
Riichi 37732, 3B-737゜/33, same Otsu θ-/
In addition to the compounds disclosed in 4tθI3gθ, Dogo 0-/9!9j9, etc., various compounds containing N or S atoms are effective.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of the compound having an acid group include polymers or copolymers having organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid as repeating units. Regarding these compounds, please refer to JP-A Sho/-ko, No. 23 and 3, Otsu/-, 221 No. 32, Shiotsu Ko, 2!2 Guj, No. 2-! ! ≦References can be made to the records of the Kushi issue and the specification of the patent application Sho-Otsu/-za 22-gu No. 0. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

In order to obtain photographic characteristics of ultra-high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or p'H/3 described in U.S. Patent No. 22/9.976. There is no need to use a highly alkaline developer close to that of 100%, and the developer can be used stably.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0. Contains more than /j mole/no, pH
1o, o~/, 2.3, especially pH//, 0~i, 2. o
A sufficiently high contrast negative image can be obtained using this developer.

Although there are no particular restrictions on the developing agent used in the developer used in the present invention, it is preferable that it contains dihydroxybenzenes, as it is easy to obtain good halftone quality. A combination of 3-pyrazolidones or a combination of dihydroxy and p-aminophenols is also used.

Examples of dihydroquine benzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2+3-dichlorohydroquinone, 2. j-
Dichlorono-idofuquinone 1.2.3-dibromohydroquinone 1.2. tG Dimethylhydroquinone is preferred, but dimethylhydroquinone is preferred.

As the developing agent for /-phenyl-3-pyrazolidone or its derivative used in the present invention, /-phenyl-3-pyrazolidone, /-phenyl-4fucu-dimethyl-goovirazolidone, /-phenyl-goomethyl-goohydroxymethyl -3-Pyrazolidone,/-Phenyl-Cuts 1. L-
Dihydroxymethino and -3-pyrazolidone, /-phenyl-3-methyl-3-pyrazolidone, /-p-aminophenylll, +-dimethyl-3-pyrazolidone, /-p
Tolyl-Hiroshi, Hiro-dimethyl-3-pyrazolidone you are.

Examples of p-aminone enol-based developing agents used in the present invention include N-methyl-p-aminephenol, p-aminephenol, N'=(β-hydroquinether)-p-aminoneenol, N-(t,t-hydroxyphenyl ) glycine, no-methyl-p-aminone enol, p-benzylaminophenol, among others, N-methyl-
p-Aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/β to 0.8 mol/l. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols, the former is 0.
05 mol/l to 0°5 mol/1, the latter 0.06 mol/l
It is preferable to use it in an amount equal to or less than β.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.4 mol/1 or more, particularly 0.5 mol/1 or more. Further, the upper limit is preferably 2.5 mol/1.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulators and buffers. The pH of the developer is 10.5-1
It is set between 2.3.

Additives used in addition to the above ingredients 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, dimethylformamide, and methyl cellosolve. , hexylene glycol, ethanol, methanol, and other organic solvents; antifoggants such as indazole compounds such as 1-phenyl-5-mercaptotetrazole and 5-nitroindazole; and penztriazole compounds such as 5-methylbenztriazole; or black bottles. (black pepper) inhibitor: may also be included, if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-106
The amino compounds described in No. 244 may also be included.

The developing solution of the present invention contains a silver stain preventive agent.
．． Compounds described in No. 347 can be used. Patent application 1986-109.74 as a solubilizing agent added to the developer.
Compounds described in No. 3 can be used. Furthermore, as a pH buffering agent used in the developer,
The compound described in No. 3 or the compound described in Japanese Patent Application No. 61-28708 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 (eg, aluminum sulfate, light bread, etc.) as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0. 4-2.
0g-Al/R. 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 5X per mole of silver in an aqueous gelatin solution kept at 55°C
In the presence of 10-' moles of iridium (III>potassium hexachloride), the aqueous silver nitrate solution, potassium iodide, and aqueous potassium bromide were simultaneously mixed for 60 minutes.

By keeping pAg at 7.8 during this period, the average particle size is 0.
．． 30μ monodisperse cubic silver iodobromide emulsion (silver iodide content 1
(mol%) was adjusted.

Further, this emulsion was washed with water according to a conventional method to remove soluble salts, and then gelatin was added. Subsequently, an aqueous potassium iodide solution of 0.1 mol % per mol of silver was added to convert the grain surface to prepare emulsion A.

Emulsion A was added with 0.5 g of 4 as a stabilizer per mole of silver.
-Hydroxy-6-methyl-L 3. 3a,7-titrazaindene, 0.1 g of 1-phenyl-5-mercaptotetrazole was added as an antifoggant.

As a panchromatic sensitizing dye, the general formula ■~20 and ↓−
4.23 per mole of silver, respectively. X
10-5 mol was added as a hydrazine derivative with the general formula (
The compound shown in III) was added as shown in Table 1.

Further, the dye compound represented by the general formula (I) of the present invention and the compounds represented by (a) and (b) as comparative compounds were added as shown in Table 1.

Furthermore, polyethyl acrylate, 5-methylbenzotriazole, and 1.3 vinylsulfonyl-2-propanol as a hardening agent were added, and 3.5 g 1
Coating was carried out so that the silver amount was 0f. The amount of gelatin applied was 1.8 g/rtr.

On top of this emulsion layer, 1°3 g/m of gelatin was added as a protective layer.
, polymethyl methacrylate-1-5 with an average particle size of 2.5μ
0++vr/n(, colloidal silica 0.15 g/
A layer containing sodium dodecylbenzenesulfonate as a coating aid, and N-perfluorooctanesulfonyl-N-propylblycine potassium salt as a charge control agent was simultaneously coated.

Each sample thus obtained was exposed to light through a 633 nm interference filter and an optical wedge, and developed at 34° C. for 30 seconds using the lower R prescription. Further, each sample was left for 10 days at 50° C. and 55% humidity, and then subjected to the same exposure and development treatment.

As a friction resistance test, a load of 0 to 100 g was continuously applied to each sample using a sapphire needle with a diameter of 0.4 mm, and then development was performed and the degree of increase in density due to the friction of the needle was evaluated.

The results were evaluated on a five-point scale, with "1" being the worst level for fogging caused by friction, and "5" being the best level.

(Developer formulation) Hydroquinone 45.0gN・Methyl p・Aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18.0g Potassium hydroxide
55.0g 5-sulfosalicylic acid
45.0g boric acid 25
．． 0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g Potassium bromide 6.0 g 2-mercaptobenzimidazole-5-sulfonic acid 0.3 g 5-methylbenzotriazole 066 g Sodium 3-(5-mercaptotetrazole)benzenesulfonate 0.2 g Butyl jetanolamine
15゜ Add 0g water
11 (pH = 11.6) The halftone quality was determined by exposing the halftone dots through a commercially available contact screen (gray negative 150 lines), observing the halftone dots formed with a magnifying glass, and assigning a score of "1" to those with poor halftone quality. The evaluation was made on a five-point scale, with a score of "5" indicating excellent halftone dot quality.

The results obtained are shown in Table 1.

Samples 6 to B and 10 to 12, and 14 to 16 of the present invention maintain high sensitivity and high contrast, and have good halftone dot quality. Furthermore, it can be seen that it has excellent abrasion resistance and storage stability.

On the other hand, Comparative Sample 1.5.9, which does not contain the hydrazine compound of general formula (III), has low sensitivity and contrast and poor halftone quality.

Also, sample 2.3.4 not containing the compound of general formula (I) and sample 17.18 containing comparative compounds (a) and (b)
It can be seen that the abrasion resistance is poor and the sensitivity change is large after being left for 10 days at 50''C and 55% temperature and humidity.

Furthermore, sample (I3) is inferior in abrasion resistance and halftone dot quality, but this is due to the large amount of hydrazine compound 111-5 added.

Compound (a) Procedural amendment Compound (b) (CH2)aSO3Na 　2HS 1゜ 2゜ 3゜

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material containing a silver halide emulsion color-sensitized with a panchromatic sensitizing dye, in which hydrazine is contained in the silver halide emulsion layer or other hydrophilic colloid layer. 1. A negative silver halide photographic material comprising a derivative and a compound represented by formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a sulfoalkyl group, a carboxyalkyl group, a sulfoaralkyl group, or a carboxysiaralkyl group. R_2 represents a substituted or unsubstituted alkyl group or aryl group. R_3 is -(CH_2)_n_1CONH(CH_2)
_m_1OH, or -(CH_2)_n_2O(CH
_2) _m_2OH, m_1, m_2, n_1
and n_2 each represent an integer from 1 to 7. However, m_1+n_1 and m_2+n_2 are each 8 or less. W represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, or a phenyl group. ]