JPH03282448A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high-contrast sensitive material having high sensitivity and nearly preventing the occurrence of black spots by using an emulsion subjected to desalting treatment for removing dissolved matter by flocculation and precipitation with modified gelatin and incorporating a hydraxine deriv. into an emulsion layer or a layer adjacent to the emulsion layer. CONSTITUTION:A silver halide photographic sensitive material having a silver halide emulsion layer on the base is formed with an emulsion subjected to desalting treatment for removing dissolved matter by flocculation and precipitation with modified gelatin and a hydrazine deriv. is incorporated into the emulsion layer or a layer adjacent to the emulsion layer. Such photographic characteristics as high contrast can be obtd. without lowering the sensitivity and the occurrence of black spots in a dot image is controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material that can be used to form ultra-high contrast photographic images.

More specifically, the present invention relates to a silver halogenide photographic light-sensitive material that is highly useful in the field of photolithography and is capable of forming halftone images with high contrast using a developer with relatively good stability.

[Background of the invention]

The photolithography process includes converting a continuous tone original into a halftone image, that is, converting continuous tone density changes into a set of halftone dots having an area proportional to the density.

This process uses photographic technology that can reproduce ultra-high contrast images, and involves photographing the original through an intersection screen or contact screen and forming a halftone image through contagious development. I've been exposed to it.

Lith-type silver halide photographic light-sensitive materials used for contagious development do not have sufficient high contrast unless they are processed with contagious developer (Lith-type developer). For example, when processed with MQ developer or PQ developer, Gamma is at most 5 or 6, and there are many fringes that must be avoided in terms of halftone dot formation.
It is said that it is essential to use it in combination with an infectious developer that has poor stability.

Therefore, a technology was developed that uses a developing solution with a high sulfite ion concentration, good stability, and rapid processing to form ultra-high contrast images comparable to infectious development. The technique disclosed in No. 106244 and the like is known. In this technology, a specific compound called a so-called high contrast agent is present in the silver halide photographic light-sensitive material, and in order to fully exhibit the high contrast characteristics of the compound, specific silver halide grains and other photographic additives are added. is combined.

This silver halide photographic light-sensitive material can be processed with a developing solution that has good preservability and can be processed quickly to obtain ultra-high contrast photographic images. In the formation of halftone dots, sandy bottle-like fog, so-called black spots, occur in the halftone dots, impairing the halftone image quality. To solve this problem, various stabilizers and inhibitors with heteroclaves are added. Attempts have been made to solve this problem, but it cannot be said to have been resolved satisfactorily.

[Purpose of the invention]

An object of the present invention is to obtain a silver halide photographic light-sensitive material that can obtain high-contrast photographic characteristics without impairing sensitivity, as well as obtain high-contrast photographic characteristics by controlling black spots generated in halftone images. The goal is to provide the following.

[Structure of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which a desalting treatment for removing dissolved substances of the emulsion causes coagulation and precipitation by modified gelatin. This is achieved by a silver halide photographic material characterized by containing a hydrazine derivative in the emulsion layer or an adjacent layer.

The present invention will be specifically explained below.

Preferred compounds as hydrazine derivatives used in the present invention are compounds represented by the general formula [I)(n)(nI) below.

- Formula (1) (wherein R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents 0 to 6, m represents 0 or 1, and n is 2 or more (In the formula, R21 represents an aliphatic group, an aromatic group, or a heterocyclic group, R22 is a hydrogen atom, an optionally substituted alkoxy group,
It represents a heterocycle, an oxy group, an amino group, or an aryloxy group, and Pl and P represent a hydrogen atom, an acyl group, or a sulfinic acid group. ) - Formula [II [) ■ Ar NHNHCRsr (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R31 represents a substituted alkyl group.) The above general formulas (I), (II), and [■] will be specifically explained.

General Formula [Equation] In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents a divalent training group, n represents 0 to 6, and m represents 0 or 1.

Here, examples of the aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc. Preferred is an aryl group. R.

Various substituents can be introduced into the aryl group or heterocyclic group represented by and R3. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, impropoxy, butoxy,
octyloxy, dodecyloxy, etc.), acylamino groups (e.g. acetylamino, pivallylamino, benzoylamino, tetradecanoylamino, σ-(2,4-di-t-amylphenoxy)butyrylamino, etc.), sulfonylamine groups (e.g. methanesulfonyl) amino,
butanesulfonylamino, dodecanesulfonylamino,
benzenesulfonylamino, urea groups (e.g., phenylurea, euthylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.),
Hydroxy group, amino group, alkylamino group (e.g.
methylamino, dimethylamino, etc.), carboxy group,
Examples include an alkoxycarbonyl group (eg, nidoxycarbonyl), a carbamoyl group, and a sulfo group. As the divalent organic group represented by R, for example, an alkylene group (
Examples include methylene, ethylene, tolyltylene, tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. Aralkylene groups include oxy groups, thio groups, seleno groups, carbonyl groups, R8 -N- group (R3 represents a hydrogen atom, an alkyl group, or an aryl group) may include a sulfonyl group and the like.

Various substituents can be introduced into the group represented by R.

Examples of the substituent include C0NI (NHR4 (R4 represents the same meaning as R1 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

Of the compounds represented by the general formula CI), preferably Ro and R2 are substituted or unsubstituted phenyl groups, and n=m
=1 and R represents an alkylene group.

Specific compounds of typical compounds represented by the above general formula [I] ■ ■ -3 -8 ■ ■ 10 ■ 1 ■ 12 ■ 3 ■ 18 ■ 19 20 ■ 21 ■ 14 ■ 15 ■ 17 22 ■ 5 ! -26 ■ 27 ■ 29 ■ 4 ■ =35 1-. 36 ■ 7 31 ■ 32 ■ 33 ■ 38 ■ 41 ■ -42 ■ 43 ■ 50 ■ 51 ■ =52 ■ 46 ■ 47 ■ 8 ■ 53 ■ 4 ■ 55 tC6[(++ Next, we will explain the general formula [I[) The aliphatic group represented by R21 N N CCRz□ R21 preferably has 6 carbon atoms.
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more helaro atoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group.

The aromatic group represented by R21 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, quinoline ring,
Among them, those containing a benzene ring are preferred, including an inquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

Particularly preferred as R31 is an aryl group.

The aryl group or unsaturated heterocyclic group of R2□ may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monomer having 1 to 20 carbon atoms in the alkyl moiety). cyclic or bicyclic), alkoxy groups (
(preferably one having 1 to 20 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably one 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).

Among the groups represented by R2□ in general formula (II), the optionally substituted alkoxy group has 1 to 20 carbon atoms and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R22 in the general formula [■], the optionally substituted aryloxy group or hexacyclic oxy group is preferably a monocyclic group, and the substituent is a halogen atom alkyl group or an alkoxy group. Among the groups represented by R2□, which include , and ano groups, preferred are an optionally substituted alkoxy group or an amino group.

A2 may be an optionally substituted alkyl group, an alkoxy group, or a cyclic structure containing a 10--3--N- group bond. However, R1! is never a hydrazino group.

R11 or R12 in the general formula [■] may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

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

R21 or R2 in the general formula [■] may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiophoretic groups,
Examples include groups described in US Pat. No. 4,355,105, such as a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. -Among the compounds represented by the formula [1[), the compounds represented by the following formula [I[-a] are particularly preferred.

-Formula (II-a) 0 -Several of the above (I propyl group, 2-cyanoethyl group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, a-hydroxy naphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2pyridyl group, pyrrolidyl group, 4-methyl-2
-pyrrolidyl group), R1 is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), and R1, and Rffi? represents a divalent aromatic group (for example, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (for example, -8O1CH*CJNH-SJNH, -
0CHJO1NH,0--CH-N-), R□ represents -R/ R/ / or -0R1, RI
R11 and R3 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group),
phenyl group (e.g. phenyl group, p-methylphenyl group, p-methoxyphenyl group), naphthyl group (e.g. σ-
naphthyl group, β-naphthyl group) or a heterocyclic group (for example, an unsaturated heterocyclic group such as pyridine, thiophene, and furan, or a saturated heterocyclic group such as tetrahydrofuran and sulfolane, and R' and R/ /R is a ring together with a nitrogen atom (e.g., piperidine, piperazine, morpholine, etc.)
It may be completely formed.

m and n represent 0 or l. When representing R11OR21, Y preferably represents a sulfur atom.

Representative compounds represented by the above formulas (II) and (I[-a) are shown below.

Specific example of general formula C11)] I-5 -1 0 1-6 1-2 0 I[-3 0 1[-7 -4 -a ■ 9 ■ 10 ■ 11 ■ 12 ■ 7 ■ Month 8 ■ 13 ■ *-NHNHCCOCH,CH,SO□C日ICI(,
OH1[-14 l-15 ■ 16 #-NliNt11. ; uυshitl, Ufl!
>1. ;tl, utl, υi■ 21 ■ 22 H3 ■ 23 ■ 24 ■ -25 ■ 26 ■ 27 ■ 28 ■ 33 ■ -35 ■ = 36 ■ 37 0 ■ 29 ■ = 30 ■ = 31 ■ 2 ■ 8 ■ 9 ■ 40 ■ 41 O 0 0 0 ■ 43 ■ 4 ■ 45 ■ 6 ■ 7 ■ 2 ■ =53 ζ ■ 54 ■ 55 CH3 ■ =48 ■ 9 ■ 50 ■ 1 ■ =56 ■ 7 ■ ■ *-NHNHCCNHCH2CH2SCH, CH, 5C
H2CI20 58 ■ 9 ■ 0 113 1[-61 Next, a method for synthesizing the compound ■■-47 of the above-mentioned specific compounds will be shown as an example.

Synthesis of compound ■-45 Synthesis scheme 45゜(-B) Compound 2-45 Compound 4-nitrophenylhydrazine 153g and 500g
Mix 1+1Ω diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50g of the obtained crystals (A) was heated and dissolved in methanol of 1000+a (2),
Compound (B) is obtained by reduction under a pd/C (palladium/carbon) catalyst in an H8 atmosphere pressurized at 50 Psi.

22g of this compound CB) in acetonitrile 200n+f
Dissolve compound (C) in a solution of f and 16 g of pyridine at room temperature.
Add 24 g of acetonitrile solution dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain 31 g of compound (D).
I got it.

Compound CD) 30g was hydrogenated in the same manner as above to obtain compound (CD).
E) 20g was obtained.

3. Dissolve 10g of compound (-E) in acetonitrile 100+Q and prepare ethylthiocyanate. Og was added and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) is purified by recrystallization.
7.0g was obtained. Compound (F) 5.0g methanol 5
Methylamine (40% aqueous solution 3 m
ff) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out and purified by recrystallization to obtain Compound 1-45.

Synthesis of compound ■-47 Synthesis scheme (B) (C) (D) (E) Compound ■-47 22 g of compound (B) was dissolved in 200 g of pyridine and poured into a stirring sieve, and p-nitrobenzenesulfonyl chloride 2 was added.
Added 2g. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). This compound (C) was subjected to the same reaction as compound 1-45 according to the synthesis scheme to obtain compound 11-47.

Next, the general formula [■] will be explained.

-Formula [111) %Formula% In the general formula CI[), Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group; Ballast groups commonly used in additives are preferred. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a 100 urea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R31 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (e.g. methoxy, ethoxy, etc.), aryloxy (e.g. phenoxy, p-chlorophenoxy, etc.),
Heterocyclic oxy (e.g. pyridyloxy, etc.), mercapto, alkylthio (methylthio, ethylthio, etc.), arylthio (e.g. phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g. pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), Alkylsulfonyl (for example, methanesulfonyl, butanesulfonyl, etc.)
, arylsulfonyl (e.g. benzenesulfonyl, etc.)
, heterocyclic sulfonyl (e.g., pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g., acetyl, benzoyl, etc.), cyano, chlor, bromine, alkoxycarbonyl (e.g., ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl (e.g., phenoxycarbonyl, etc.) , carboxy, carbamoyl, alkylcarbamoyl (e.g., N-methylcarbamoyl, N,
N-dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-phenylcarbamoyl, etc.), amine, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino, naphthylamino, etc.) , acylamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy, etc.), alkyl Aminocarbonyloxy (e.g. methylaminocarbonyloxy, etc.)
, arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), arylsulfamoyl (e.g., 1f1 phenylsulfamoyl, etc.). Can be mentioned.

Even if the hydrogen atom of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g., ethoxalyl, etc.), good.

Typical compounds represented by the above-mentioned formula (DI) include those shown below.

1[-1 m-2 1[[-3 -4 -5 ! [[-11 ■-12 -13 I[[-14 ■ 5 11[-6 -7 11[-9 ■-10 ■ -16 - 17 Ill - 18 ■ 9 ■ -20 Ill-21 ■-22 ■- 23 ■-24 ■-25 ■ 1 ■-32 ■ -33 ■-34 ■-35 ■ 6 ■-27 ■-28 ■-29 ■-30 ■ -36 ■-37 ■ 8 ■-39 1 *-NHN )ICCHaOCHzCH BA)CH,CB2
0H ■-40 ■-44 ■-41 ■-45 ■-42 ■-46 ■-43 ■-47 ■-48 ■-49 ■-50 Next, a synthesis example of compound II[-5 will be described.

Synthesis of compound m-s Synthesis scheme Compound m-5 was obtained according to the synthesis method of compound 1[-45.

Formula C contained in the silver halide photographic material of the present invention
The amount of the compounds I), (I[) and (I[[) is preferably from 5X10-' to 5X101 moles per mole of silver halide contained in the silver halide photographic material of the present invention, More preferably 5XlO-6 to l
X 10-'' mole range.

In the present invention, the agglomerating gelatin agent refers to a polymeric aggregating agent capable of agglomerating silver halide grains together with a protective colloid, particularly an aggregating agent for modified gelatin in which at least 50% or more of the amino groups of gelatin molecules have been substituted. It is. Examples of substituents for amino groups in gelatin are given in U.S. Pat.
, No. 691.582, No. 2,614,928, No. 2,
It is described in No. 525.753.

Useful substituents include (1) acyl groups such as alkylacyl, arylacyl, acetyl, and substituted or unsubstituted benzoyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; (3) alkylsulfonyl and arylsulfonyl. sulfonyl groups such as (4) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) linear monobranched alkyl groups having 1 to 18 carbon atoms, (6
) Substituted and unsubstituted aryl groups such as phenyl, naphthyl, pyridyl, aromatic heterocycles such as furyl, and the like.

Among them, 1. Preferred modified gelatin has an acyl group R8 (-CORI) or a carbamoyl group (-CONR,)
This is due to

R1 is a substituted or unsubstituted aliphatic group (for example, a carbon number 1-
18 alkyl groups, allyl groups), aryl groups, or aralkyl groups (for example, phenethyl groups), and R2 is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.

Particularly preferred is the case where R1 is an aryl group and R8 is a hydrogen atom.

Specific examples of agglomerated gelatin agents that can be used in the present invention are illustrated below using amino group substituents, but the present invention is not limited thereto.

Exemplary agglomerated gelatin agent (amino group substituent) -IG-2 COCJs (t) COCH3-7- -11 -12 The agglomerated gelatin agent can be used in any step during the production of a silver halide photographic emulsion, but is preferably Use after the desalting step, particularly preferably during the desalting step, is more effective since it does not cause softening of photographic performance. There is no particular limit to the amount of the flocculated gelatin agent added, but when used for desalting, it is appropriate to add (Ll-10 times the amount (weight) of the substance (preferably gelatin) contained as a protective colloid after desalting. It is particularly preferably 0.2 to 5 times the amount (by weight).

The agglomerated gelatin agent aggregates silver halide grains together with a protective colloid. After adding the agglomerated gelatin agent, the pH is adjusted to perform halogen coagulation at a pH of 5.5 or lower, particularly 4.0. 8-2 is preferred. pHl
There are no particular restrictions on the acid used for the adjustment, but organic acids such as acetic acid, citric acid, and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid are preferably used. Heavy metal ions such as magnesium ions, cadmium ions, lead ions, zirconium ions, etc. may also be added to the aggregated gelatin agent.

Removal of dissolved substances (desalting) may be repeated once or several times. When repeating several times, the flocculated gelatin agent may be added each time the removal is performed, or the flocculated gelatin agent may be added only at the beginning.

In the method for producing a silver halide photographic emulsion of the present invention, gelatin is usually used as a binder or protective colloid, but other materials such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc. Proteins: Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, etc.; Derivatives: polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide,
A wide variety of synthetic parent polymeric materials can be used, such as single or copolymerized polyvinylimidazole, polyvinylpyrazole, and the like.

Next, the silver halide used in the silver halide photographic material of the present invention will be explained. Silver halide of any composition can be used. For example, silver chloride, silver chlorobromide,
There are silver chloroiodobromide, pure silver bromide, and silver iodobromide. The average diameter of the silver halide grains is preferably in the range of 0.05 to 0.5 μm, particularly 0.05 to 0.5 μm. lO~
A thickness of 0.40μ is suitable.

Although the particle size distribution of the silver halide grains used in the present invention is arbitrary, it is preferable that the monodispersity value defined below is in the range of 1 to 30, and more preferably in the range of 5 to 20. .

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

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

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

Furthermore, silver halide can be sensitized by various chemical sensitizers. As the sensitizer, for example, activated gelatin, sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allyl inthiacinate, etc.),
Selenium sensitizers (N, N dimethyl selenourea, seleno element, etc.), reduction sensitizers (triethylenetetramine, silver chloride, etc.)
tin, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2
-Aurosulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroole-
Various noble metal sensitizers typified by sodium chloride, sodium chlorovaladite, etc. can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

The performance of the silver halide grains used in the present invention can be improved by preferably applying them to grains having surface sensitivity higher than internal sensitivity, that is, silver halide grains that give so-called negative images.

Further, the silver halide emulsion used in the present invention includes mercapto compounds (1-7 enyl-5-mercaptotetrazole, 2
-Mercaptobenzthiazole), benzotriazole M (5-bromobenzotriazole-5-methylbenzotriazole), benzimidazoles (6-nidropenzimidazole), and the like can be used to stabilize or suppress fog.

The photosensitive silver halide emulsion layer or its adjacent layer may contain research disclosure materials for the purpose of increasing sensitivity, increasing contrast, or promoting development.
Compounds described in Section XXI B-D of No. 17463 can be added.

Preferably, it is a compound represented by the following formula [51].

General formula [5] % formula % can be obtained by treating with the above chemical sensitizer [where R0 represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n is an integer from 10 to 200] represents.

] Specific examples more preferable than the compound represented by the general formula [5] will be given, but the invention is not limited thereto.

5 1 HO (CHzCHzO)nHn=10
5-2 HO(CHzCHzO)nHn=30
5 3 HO(CH* CH20)n Hn
= 505-4 HO(CHzCHzO)nH
n405-5 HO(CHzCH20)nHn
=1505-6 HO(CH2CHzO)nH
n.200-7 -11 -12 -13 -8 -9 5 -16 -17 These compounds are commercially available and can be easily obtained. These compounds have a content of 0.0% per mole of silver halide. It is preferable to add 0.02 to 4.0 mol of Ol.
-2 mol is more preferred.

It is also possible to include two or more types of compounds having different values of n.

The silver halide emulsion used in the present invention includes a sensitizing dye,
Plasticizers, antistatic agents, surfactants, hardeners, etc. can also be added. General formula N according to the present invention ], f2 L
When adding the compound [3] to the hydrophilic colloid layer,
Gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at a concentration of log/g'' or less.

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

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

Typical examples of 10-(CH=CH)n-OFI type developing agents include hydroquinone, and others include catechol and pyrogallol.

In addition, typical HO - (CH= CD) n - NH type developers include ortho and para aminophenols or aminopyrazolones, and N-methyl-p
-aminophenol, N-β-hydroxyethyl-p-
Examples include aminophenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol.

Examples of the heterocyclic developer include 1-7enyl-3-hyrazolidone, l-7enyl-4,4-dimethyl-3-pyrazolidone, l-7enyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and l-phenyl. -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Examples include pyrazolidones and the like.

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

Fourth Edition) pages 291-334 and Journal of the American Chemical Society (Journal, of the Amer.
Developers such as those described in Vol. 73, p. 3.100 (1951) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH using caustic alkali, alkali carbonate, or amines, etc. used in general black and white developers, and providing a buffer function;
and inorganic development inhibitors such as bromkaline and 5-methylbenzotriazole, 5-methylbenzimidazole, 5-
Organic development inhibitors such as nitroindazole, adenine, guanine, 1-7znyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, alkyl Do not add surfactants such as sodium arylsulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, ionic strength regulators such as sodium sulfate, etc. Optional. The developer used in the present invention includes:
Alkanolamines such as jetanolamine and triethanolamine, and glycols such as diethylene glycol and triethylene glycol may be contained as organic solvents. In addition, alkylamino alcohols such as diethylamino-1,2-propanediol and butylaminoglobanol are particularly preferably used [Example] Specific examples of the present invention will be described below, but embodiments of the present invention are Not limited to these.

Example 1 (Preparation of silver halide emulsion grains) A silver halide emulsion having a silver halide composition of 98 mol % silver bromide and 2 mol % silver iodide was heated at 50°C, pAg 7.8, p
Prepared under H2,0 conditions. A simultaneous mixing method was used for supplying silver ions and halide ions, and at that time, the supply amount was increased in proportion to the surface area as the formed silver halide grains grew. Furthermore, just before the end of particle formation, 21rCI26
6.times.10-' moles per mole of silver were added, and after completion of grain formation, partial halogen substitution was carried out using 0.3 mole of potassium iodide per mole of silver.

The resulting emulsion consisted of cubic grains with an average grain size of 0-2 μm and a coefficient of variation of 15%.

(Desalting) The obtained emulsion was adjusted to pn 5.5 with caustic soda, and then divided into portions, each of which was desalted under the following conditions.

a) Add 80 ml of 10% ossein gelatin solution to 1.0 kg of the comparative divided emulsion (silver content: 44 g, 1 4 g of ossein gelatin) at 40°C, stir for 10 minutes, and then add 5% polynaphthalene sulfonic acid solution. 90ml of 20% magnesium sulfate and 90mΩ were added. After stirring for 5 minutes,
After allowing the emulsion to settle, 800 ml of supernatant liquid was removed.

Next, add 800 m of pure water (2) at 40 °C and stir for 5 minutes, then add 30 + n1 of 20% magnesium sulfate solution.
After stirring for 5 minutes, the mixture was allowed to stand still, and 800 ml of supernatant liquid was removed.

A similar desalting operation was carried out one more time using 30 ml of 20% magnesium sulfate.

The liquid temperature during the operation was maintained at 40°C.

Obtained t; The following compounds [A] [B] were added to the emulsion.
10% ossein gelatin solution containing mixture of [C]8
0 m4 was added and redispersed at 55°C to obtain the desired emulsion.

EA, EB] [C] Divide; 80 mQ of a 10% modified gelatin solution was added to 1.0 kg of the above emulsion (silver content: 44 g, 4 g of ossein gelatin) at 40°C as shown in Table 1, and stirred for 10 minutes. did. After that, the pH was adjusted to 4.4 with a 5% sulfuric acid solution, and after stirring for 5 minutes, the emulsion was allowed to settle.
800 mQ of supernatant liquid was removed.

Next, 800 ml of pure water at 40°C was added, the pH was adjusted to 5.7 with 5% caustic soda, and the mixture was stirred and dispersed for 5 minutes.

Furthermore, the same desalting operation as above was carried out twice using a sulfuric acid solution and a caustic soda solution.

The liquid temperature was maintained at 40°C during the operation.

Compounds similar to a) [A] [B],
10% ossein gelatin solution B containing a mixture of
Omc was added and redispersed at 55°C to obtain the desired emulsion.

The I)Ag of both a) and b) obtained emulsions at 40°C is 7
．． It was 6.

(Preparation of silver halide photographic light-sensitive material) An undercoat layer with a thickness of 0.1 μm on both sides (Japanese Patent Laid-Open No. 59-1994
A silver halide emulsion layer having the following formulation (1) with a gelatin amount of 2.0 was applied on one undercoat layer of a polyethylene Tele 7 tart film having a thickness of 1100p (see Example 1 of No. 1).
g/m2, silver amount is 3.2 g/m2, and on top of that, a protective layer of the following formulation (2) is applied with a gelatin amount of 1.
．． og/m2, and on the other undercoat layer on the opposite side, apply a backing layer according to the following recipe (3) so that the amount of gelatin is 2.4 g/m'. Furthermore, on top of that, a protective layer of the following formulation (4) is applied with a gelatin amount of 1-0.
Samples Nos. 091 to 16 were obtained by applying the coating in such a manner that the coating was applied at a rate of g/m2.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0g/m" Silver halide emulsion A silver amount 3.2g/m" Antifoggant: Adenine 10mg/m' Stabilizer 4-methyl-
6-Hydroxy-1,3,3a,7-chitrazaindene 30mg/m" Surfactant: Saponin 0.1g/m" Polyethylene glycol Molecular weight 4000 0.1g/m" Latex polymer: Sensitizing dye: However, the above sensitization The dye was adsorbed onto the silver halide emulsion grains for 1 hour at a temperature of 60°C.

Prescription (2) [Emulsion protective layer composition] Gelatin matting agent: 0.9 g/m of silica with an average particle size of 3.5 μm, 3 mg/m is surfactant S-2: CH2C00CHz (C2Hs) CaH*surfactant:
Saponin 0.1g/D2 Hardener: Formalin prescription (3) (Backing layer composition) 30mg/m" CH25○3H Formula (4) [Backing protective layer composition] Gelatin Ig/rn' Matting agent: Average particle size 3. 0-5.0 μm polymethyl methacrylate 50 mg/m” Surfactant S-2
: lomg/m" Hardening agent: Glyoxal 25mg/m": H-135m
g/m2 The obtained sample was subjected to a halftone quality test according to method 1 below.

(Testing method for halftone dot quality) Attach a part of the screen (150 lines/inch) with a halftone dot area of 50% to the step wedge, place the sample in close contact with this screen, and expose the sample to a xenon light source for 5 seconds. The sample was developed under the following conditions in an automatic processing machine for quick processing using the following developer solution-1 and the following fixer, and the halftone dot quality of the sample was observed with a 100x magnifying glass. The item was ranked as "5", and the following five ranks were assigned as "4", "3", "2", and "l". Note that the ranks rlJ and "2" are at levels that are not preferred in practice.

Black spots in the halftone dots are evaluated in the same way, and the highest rank is "5" when there are no black spots in the halftone dots. 4", "
The evaluation was made in descending order of rank: "3", "2", and "1".

In addition, in rank NJ and "2", the black bottle is also large and is at a practically unfavorable level.

In addition, the obtained sample was measured with a Konica digital densitometer PDP65, and the sensitivity at a concentration of sample N011 of 3.0 was 10.
The relative sensitivity is expressed as 0, and the gamma is expressed as the tangent between the densities 0.3 and 3.0.

1g Sodium sulfite 60g Hydroquinone 35g 3-(diethylamino)-1,2 propanediol 30g Sodium bromide 3.0g 5-methylbenzotriazole 0.1g 1-7enyl-5-mercaptetrazole 0.08g 1-phenyl-4,4
-Dimethyl- 3-pyrazolidone 0.2g Phenylpicolium bromide 2.5g Water was added to make 1Q, and the pH was adjusted to 7 with sodium hydroxide.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 2
40m12 Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g (composition) Pure water (ion exchange water) 17m (1 sulfuric acid (50% w/w aqueous solution) 4.7g aluminum sulfate (A Qx o s equivalent content is 8.1%) (w/w aqueous solution) 26.5 g When using a fixer, the above compositions were dissolved in 500 mQ of water in the order of composition 1 and finished to Iff.The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development geographical conditions) (Process) (Temperature) (Time) Development
40°C15 sand and mud Washing at 35°C15 sand and water Drying at 50°C for 10 seconds The results are shown in Table 1.

From the results in Table 1, it can be seen that the samples of the present invention have high sensitivity, high gamma, and good black and white areas.

Example 2 Everything was carried out in the same manner as in Example 1, except for developing with a developer having the following formulation.

The results are shown in Table-2.

Developer formulation 2 Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Sodium phosphate (decahydrate) Hydroquinone N,N-diethylethanolamine Sodium bromide 5-methylbenzotriazole 1-phenyl-5-mercabutotetrazole meth
- 5g 22.5g 5g 3g 0.25g 0.08g 0.25g

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material that has high sensitivity, high contrast, and less occurrence of black spots.

Water was added to make 112, and pn was adjusted to 11.7 with sodium hydroxide.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a desalting treatment for removing dissolved substances of the emulsion is performed by flocculating and precipitating with modified gelatin, and the emulsion is A silver halide photographic material containing a hydrazine derivative in a layer or an adjacent layer.