JPH0238A - Silver halide photographic sensitive material having high contrast - Google Patents

Abstract

PURPOSE:To obtain the title material having a high contrast and a less tendency for generating a dye stain, even at the time of rapidly developing it by incorporating a specified compd. in a silver halide emulsion layer and an another specified compd. in a hydrophilic colloid layer, respectively. CONSTITUTION:The compd. shown by formula IV is incorporated in the silver halide emulsion layer, and at least one kind of the compds. shown by formulas I, II and III is incorporated in the hydrophilic colloid layer. In formula I, R1 and R2 are each aryl group, R is an org. binding group. In formula II, R21 is an aliphatic group, R22 is hydrogen atom, P1 and P2 are each hydrogen atom. In formula III, Ar is an antidispersible group, R31 is a substd. alkyl group. In formula IV, Z is a nonmetallic atom group, R<41> and R<42> are each alkyl group, R<43> and R<44> are each hydrogen atom. The photosensitive material having the high contrast and the less tendency for generating the dye stain after processing it even at the time of rapidly developing the material with a developer having a high sulfite acid ion concn. is obtd. by applying the emulsion layer and the colloid layer as mentioned above on a supporting body.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a silver halide photographic light-sensitive material that is spectrally sensitized and has sensitivity to all colors, and in particular has green light and red light sensitivity. The present invention relates to a silver halide photographic light-sensitive material which can obtain a high-contrast halftone image even in relatively rapid development and which has extremely little dye staining after processing.

[Prior Art] It is known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is about 0.5μ
Silver halide consisting of a silver chlorobromide or silver chloroiodide emulsion with fine grains of m or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. A method is known in which a high-contrast halftone dot image or line image is obtained by processing a photosensitive material with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions.

This type of silver halide light-sensitive material is known as a lithium-type silver halide photographic light-sensitive material, and has an area of a size proportional to the continuous tone density change of the original during the photolithography process. It is used to convert to a set of halftone dots. Such conversion involves photographing the original through a cross-line screen or contact screen using a silver halide photographic light-sensitive material, which then has a very low concentration of sulfite ions and contains only a hydroquinone developing agent. A halftone image is formed by developing with a so-called Lith type developer. This lithium-type silver halide photographic light-sensitive material is produced using a conventional developer with a high concentration of sulfite ions.
For example, even if processed with a commercially available developing solution for photographic paper, the gamma is only 5 or 6, and fringes, which must be avoided in halftone dot formation, occur frequently. It is said that the combination with a developer is essential. Regarding this developer, please refer to the Journal of the Franklin Institute (J, A.

CYule: J, Franklin In5tr
tuts), Vol. 239, p. 221 (1945), and contains essentially only hydroquinone as a developing agent, and has a low concentration of sulfite ions, which act as an antioxidant for the developing agent. It is a developer.

Such developers have poor shelf life and are susceptible to auto-oxidation, so in order for plate makers to consistently obtain high-quality halftone negative or halftone positive images, they must reduce the activity of the developer, which decreases over time. Although it is necessary to manage the developer to maintain a constant value, this operation inevitably becomes complicated.

Furthermore, in Lith development processing, in addition to managing the developer to keep the activity constant, there are two other problems: the processing speed is slow.
There are two major disadvantages.

The trend in printing plate making in recent years has been to shorten the printing process and shorten the time, and there is an increasing demand for processing speed of plate making film.

For example, Japanese Patent Application No. 59-240147 uses a silver halide photographic light-sensitive material containing a tetrazolium salt as a technique for obtaining an extremely high contrast image suitable for plate making using a developer with high stability. A method is disclosed. This method allows the use of a stable developer with a high concentration of sulfite ions, and enables rapid processing with a development time of around 30 seconds and a drying time of 90 to 100 seconds, which was not possible with conventional lithography. be.

On the other hand, silver halide photographic materials for plate making are generally required to have so-called orthotype photosensitivity, which is photosensitivity in the green area.

Since a photosensitive silver halide emulsion alone has a narrow wavelength range of sensitivity, a spectral sensitizer is used for the purpose of expanding the wavelength range of sensitivity to longer wavelengths. For example, as a device that imparts sensitivity to green light,
No. 28, No. 40-392, No. 43-10251, No. 43-22884, British Patent No. 815,172, No. 9
55°961, 955,912, 142,22
No. 8, U.S. Patent No. 1,942°854, U.S. Patent No. 1,950.
No. 876, No. 1,957,869, No. 2,238,2
No. 31, No. 2,521,705, No. 2,647,05
No. 9, Special Publication No. 43-2606, No. 44-3644,
No. 46-18106, No. 46-18108, No. 48
-15032, 49-33782, 4-34
No. 252, No. 58-52574, U.S. Patent No. 2,839
, No. 403, No. 3,567.458, No. 3゜625.
Examples include cyanine dyes and merocyanine dyes described in specifications such as No. 698.

[Problems to be solved by the invention] At the same time, these spectral sensitizers increase the sensitivity in a specific wavelength range, and at the same time, they have major negative characteristics such as: (1) being affected by other additives; (2) There should be no change in photographic properties such as a decrease in sensitivity or an increase in capri even after the passage of time; (3) There should be no dye staining after processing, etc. However, when relatively rapid development as described above is performed, dye staining after processing increases, which is a big problem in practice.

In order to reduce dye staining, it is necessary to use a material that has little staining property against hydrophilic colloids such as gelatin, and which easily flows out into the processing solution.
It is sufficient to use a spectral sensitizer with high solubility, and various compounds have been proposed in the past, but spectral sensitizers have a major influence on the development effect that provides the extremely high contrast required for plate making. This often causes problems such as a decrease in contrast, making it difficult to apply the means for solving dye stains in ordinary light-sensitive materials to silver halide photographic light-sensitive materials that undergo high-contrast development.

[Object of the Invention] The object of the present invention is to solve the above-mentioned problems, and to provide an extremely high contrast by rapid processing using a normal developer having high photosensitivity and high sulfite ion concentration, and An object of the present invention is to provide a silver halide photographic material with extremely little dye staining after processing.

[Means for Solving the Problems] As a result of various studies, the present inventors have developed a support and a hydrophilic colloid layer coated on the support, including at least one silver halide emulsion layer. In the silver halide photographic light-sensitive material, the silver halide grains contained in the hydrophilic colloid layer are spectrally sensitized by a compound represented by the following general formula [4], and the hydrophilic colloid layer has a compound represented by the following general formula [4].
1], [2].

It has been found that the above object can be achieved by a silver halide photographic material containing at least one of the compounds shown in [3].

General formula [41 Z represents an atomic group necessary to complete an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus,
These nuclei may have substituents on carbon atoms.

Specific examples of substituents include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), unsubstituted alkyl groups having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) , an alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group,
butoxy group), hydroxyl group, alkoxycarbonyl group having 2 to 6 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), alkylcarbonyloxy group having 2 to 5 carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), Examples include phenyl group and hydroxyphenyl group.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4.5-dimethyloxazole, 4-phenyloxazole, etc. as the oxazole nucleus; benzoxazole, 5-chlorobenzoxazole, etc. as the benzoxazole nucleus; 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6- Methylbenzoxazole, 6-medoxybenzole, 5,6-dimethylbenzoxazole, 6-chloro-5-methylbenzoxazole, etc.
Examples of the naphthoxazole nucleus include nuclei such as soot[1,2-d]oxazole, na71-[2,1-d]oxazole, and naphtho[2,3-dloxazole.

141 represents an unsubstituted or substituted alkyl group.

Examples of substituents include hydroxy group, sulfonate group,
Carboxyl group, halogen atom (e.g. fluorine atom, chlorine atom), unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (alkoxy group may be further substituted with a sulfo group or hydroxy group), 2 carbon atoms ~5 alkoxycarbonyl groups, alkylsulfonyl groups having 1 to 4 carbon atoms, sulfamoyl groups, unsubstituted or substituted carbamoyl groups (including substituted carbamoyl groups substituted with alkyl groups having 1 to 4 carbon atoms), substituted phenyl groups ( Examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, etc.), a vinyl group, and the like.

Specific examples of the R-free alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of substituted alkyl groups include 2-hydroxyethyl group, 3-hydroxypropyl group as hydroxyalkyl group, 2-sulfoethyl group, 3-hydroxypropyl group as sulfoalkyl group, etc.
-Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2
-Chloro-3-sulfopropyl group, etc., 2-sulfonate ethyl group, 3-sulfonate propyl group, carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2.2.2-1-lifluoroethyl group, 2-, (3-sulfopropyloxy)ethyl group, 2-(2-hydroxyethoxy)ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group as a sulfamoylalkyl group, 2-carbamoylethyl group, 2-N.

N-dimethylcarbamoyl, ethyl group, etc., 7enethyl group, p-carboxyphenethyl group, sulfoaralkyl group include p-sulfophenethyl group, 0-sulfophenethyl group, p-hydroxyphenethyl group, phenoxyethyl group, and the like.

R4! is an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxy7enyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group, or a substituent (CHz Seri 2
9-OTCHadingA'k table t. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or an alkoxy group having 1 to 8 carbon atoms, and n represents an integer value of 1 to 4.

The above six groups represented by the R eye also include those having substituents. For example, those in which the alkyl moiety of the above group is substituted with a halogen atom can also be preferably used.

Examples of R42 include an alkoxycarbonylalkyl group in which each alkyl group is substituted with a halogen atom (e.g., methoxycarbonylfluoromethyl group, ethoxycarbonylfluoromethyl group, fluoroethoxycarbonylethyl group, etc.), a hydroquine group (e.g., 2- Hydroxyfluoroethyl group, 2-hydroxyfluoropropyl group, 3-hydroxyfluoropropyl group, 2.3
-dihydroxyfluoropropyl group, etc.), hydroxyalcokyne alkyl group (e.g. hydroxymethoxyfluoromethyl group, 2-(2-hydroxyfluoroethoxy)
ethyl group, 2-hydroxyfluoroethoxymethyl group, etc.), carbamoyl alkyl group (N-alkyl substitution, N,
N-dialkyl substitution, N-hydroxyalkyl substitution, N
-alkyl-N-hydroxyalkyl-substituted, N,N-di(hydroxyalkyl)-substituted substituted carbamoyl alkyl groups, and carbamoyl alkyl groups of 5- and 6-membered cyclic amines) (e.g., 2-carbamoylchloroethyl groups, 2-carbamoylchloroethyl groups, -N-(2-hydroxyethyl)carbamoylchloroethyl group, N-hydroxyfluoroethylcarbamoylmethyl group, N,N-cy(2-hydroxyfluoroethyl)carbamoylmethyl group, 2-N,N-di(2-hydroxy ethyl) carbamoylchloroethyl group, N, N-
dimethylcarbamoylchloromethyl group, morpholinocarbamoylchloromethyl group, piperidinocarbamoylmethyl group, etc.), hydroxyphenyl group, hydroxyalkylphenyl group having 7 to 9 carbon atoms (e.g. p-(2-hydroxyfluoroethyl)phenyl l, m -(1-hydroxyfluoroethyl)phenyl group, etc.), or a substituent (CH
, red A or (CH, cliff 0 [cH, represents 9-A.

Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (for example, methyl sulfonyl group, ethylsulfonyl group, etc.)
and the sulfonamide group preferably has 1 to 4 carbon atoms.
sulfonamide groups (for example, N-methylsulfonamide, l,N,N-dimethylsulfonamide groups, etc.), alkylsulfonylamino groups, etc.), and the alkylsulfonylamino group preferably has 1 to 4 carbon atoms. The lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.). n represents an integer value of 1-4.

R4m and R4' may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably one having 1 to 4 carbon atoms, such as a methyl group or an ethyl group), or an alkoxy group (preferably one having 1 to 4 carbon atoms). methoxy group, ethoxy group, etc.), alkylsulfonyl group, sulfo group, chlorine atom, fluorine atom, or carboxyl group.

Particularly preferred compounds of the above general formula [4] include R41 in which R41 is a sulfo group or a carboxyl group and/or
or a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a hydroxyl group, specifically sulfoethyl group, sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3-sulfo-
Examples include 2-hydroxypropyl group.

Next, typical specific examples of the compound represented by the above general formula [4] used in the present invention will be given, but the compounds used in the present invention are limited to these [4]-1 [4]-2ゝ-13 [4]-] 34]-[4]-5 [4]-] 94]-10 [4]-]1 [4]- [4]-] 74]-8 [4]-12 [ 4]-13 [4] OCH.

[4]-15 [4]-16 [4]-17 [4]-21 [4]-22 [4]-23 OCH3 OCH.

H3 [41 [4]-19 [4] [41 [4]-25 [4]-26 [4]-27 [4]-28 [4]-29 [4]-33 [4]-34 [4 ]-35 [4]-30 [4]-31 [4]-32 [4]-36 [4]-37 The compound represented by the above-Taisei [4] used in the present invention is No. 549, 46-18105
No. 46-18106, No. 46-18108, No. 47-4085, No. 58-52574, U.S. Patent 2
, 839.403, 3,384.486, 3.
No. 625.698, No. 3,480,439, No. 3,5
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 67.458 and the like.

The merocyanine dye represented by the above general formula [4] used in the present invention can be added and dispersed in a silver halide emulsion by a conventionally known method. For example, JP-A No. 49-44895, JP-A No. 50-11
The method of dispersing and adding with a surfactant described in the specification of No. 419, JP-A-53-16624, No. 53-1
No. 02732, No. 53-102733, U.S. Patent No. 3
, 469.987 and 3,676.147, a method of adding as a solid solution as described in the specification of East German Patent No. 143.324, etc. can be mentioned. Other merocyanine dyes can be used in water-soluble solvents such as water, ethanol, methanol,
It may be dissolved in a solvent such as acetone, n-propertool, fluorinated alcohol, pyridine, etc. alone or in a mixture thereof and added to the emulsion. It may be added at any time during the emulsion manufacturing process, but it is preferably added during chemical ripening or after chemical ripening. The amount of the merocyanine dye used in the present invention is the amount for spectral sensitization of the silver halide emulsion, for example, from 10-' to 2 x 10-' mol per 1 mol of silver halide.
Preferably it is 10-4 to 2 x 10-'' moles.

Further, the merocyanine dye used in the present invention is, for example,
Special Publication No. 43-4933, No. 43-4936, No. 46
No. 18107, No. 46-1999, No. 47-1111
No. 4, No. 48-1762, No. 48-1762, No. 4
No. 8-38408, No. 56-38937, No. 58-5
No. 2574, U.S. Patent No. 2,519.0 Old No. 3,74
Supercolor sensitization can be achieved by using it in combination with other dyes disclosed in specifications such as No. 5,014 in any quantitative ratio.

General formulas [1], [2], and [3] will be specifically explained below.

General formula [l] In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is 0 to 6, and m is O
or represents l.

Here, examples of the aryl group represented by R3 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., which are preferably used as R1 and R2. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R and R3. Examples of substituents include halogen atoms (e.g., chlorine, heptadoxylate, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, impropoxy, butyl), etc.
・oxy, octyloquine, dodecyloxy, etc.), acylamino groups (e.g. acetylamino, pivallylamino, benzoylamino, tetradecanoylamino, α-(
2,4-di(-amylphenoxy)butyrylamino, etc.), sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (
(e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy groups, amine groups, alkylamino groups (e.g., methylamine, dimethylamino, etc.), carboxy groups, alkoxycarbonyl groups (e.g. , Etquin carbonyl), carbamoyl group, sulfo group, etc. Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. The bond may contain an oxy group, thio group, seleno group, carbonyl group (specifically aryl group), sulfonyl group, etc. Various substituents can be introduced into the group represented by R.

Examples of the substituent include -C0NIINIIR, (R
4 represents the same meaning as R1 and R3 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group,
Examples include a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

- Taisei [Among the compounds represented by 11, preferably R3
and R3 is a substituted or unsubstituted phenyl group, and n=
A compound in which m=1 and R represents an alkylene group.

The representative compound represented by Taisei [1] above is ■ ■ ■7 ■ ■ ” ■ ■ ■ tc511. .

■ ■ =42 c6t1w =53 tc, II+l tc, I+,.

■■ Next, the aliphatic group represented by R21, which will be explained in general formula [2], 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 heteroatoms 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 R2 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.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrorazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a deazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R21 is an aryl group.

The aryl group or unsaturated hetamine group of R2I may be substituted, and typical substituents include linear, branched or cyclic alkyl groups (preferably monomers in which the alkyl moiety has 1 to 20 carbon atoms). 2 rings), alkoxy groups (preferably those having 1 to 20 carbon atoms), 5-substituted amino groups (preferably amine groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino group (preferably carbon number 2-3
0), a sulfonamide group (preferably having 1 to 30 carbon atoms), and a ureido group (preferably having 1 to 30 carbon atoms).

Among the groups represented by R22 in general formula [2], 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 Ro in general formula [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, Among the groups represented by R22, which include a cyano group, preferred are an optionally substituted alkoxy group or an amino group.

It may be a cyclic structure containing an alkyl group, an alkoxy group, or a 10--3--N- group bond that may be substituted with A or R. However, R1 is never a hydrazino group.

R21 or Ro in the general formula [2] 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.

General formula [R21 or R2 of 21! may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
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 general formula [21], the compounds represented by the following general formula [2-al] are particularly preferred.

General formula [2-al In the above general formula [2-al, Rzs and R24 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, -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-hydroxynaphthyl group, cyclohexyl group) group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-
2-pyrrolidyl group), R16 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), R24 and R2F represent a divalent aromatic group (e.g. phenylene group or naphthylene group),
Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -5OzCIIzCIItNIISO*
NIl, -0CH, SO! Nll, -0--CI-N
-), Ro represents -NR/Rl/ or -OR,, R
', R'' and R29 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), phenyl groups (e.g. phenyl Ts, 9-methylphenyl group, p-methoxyphenyl group), or naphthyl It represents a group (eg, α-naphthyl group, β-naphthyl group), and m and n represent 0 or ■.

R2, is OR2, Specific example of general formula [21] When expressing Y is I Preferably it represents an oxatom.

The above general formulas [21 and [2 A typical example represented by al. C=0 C.F.

-[6 ■ *-N11N11CCOCII, CIl, So, CI,
C1,OH method-NIINIICCOCH,Cfl□5C
H2CH20HI =40 =33 -48 * ■ turbidity 1l -NIIN)IccN)Ic, ! H□Next, a method for synthesizing the compound 2-45°2-47 from among the above-mentioned specific compounds will be shown as an example.

Synthesis of compound 2-45 Synthesis scheme (B) (A) α-compound 4-nitrophenylhydrazine 1539 and 500
Mix mQ of diethyl oxalate and reflux for 1 hour. As the reaction progresses, ethanol is removed! & Later, it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 5 of the obtained crystals (A)
Dissolve 0g in 1000ml of methanol by heating, and
Compound (B) is obtained by reduction under a /C (palladium/carbon) catalyst in a H2 atmosphere pressurized at 50 Psi.

Add this compound (B) 229 to acetonitrile 200+n2
and pyridine 169 at room temperature.
A solution of No. 49 in acetonitrile was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

Compound (D) 309 was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

10 g of compound (E) was dissolved in 100 rnQ of acetonitrile, 3.09 g of ethyl isothionanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by crystallization.
．． Obtained 0g. Compound (F) 5.09 methanol 5
Methylamine (40% aqueous solution 81a) was dissolved in 0 mff.
) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme (B) (C) (D) (E) Compound 2-47 Dissolve compound (B) 229 in 200 mQ of pyridine and add p-nitrobenzenesulfonyl chloride 2 to a stirrer.
Added 29. 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 2-45 according to the synthesis scheme to obtain compound 2-47.

Next, general formula [3] will be explained.

Taisei [3J].

Otori Ar NIINII CR1+ In Taisei [3], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, but the diffusion-resistant group is commonly used in immobile photographic additives such as couplers. Preferred are ballast groups. 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 silver halide adsorption promoting groups include thiourea group, thiourethane group, heterocyclic thioamide group, merno-J buto-heterocyclic group,
Included are the groups described in U.S. Pat. No. 4,385,108, such as triazole groups.

R11 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, and examples thereof include groups such as methyl, ethyl, propyl, butyl, in70biru, pentyl, and cyclohexyl.

Substituents introduced into these alkyl groups include alkoxy (e.g. methoxy, ethoxy, etc.), aryloxy (e.g. phenoxy, p-chlorphenoquine, etc.), peterocyclic okyne (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 (e.g., 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.), aryloxy Carbonyl (e.g. phenoxycarbonyl, etc.), carboxy, carbamoyl, alkylcarbamoyl (e.g. N-methylcarbamoyl, N,N-
dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-phenylcarbamoyl, etc.), amino, alkylamino (e.g., methylamine, 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, benzoyl), (oxy, etc.), alkylaminocarbonyloxy (aminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), arylsulfamoyl (e.g., phenylsulfamoyl, etc.) 6
Examples include groups.

The hydrogen atom of hydrazine is a sulfonyl group (e.g., methanesulfonyl syl group (e.g., acetyl, trifluoroacetyl, etc.))
, oxalyl group (eg, ethoxalyl, etc.)).

Representative compounds represented by the above general formula [3] include:
There are the following.

=28 I sul+tr 3 =24 *-N11N+1CCH□0C11ICI+20C1,
CII, OII Next, a synthesis example of compound 3-5 will be described.

Compound 3- Synthesis of 5 Synthesis scheme Compound 3 was prepared according to the synthesis method of compound 2-45. It's a good deal.

General formula [
1], [2], and [3] are 5 x 10-' to 5 x lQ- per mole of silver halide/10 contained in the silver halide photographic light-sensitive material of the present invention. The silver halide photographic material of the present invention preferably comprises a support and at least one silver halide emulsion layer and at least one hydrophilic colloid layer on the support. The silver halide emulsion layer is coated directly on the support, or coated via a hydrophilic colloid layer that does not contain the silver halide emulsion, and the hydrophilic colloid layer is coated on the support. It may be coated as a protective layer on the silver halide emulsion layer or between the support and the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. In this case, the silver halide emulsion layer may have an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer between the silver halide emulsion layer and the protective layer. Good too. The layer containing the hydrazide compound of the present invention includes a silver halide emulsion layer and/or a silver halide emulsion layer.
Or the various hydrophilic colloid layers described above.

In the most preferred embodiment of the present invention, the hydrazide compound of the present invention is contained in a silver halide emulsion layer, and the hydrophilic colloid contained in the silver halide emulsion layer and the hydrophilic colloid layer is gelatin or a gelatin derivative. It is a silver oxide photographic material.

In order to incorporate the hydrazide compound of the present invention into the silver halide emulsion layer and/or the hydrophilic colloid layer, the hydrazide compound is dissolved in appropriate water and an organic solvent and then added, or a solution dissolved in an organic solvent is added to the gelatin layer. Alternatively, a method of adding after being dispersed in a hydrophilic colloid matrix such as a gelatin derivative or a method of adding after being dispersed in latex can be mentioned. The present invention may use any of these methods.

The hydrazide compound used in the present invention can obtain preferable image characteristics even when used alone. Also,
Two or more of these hydrazide compounds may be used in combination in an appropriate ratio without adversely affecting image characteristics.

Furthermore, the hydrazide compound of the present invention and the hydrazide compound of the present invention may be used in an appropriate ratio.

One preferred embodiment of the present invention is to add the hydrazide compound according to the present invention to a silver halide emulsion layer. In another preferred embodiment of the present invention, the hydrophilic colloid layer is added to a hydrophilic colloid layer directly adjacent to a hydrophilic colloid layer containing a silver halide emulsion layer, or to an adjacent hydrophilic colloid layer via an intermediate layer. .

In another embodiment, the hydrazide compound according to the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, ethers, esters, etc., and a silver halide photographic light-sensitive material is prepared by an overcoating method or the like. It may be incorporated into the silver halide photographic material by directly coating the outermost layer on the side of the silver halide emulsion layer.

In the present invention, combined with the hydrazide compound of the present invention,
Particularly favorable results are obtained when an anion that reduces the hydrophilicity of the hydrazide compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid,
A base of organic acids such as sulfonic acid and sulfonic acid, anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalenesulfonic acids Anions, dialkyl sulfosuccinate anions such as lauryl sulfate ayunes, tetraphenyl borons, di-2-ethyl hequinyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethanoxy sulfate anions , stearate anions, polyacrylate anions, and the like.

Such anions may be mixed in advance with the hydrazide compound of the present invention and then added together with the hydrophilic colloid layer, or may be added alone to the tedozolium-free silver halide emulsion layer or the hydrophilic colloid layer of the present invention. can be added to.

The silver halide used in the silver halide photographic light-sensitive material of the present invention has an AgCQ/A9Br ratio of 100/0.
Silver chlorobromide of 2/98 to 2/98 is preferred, AgCQ/A
Particularly preferred are those having a 9Br ratio of 90/10 to 50/50.

In addition, the average grain size of silver halide grains is 0.10 μm to 0.
．． 40 μm, and the coefficient of variation of the particle size distribution expressed as (standard deviation of particle size distribution)/(average particle size) x 100 is 15%.
The following monodisperse types are preferred.

The silver halide photographic material used in the present invention can be produced by methods known in the photographic material industry. Namely, photographic emulsion preparation methods, sensitization methods, additives, hydrophilic colloids,
These include binders, supports, processing agents, processing methods, etc.

Examples of the imaging agents for the black and white silver halide photographic light-sensitive material of the present invention include the following.

HO-e CH-CHin A typical example of an OH type developing agent is hydroquinone.

In addition, as the HOfCH=CHkenNH, type developer, ortho and rose aminophenol or aminopyrazolone are typical, and 4-aminophenol, 2-aminophenol,
-Amino 6-phenylphenol, 2-amino-4-
Chloro-6 phenylphenol, 4-amino-2-7
Dynylphenol, 3,4-diaminophenol, 3-
Methyl-4,6-diaminophenol, 214-cyamylsorcinol, 2,4,6-dolyaminofetu, N-methyl-p-aminephenol, N-β-hydroxyethyl-p-aminephenol, p. Examples include hydroxyphenylaminoacetic acid and 2-aminonaphthol.

Examples of petrocyclic type developers include l-phenyl-3-pyrazolidone, ■-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-7z- 4-methyl-
Examples include 4-hydroxymethyl-3-pyrazolidone.

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

Fourth Edition, pages 291-334 and Journal of the American Chemical Society.
an Chemical 5ociety) Volume 73,
3.100 (1951) etc. can be effectively used in the silver halide photographic material of 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. Furthermore, even if a sulfite salt such as potassium sulfite or ammonium sulfite is used as a preservative in the developer used for processing the photosensitive material of the invention, the effects of the invention will not be impaired, and one of the effects of the invention is It can be mentioned as a feature. Others - caustic alkali, such as those used in general black and white developers;
pH adjustment and buffer function using alkali carbonates or amines, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, benzyl alcohol, Development accelerators such as polyalkylene oxide, sodium alkylaryl sulfonates, surfactants such as natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, sodium sulfate, etc. It is optional to add an ionic strength regulator or the like.

The silver halide photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor, thereby obtaining photosensitive characteristics with extremely excellent storage stability.

The pH value of the developer having the above composition is 9 to 13,
From the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 12.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
The temperature is preferably 0°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes.
Particularly preferably within 40 seconds often brings about good results. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, pre-coating, neutralizing, etc., and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

[Example] A silver chlorobromide emulsion was prepared using the following solutions of liquid A, liquid B, and liquid C.

<Solution A> Ossein gelatin 179 Polyisoglobylene-polyethylene oxydisuccinic acid ester sodium salt 5 mff 1θ% ethanol solution Distilled water 1280 cc <Solution B> Silver nitrate 1709 Distilled water 410 mQ Solution C> Sodium chloride 40.9 g Potassium bromide 35 .7g polyisopropylene oxydisuccinate sodium salt lθ%
Ethanol solution 3mff ossein gelatin
11g distilled water
EA after heating 40.7raQ solution A to 40℃
Sodium chloride was added so that the g value was 160 mv.

Next, solutions B and C were added by a double jet method using the mixer described in JP-A-57-92523 and JP-A-57-92524.

After addition of liquids B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, and then desalted and washed with water in a conventional manner.
After adding 600 ml of an aqueous solution of ossein gelatin (containing ossein gelatin 309) and dispersing by stirring at 55° C. for 30 minutes, the solution was adjusted to 750 IIQ.

Next, this emulsion was subjected to total sulfur sensitization, and 6-methyl-4-hydroxy-1,3,3a,7-chitrazaindene was added as a stabilizer. The emulsion was divided, and as shown in Table 1, compounds of the general formulas [1], [2], [3] according to the present invention, or the sensitizing dyes ([4]-(
a) to (k), 3 x 1 G-' mol/Ag 1 mol were added to each for color sensitization, and a hydrazide compound (
2] -8 was added at 700+ag/Ag 1 mol, and sodium n-dodecylbenzenesulfonate was added at 600mg/A.
g 1 mol, styrene-maleic acid copolymer 2 g/Ag
1 mol of Ag and 3.5 g of Ag/lI2 on the polyethylene terephthalate film, gelatin amount of 2.09/l"
I applied it to make it look like this. At that time, the amount of gelatin is 1.0g/m'
Sodium l-decyl-2-(3-inpentyl)succinate-2-sulfonate was added as a vehicle to 30+1
g/+*”s Formalin 25119/r as a hardening agent
Multi-layer coating of hard film protective layer containing "a" [4] - (d) [4] (e) [41 (f) H Comparative sensitizing dye [4] - (a) [41 (b) [4] -(c) [4] -(g) [4]-(h) [4] (i) [4]-(D [4]-(k) The above sample piece was treated with a developer having the following formulation and a commercially available The film was processed using an automatic developing machine with a developing tank capacity of 40 I2 using a fixer.

[Development processing conditions] (Process) (Temperature) Development 40°C Fixing 35°C Washing with water 30°C Drying 50°C [Developer composition] (!Il composition A) (Time) 15 seconds 10 seconds 10 Wait for 10 seconds and take 3 pieces of each sample. One piece is exposed to stepwise light using a tungsten tip using a photosensitive needle and an optical wedge. contact screen GNNo. 2 (150L
) was used to expose the shaded areas to xenon light. Also,
One piece of the ball was subjected to the following processing without being exposed to light.

(, Phosphoric acid (composition) 5g When using a developer, it was dissolved in the order of the above composition A1 in 500mQ of pure water and finished to 1Q and used.

For developed samples subjected to wedge exposure, draw a photographic characteristic curve and calculate the sensitivity at an optical density of 2.5 for sample N.
Relative values are calculated based on o and I, and gamma is an optical density of 1.
The janθ values of the straight line portion from 0 to 2.5 are shown.

The quality of the formed mesh (dot quality) was evaluated for those that were photographed using a Canon optical camera for printing and plate making.

For dot quality, for so-called 50% dots where the area of the halftone area and the clear area are equal, the state of the fringe (blur) that occurs around the halftone dot is visually judged, and the smaller fringe is evaluated as 5.
Evaluation was made on a five-point scale.

In other words, 5% is excellent, and 1 is extremely poor. If the 50% dot quality is less than 3N,
Generally this cannot be tolerated.

In addition, for samples processed without exposure, 4 films were stacked and the remaining color of the film was visually evaluated and evaluated on a 5-point scale. showed that. For general plate making, residual color below "3" is considered to be a major drawback.

As shown in Table 2, it can be seen that only the samples color-sensitized by the sensitizing dye represented by the general formula [4] according to the present invention have high relative sensitivity, extremely high contrast, and have little residual color.

<Example 2> A sample was prepared in exactly the same manner as in Example 1.

However, the sensitizing dyes include [4]-4, [4]-14, and [4]
-24 was added in the amount shown in Table 3. Further, as hydrazide salts, general formulas [1] and [2] according to the present invention are used.

[3], the contrast compound (a”e) is 7 as shown in Table 3.
0019/Ag1 mol was added. After preparing the samples, three pieces of samples were prepared in the same manner as in Example 1, and the wedge-exposed shading indicates exposed and residual color samples.

(a) (b) (c) (d) The structure of the contrast hydrazide compound is as follows. (e) The compound represented by formula [4] is different from the sensitizing dye having a similar structure, and When used in combination with the compounds shown in [1], [2'l, and [3], yflIX produces specifically high-contrast images with extremely little dye staining. As a result, a silver halide photographic light-sensitive material is produced which can produce an image of extremely high contrast even by short-time processing using a developer with a high sulfite ion concentration and good stability, and which has extremely little dye staining after processing. It became possible.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a support and a hydrophilic colloid layer coated on the support, including at least one silver halide emulsion layer, wherein the hydrophilic colloid layer contains: The silver halide grains are spectrally sensitized with a compound represented by the following general formula [4], and the hydrophilic colloid layer contains at least one of the compounds represented by the following general formulas [1], [2], and [3]. A silver halide photographic light-sensitive material characterized by containing one type of silver halide photographic material. General Formula [4] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z represents a group of nonmetallic atoms necessary to form an oxazole nucleus, benzoxazole nucleus, or naphthoxazole nucleus. R^4^1 represents an unsubstituted or substituted alkyl group. R^4^2 represents an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or a lower alkoxy group, and n represents an integer value of 1 to 4. R^4^3, R^4^4
may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a chlorine atom or a carboxyl group. ] General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.)