JPH0224643A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity, contrast, and reproducibility of printing areas and dots by incorporating planar silver halide particles having a specific projection area diameter into emulsion layers. CONSTITUTION:The planar particles having 0.6-0.2mu projection area diameter are incorporated as the silver halide particles into the emulsion layers contg. a hydrazine deriv. of the negative type silver halide photographic sensitive material. The aspect ratio of the planar particles is preferably 3.0-7.0. The ratio at which the particles occupy in the emulsion layers into which the planar silver halide is incorporated is preferably >=50%, more particularly preferably >=90% as the halogen compsn. of the planar particles. Silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, and silver iodochloride are preferable as the halogen compsn. of the planar particles. The content of the silver iodide in case of the silver iodobromide <=10%. The planar particles formed from the (111) face, (100) face or the mixed faces of the (111) face and the (100) face are selected as the planar particles.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applied to silver halide photographic materials (particularly negative materials) that are used in the field of photoengraving and are capable of rapidly forming ultra-high contrast images using a highly stable processing solution. (type).

(Prior Art) It is known that certain silver halides can be used to form extremely high contrast photographic images, and methods for forming such photographic images are used in the field of photolithography.

Conventionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is kept extremely low (usually 0). .1 mol/2 or less). Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4,224,401 and U.S. Pat.
, 168,977, 4.166 742, 4,311.781, 4.272,606, 4.211.857, 4.243,739, etc. There is a method using a hydrazine derivative described in . According to this method, photographic properties with ultra-high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. A dramatic improvement in comparison.

However, ultra-high contrast image forming methods using these hydrazine compounds strongly promote contagious development, so when photographing character manuscripts with low contrast (especially fine lines in Mincho fonts), even areas that should be thin white backgrounds are There was a problem with the text turning black, making the text so black that it became unreadable. Therefore, if you reduce the exposure to match the fine lines of the Mincho font, the Gochinoku characters will become worse.
There was a problem with the exposure latitude. A similar problem also occurs in halftone image photography, which has disadvantages in image quality in that even the parts of the halftone dots that appear as a white background are easily blackened, and the halftone gradation becomes very short.

The cause of this is that the contagious development of high-contrast development using hydrazine compounds causes unexposed areas adjacent to exposed areas to be developed.In particular, light is transmitted to adjacent areas due to scattering of particles, etc. This phenomenon becomes even more noticeable when there is bleeding.

A method for reducing scattering of particles is to make the particle size smaller than the wavelength of the exposing light, but as the particle size becomes smaller, the sensitivity decreases and there is a problem that it cannot be practically used in a plate-making camera.

In order to solve this problem, Japanese Patent Application No. 10177/1983 proposes that the aspect ratio is 7.1 to 8.8 and the projected area diameter is 0.35μ
Tabular grains of ~0.5μ are described. However, although this particle can provide better image quality than cubic particles, although the reason for this is unclear, perhaps due to its high aspect ratio, further improvement has been desired. Furthermore, there is also the problem that it is difficult to stably prepare fine tabular grains with a high aspect ratio.

(Objective of the Invention) The first object of the present invention is to provide a silver halide photographic light-sensitive material that has high sensitivity, high contrast (for example, rlO or higher), and good reproducibility of image lines and halftone dots (wide exposure latitude). It is to provide.

The second purpose is to create a system using a hydrazine compound.
An object of the present invention is to provide an ultra-high contrast image forming method that can stably maintain performance using a stable developer.

The above-mentioned object of the present invention is to provide a negative-working silver halide photographic material having at least one silver halide emulsion layer on a support, the emulsion layer or other hydrophilic colloid layer containing a hydrazine derivative. This was achieved using a silver halide photosensitive material characterized in that the silver halide grains in the emulsion layer are tabular grains with a projected area diameter of 0.6 to 0.2 .mu.m.

The combination of a tabular emulsion and a hydrazine derivative was disclosed in JP-A-58
-108528, 58-111938, RESEAR
CHDISCLO3UREN(L22534 (198
(January 3)... etc., but c+)re-
It is a shell-type auto-type sheet positive emulsion, and does not mention ultra-high contrast negative-type silver halide photographic light-sensitive materials.

The above-mentioned Japanese Patent Application No. 10177/1987 describes an ultra-high contrast negative-working silver halide photographic material using a hydrazine compound, but it has not yet achieved sufficient image quality and exposure latitude.

The improvement in exposure latitude due to the combination of tabular grains adsorbed with sensitizing dye and hydrazine is that the tabular emulsion has a large ratio of surface area to volume (hereinafter referred to as specific surface area) and can adsorb a large amount of sensitizing dye on its surface. It is thought that it is possible to achieve both high contrast and exposure latitude by suppressing a decrease in resolution due to the ability to absorb light sufficiently and the tabular emulsion itself having low light scattering properties.

Although fine particles are preferable in order to reduce parental scattering, it has been found that particles with an aspect ratio of 7 or more provide better image quality and a preferable aspect ratio without changing the exposure latitude.

The present invention uses a fine-grain tabular emulsion having a preferable grain size and a preferable aspect ratio to provide a hydrazine high-contrast photosensitive material with high sensitivity, high image quality, and a wide exposure latitude. That is, the aspect ratio of the tabular grains of the present invention is preferably 3.0 to 7.0.

In the tabular silver halide emulsion with an aspect ratio of 3 used in the present invention, the grain diameter is 0°6 to 0.2μ.
It is. Also, the thickness is 0.2μ or less, preferably 0.02μ
μ~0.18μ.

Here, the aspect ratio is a value obtained by dividing the particle diameter by the particle thickness, and the particle diameter in this case is expressed by the diameter of a circle having the same area as the projected area of the particle.

The average aspect ratio in the present invention refers to the average aspect ratio of all the tabular silver halide grains, and the average aspect ratio may be calculated by calculating the aspect ratios of all the tabular grains individually and averaging them, The average grain diameter and average grain thickness of all tabular grains may be determined and the ratio thereof may be determined.

The aspect ratio of the tabular grains is 3 or more, preferably 5 to 7 depending on practical requirements.

Regarding the proportion of tabular silver halide grains in the emulsion layer containing tabular silver halide grains used in the present invention, it is preferably 50% or more, and 70% or more of the total projected area. More preferably, it is most preferably 90% or more.

These tabular silver halide grains were produced by
6, Japanese Patent Application No. 61-48950, etc., it is also possible to monodisperse the dispersibility of silver halide grains in terms of grain size and/or thickness.

Here, the monodispersity of tabular silver halide grains means that 95% of the grains are within ±60% of the number average grain size.
Preferably, it refers to a dispersion system whose size falls within ±40%. In the present invention, a herbaceous emulsion with a variation within ±22% is more preferred. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

The halogen composition of the tabular grains is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, or silver iodochloride. In the present invention, silver iodobromide, silver bromide, filled silver iodide, and silver chlorobromide are particularly preferred. In the case of silver iodobromide, the silver iodide content is usually 10% or less, preferably 5 mol% or less,
More preferably, it is 1 to 3 mol or less.

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions.

For example, when silver iodobromide is used, the silver iodobromide tabular grains may have a layered structure consisting of a plurality of phases each having a different iodide content. Japanese Unexamined Patent Publication 1983
-113.927, JP-A-58-113.928,
JP-A-59-99゜433, JP-A-59-119,3
Preferred examples of the halogen composition of tabular silver halide grains and the intra-grain distribution of halogen are described in No. 44 and JP-A-59-119,350.

In the case of silver chlorobromide, it can be prepared using the method described in JP-A-58-111936.

In the case of silver bromide, fine tabular grains of 0.6 μm or less as described in JP-A-63-11928 are preferred.

The tabular grains can be selected from those formed from (III) planes, (100) planes, or a mixture of (111) planes and (100) planes.

Regarding the formation site of the latent image, the particles may be such that the latent image is mainly formed on the surface of the particle, or the particle may be such that the latent image is mainly formed inside the particle. Furthermore, particles may be used in which a latent image is formed on the particle surface and inside the particle.

Next, a method for producing tabular silver halide grains will be described.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, relatively low pBr of 1.3 or less
It can be obtained by forming seed crystals containing 40% or more of tabular grains by weight in an atmosphere of 4ia, and growing the seed crystals while simultaneously adding silver and halogen solutions while keeping the pBr value at the same level.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc.

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas.

These halogenated 1i! A solvent is added during the production of tabular silver halide grains of the present invention in order to accelerate grain growth. Addition rate and amount of silver salt solution (e.g. AgN01 aqueous solution) and halide solution (e.g. 2 volumes of KBr water),
A method of increasing the concentration of addition is preferably 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 10-5 moles of iridium salt or complex salt thereof per mole of iridium, and the silver iodide content on the grain surface is low. It is a silver haloiodide with a higher than average silver iodide content. By using an emulsion containing such A-capitalized silver, photographic characteristics with higher frequency range and higher gamma can be obtained.

The silver halide emulsion used in the method of 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 chemical sensitization methods, and any of these may be used alone or in combination.

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

- Ship formula (]) In the formula, R represents an aliphatic group or an aromatic group, and R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarnebonyl group. , G1 is a carbonyl group, a sulfonyl group, a sulfoxy group, A2 is both a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group. Represents a substituted acyl group.

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

The aromatic group represented by R1 in general formula (1) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be combined with a monocyclic or bicyclic aryl 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 R5 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 group (preferably 1 to 30 carbon atoms)
) etc.

-a The alkyl group represented by R2 in formula (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, or phenyl 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 is, for example, a norogen atom, an alkyl group,
It may be substituted with a cyano group, carboxyl group, sulfo group, etc.

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.

The acyloxy group is preferably a monocyclic one, and the substituent includes a halogen atom and the like.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
Preferred are alkylamino groups and arylamino groups, which may be substituted with alkyl groups, halogen atoms, cyano groups, nitro groups, carboxy groups, etc. Carbamoyl groups include unsubstituted carbamoyl groups and those having 1 to 10 carbon atoms. An alkylcarbamoyl group and an arylcarbamoyl group are preferred, 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, preferred is G.

is a carbonyl group, a hydrogen atom, an alkyl group (e.g., methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.), an aralkyl group (e.g., 0-hydroxybenzyl group), group), aryol group (e.g. phenyl group, 3,5-
(dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

When G is a sulfonyl group, R is an alkyl group (e.g. methyl group), 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 G is a sulfoxy group, preferred R2 is a cyanobenzyl group, a methylthiobenzyl group, a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group, and a phenyl group are preferred, and a fenoquine group is particularly preferred.

When G is an N-substituted or unsubstituted iminomethylene group,
Preferred Rt is 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 R3, 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 ([) is most preferably a carbonyl group.

Also, R2 splits the G1 Rz part from the remaining molecules,
A ring that generates a cyclic structure containing atoms of the G Rz moiety,
It may be one that causes a chemical reaction, specifically one that can be represented by the general formula (a).

General formula (a) R3Z + In the formula, Zl attacks G1 nucleophilically, GR, -Z,
A group capable of splitting a moiety from a residual molecule, R1 is R7
When one hydrogen atom is removed from , Zl makes a nucleophilic attack on G, and a cyclic structure can be generated with G, , R, and Zl.

More specifically, Zl easily undergoes a nucleophilic reaction with G when the hydrazine compound of general formula (1) generates the following reaction intermediate by oxidation etc. R, -N=N-G, -R, -Z.

R, -N=A group that can split N from G, specifically OH, SH or NHR, (R is a hydrogen atom, an alkyl group, an aryl group, -COR, or -SOx
(where R2 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), G such as C0OR, etc.
, may be a functional group that directly reacts with (where O
H, SH, NHR.

Even if COOH is temporarily protected to generate these groups by hydrolysis with alkali etc. ○ N
R? ]111 good) or CRb CRb (Rh.

(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 also be a functional group.

Furthermore, the ring formed by G, R3, and Z is preferably 5R or 6R. Among those represented by general formula (a), preferred are general 2〇)) and (
C) can be mentioned.

+CR,' L 27C II B of the general formula, where RhI to R, a represent a hydrogen atom, an alkyl group, (preferably one having 1 to 12 carbon atoms) an alkenyl group (preferably one having 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 5R ring or a 6-membered ring which may have a substituent, m and n are 0 or 1, and (n+m) 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.

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

General formula (C) Rc (-N-)7-(-CRe'Rc''-)T2
In formula 1, Rc' and R% represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom,
It can be the same or Tatsumi.

Re3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p i′! , o or 1, and 9 represents 1-4.

Rc', Rc! and R% may be bonded to each other to form a ring as long as Z and Z have a structure in which they can make an intramolecular nucleophilic attack on G1.

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

q preferably represents 1 to 3; when 9 is 1, ρ represents 1 or 2; when q is 2, p represents 0 or l; when q is 3, ρ represents 0 or l; when 9 is 2 or CR when 3
c'Rc'' may be the same or different.

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

A+ and Az are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl M (preferably phenylsulfonyl groups or Hament's sum of substituent constants is -0
, 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or Hame 7) substituted so that the sum of the substituent constants is -0.5 or more. a benzoyl group, or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group) )) A hydrogen atom is most preferred as A2 and At.

R5 or R2 in the general formula (1) 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, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

R5 or Rz in the general formula (1) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
347, JP-A No. 59-195.233, JP-A No. 59-2
No. 00231, No. 59-201.045, No. 59-2
No. 01.046, No. 59-201.047, No. 59-
201,048, 59-201,049, JP-A-61-170,733, JP-A-61-270.744,
Patent Application No. 62-948, Patent Application No. 62-67.508, No. 6
Examples include groups described in No. 2-67.501 and No. 62-67.510.

-i Specific examples of the compound represented by formula (I) are shown below.

However, the present invention is not limited to the following compounds.

■-3)! -5) J-10) I-6) ■ Correct -9) cH, c) IzCHzSH ■ H ■-18 H ! -22)! -30) LLS1111! -32) I -41) HI] -38) J In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO5LIRE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4,38
No. 5,108, No. 4,459.34T, No. 4,560
, No. 638, No. 4,478,928, British Patent No. 2,0
11,391B, JP-A-60-179734, JP-A-61-170,733, JP-A-61-270.744,
No. 62-948, EP No. 217,310, Patent Application No. 1983
-175.234, 61-251,482, 6
No. 1-268,249, No. 61-276.283, No. 62-67.508, No. 62-67529, No. 62
-67.510, 62-58.513, 62-
No. 130,819, No. 62-143,469, No. 62
-166.117 can be used.

The amount of hydrazine derivative added in the present invention is halogenated! lXl0-6 mole to 5X per mole of barley
It is preferable to contain 10-" mol, especially lXl0-"
The preferred amount to be added is in the range of 'mole to 2 x 10-' moles.

In the present invention, a compound of general formula (II) can be used as a nucleation accelerator.

General formula (II) / / / X represents a divalent linking fund consisting of an atom or group of atoms selected from hydrogen, carbon, nitrogen, oxygen, and sulfur atoms. A is a panoramic view of the covalent linking group. Bl-m represents an amino group, an ammonium group, or an arsenic-containing heterocycle, and the amine group may be substituted. m is /, 2 or 3
, where n is 0 or / full view. ) The group represented by Y that adsorbs to silver halide includes a variety of chemical compounds containing organic compounds.

When Y is a nitrogen-containing heterocyclic compound, the general formula (1)
The compound is represented by the following general formula CI[).

General formula (I[) In the formula, lbaOmanoba/''t-thorny, m is /, 2mano is 3zenshiwa, n is Q-4 is / full view.

÷(X←A−B)□ has the same meaning as that in the general formula (I), and QI′i carbon atom, nitrogen atom, oxygen atom,
Composed of at least one type of sulfur atom! Or represents a group of atoms necessary to form a 4-membered heterocycle.

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

Examples of the heterocycle formed by Q include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, Examples include azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, and quinolines.

M is a hydrogen atom, an alkali metal atom (e.g. sodium atom, potassium atom, etc.), an ammonium group (e.g. trimethylammonicum group, dimethyl/dyl ammonium group, etc.), under alkaline conditions M = H or an alkali metal atom; Vine group (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.) t-table waste.

These heterocycles include nitro atoms, halogen/no atoms (for example, salt purple atoms, bromine atoms, etc.), mercapto groups, cyano groups, and substituted or unsubstituted alkyl groups (e.g., methyl groups, ethyl alcohols, globils, etc.). i, t-, + chilli, cyanoethyl ■, methoxyethyl, methylthioethyl i
,NaL aryl (e.g. (gephenyl(, μm methane h*y7 midophenyl, ≠-methylphenyl i,
3. tA-dichlorophenyl, naphthyl 4, etc.),
Alkenyl hen (resuege allyl toad, etc.), aralkyl 3 (
f,] evahencil, ≠-methylbenzyl, phenethyl, etc.), alkoxy groups (e.g., methoxy group, ethoxy, 4), aryloquine (e.g., evahenoxy, ≠-meth, diphenoquine, etc.), (No.), Alkylthio (
For example, methylthio, ethylthio, methoxyethyl, -, +), arylthio (for example, phenylthio)
, sulfonyl group (1"IL): methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group,
'4), lupamoyl group (e.g. % substituted carbamoyl, methylcarbamoyl, phenylcarbamoyl, etc.), sulfamoyl group (e.g. fully substituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), Carbonamides (1te1) (boa seven-domains, benzamides, etc.), sulfonamides (e.g. methanesulfonamides, benzenesulfonamides, etc.)
, p F luenesulfonamide toad, etc.), aralkyl child (jelly is acetyl oxine flea, penzoyl oxine lily, 4
), sulbonyl bankinzi (shio:]e; gomethanesulfonyl oson jin, go), ureido group (yl" is an arbitrary ureido group, methylureido group, ethylfreido, funinylureido group, etc.), Thiouraid dried (gae 1-!'
Non-violet-substituted thioureido group, methylthioureido i, 4)
, A/Ruzawa ((Da1e: Bua seven chillmo, benzoyl strange,
hemorrhoids), hete = ring (resage/-molbolinomo, /-piperidi7 group, -1 pyridyl group, ≠-pyridyl group, -1 chenyl group, /-pyranolyl group, /-imidanlyl group, l
-tetrahydrofuryl, tetrahydrofuryl, g)
, Omo/carinyl group (+i': g-, methane carbonyl group, phenosodicarbonyl group, etc.), oxycarbonylamino group (e.g., methoxycarbinylamino group, phenoquinyl carbonyl group, - monoethyl hequinyl fluoride, luponylamino, etc.), amino groups (for example, @giriamino=, dimethylamine, methoxyethylamino, aniIJ, etc.), carbo/shuku de sho, that term, suru. Non-sukma-zhi may also be a monomer with seven salts, hydroquine groups, etc.

X 7)” W D T' l [[D ):!n%Jeds -S-0--N- II II ll-C as 4 spores
--8 (J--08- etc. are confused, but 11] 1 These slow groups are straight-chained or separated altholene (shio 1 je (gomethylene), Ethylene cloud, propylene group, phthalate, hexylene group, /-mether ether/
丞、"%) k may be bonded via k 5 几1, R
2, this 3, le 4, R5, ordinary. , 几7, R8, R93 and ``10 are hydrogen atoms, 7) 1, respectively, are substituted or fully substituted alkyl groups (e.g. methyl, ether, pucovir,
n-butyl pressure, number), = Ei or Mudokan's aryl bottle (9th gophenyl bottle, co-methylphenyl bottle, etc.)
, Hitomoku or giant 1-substituted alkenyl (relie is pucobenyl L/-methylvinyl cloud, No.), 1h hani Ikyo or fully substituted aralkyl child (de1'e'gobenzil),
Ding representing phenethyl (Yu, 碍).

Aζ 21 plane of luck is complete, and as two renary balls, Wataru Wataru 7t is a branched alkylene group (e.g. methylene group, ethylene group, propylene group, methylene group, hekyl group a, i
-methyk: L f L/ 74, etc.), (1 chain meaning is a branched alkenylene group (Example 1 Egevinylene J, /-
Methylvinylene, etc.), straight chain or 7t branched aral life group (vl) (bubenzylidene, etc.), arylene A (f:jiH, -f phenylene, naphtele/, etc.)
etc. The above-mentioned boxes X and A that are AT-substituted may be further replaced by Tadasai O's group.

B10: lt summons or ≠ Amin Tadashi is one role type (■
) and folded in a folded shape (■). charcoal = 6
' to 30 alkyl, alkenyl, or aralkyl groups, and these groups are straight-chain (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl group, benzyl group, /-naphthylmethyl group, etc.), branched (e.g. isopropyl group,
It may be t-octyl, etc.) or cyclic (eg, cyclohexyl, etc.).

Furthermore, FLl 1 and kLl 2 may be connected to form a ring, in which all seven or more heteroatoms (such as oxygen atoms, sulfur atoms, and mercury atoms) are included. It may be cyclized to form a saturated heterocycle, such as a pyrrolidyl group, a piperidyl group, a morpholif group, and the like. Examples of the #transformed silkworms of 几11, FL, and 12 include carxyl group, sulfo group, cyano group, norogen atom (for example, fluorine atom, chlorine atom, and bromine atom), hydroxyl group, and carbon. Alkoxycarbonyl groups of up to 20 carbon atoms (e.g., methoxycarnyl group, ethoxycarinyl group, phenoxycarmenyl group, benzyloxycarminyl group, etc.), alkoxy groups of up to 20 carbon atoms (e.g., methoxycarnyl group, ethoxy group, benzyloxy group) , phenethyloxy group, etc.), a monocyclic aryloxy group with a carbon number of 0 or less (e.g., phenoxy group, p-tolyloxy group, etc.), an acyloxy group with a carbon number of 20 or less (e.g., acetyloxy group, propionyloxy group, etc.) , an acyl group having 20 or less carbon atoms (914, acetyl group 1, propionyl group, benzoyl group, mesyl group, etc.),
Carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinosulfonyl group, Pi is lysinocarzenyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group,
Morpholinosulfonyl group, py(lysinosulfonyl group, etc.), acylamino group with carbon d20 or less (e.g. acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, p-toluene group, etc.) sulfonamides, etc.)
, carbon amide group having 20 or less carbon atoms (e.g. methylcarbonamide group, phenyl carnoamide group, etc.), ureido group having 20 or less carbon atoms (e.g. methylureido group,
(such as a funinylureido group), an amine group (synonymous with general formula (■)), and the like.

The ammonium group of B is represented by the general formula (■).

(Zo).

(In the formula, B13 R14, B15 are the above-mentioned general formula ('
It is a group similar to FLll and R12 in VI[), and Ze represents an anion, for example, ... lightiore (f'J, jbaC!!e, B r'', xe6, etc.),
Sulfonate ions (e.g. trifluoromethanesulfo f-1, ha:17) luenesulfonate, benzenesulfonate, parachlorobenzenesulfonate, etc.), sulfate ions (e.g. ethyl sulfate, methyl sulfate, etc.), perchlorade, Examples include tetrafluoroborate. p represents Omanoha/i, and is O when the compound forms an inner salt. ) The element-containing heterocycle of B contained at least 7 or more nitrogen atoms! or a t-membered ring, in which the substituent t
- or may be condensed with another ring. Examples of the continuous heterocycle include an imidazolyl group, a pyridyl group, and a thiazolyl group.

Among general formulas (11), preferred are compounds represented by the following general formulas (l[I), (IV), (V), or CM).

General formula (III) General formula (1'v') General formula (V) General formula (■) ()C+-A-B Same as that of (1). Zl, Z2 and Z3 have the same meaning as +X square, AB in the general formula (II), or a halogen atom, an alkoxy group having 20 or less carbon atoms (e.g. methoxy group), hydroxyl, hydroxyamino, substituted and an unsubstituted amine group, and its substituents include Bll, R in the general formula (■)
' Can be selected from 12 substituents. However, Z.
At least one of Z2 and Z3 is +Xu-A-B
It is synonymous with roru.

Further, these heterocycles may be substituted with a substituent applicable to the heterocycle of general formula ([).

Examples of compounds represented by the general formula (and) are shown below, but the present invention is not limited thereto.

/ /2 /3゜/4t KoO, 2U (CH2+2NH2 λ3 2hiro3/ .27 KoL 3! 3rih μO 4t≠ 1, t! ψYug2 α The bale-forming accelerator used in the invention is , Berichte der Deutschen Hemitsien Geselschaft (Be
Richte der I)eutschen
Chemischen Ge5ellschaft)
+2J', 77 (/19ri, Tokukaisho!0-37113
No. 4, same! /-J, 2J No. 7, US Pat. No. 3,2, No. 27, US Pat.
Chemischen Gesellschaft) J
2, zlr (ir19), 2y, 21. t13 (/
lr5'J), Jerfk-yFpu Chemical Engineering (J, Chem, Soc,)/ri3x, 1rot
, Journal of the American Chemical Society (J, Am.

Chem, Sac, )7/, t, tooo (/riμri)
, US patent r, tr! , Jr. No. 2, ! It/
.

2≠ issue, Adoptions in Heterocycle IJ
7ri-chemistry (Advanceo InHet
erocyclic chemistry)! Ps
/ l j (19AJ'), Organic 5 synthesis IV
,! 2ri (/rit3), Journal of the American Chemistry Society (J, Am, Chem,
Soc,)≠! , 23ri 0 (1923), Chemische Beric'hte
the law of nature,! Jj (/J'7J), Tokuko Showa 410-28'41
9Δ1. Tokukai Akira! O-♂ri No. 034L, US Patent 3.
IO≦, Hirobu No. 7, 3,4120. t70, same,
2'7/.

, No. 22, 3. /37. ! No. 71, 3. /4tr
, ott issue, same! ,! //, AtJ issue, same 3゜OtO,
No. 02f, 3, 27/, /! No. 41, 31 pieces! /,
tri No. 7, same 3. ! Rir, T Tata, same 3. /4#, O
tt issue, special public show 413-'A/J! No. 3, U.S. Pat. Otsu/, t, t/A, same 3. ≠Ko, g64, same 3.
07/, l/-tj, same λ.

t4uu, tor, same 2. II-till, tOt No., 2.4t4#) No. 07, same, ri 36,410≠ No. JP-A No. 7-202. ! No. 31, same! 7-lbu7,02
No. 3, No. 77-/J4t, No. 737, to-to.

No. 139, same jr! -/! 2.23! Same issue! 7-7 da, f j J issue, same! Tar/Otoko,! ≠ and the same number. −
730, 7j No. 7, same t O-/j r, j 44
,! No. ', TFfJtr-x3. rsr issue, same sr-
/z9,329, same 3 ter/! ri, No. 742, same tO
-2/7,3! J' No., same J/-J' 0.131
No., Special Public Show No. 29,390, No. 4O--2F, J
"No. 11, 40-/JJ, No. 1, 7/-/
, 4' j No. 7, etc., it can be easily synthesized.

The optimum amount of these accelerators to be added differs depending on the type of compound, but 1. OXl0- to 0.5 g/rd, preferably 5. It is desirable to use it within the range of OXl0-' to 0.1 g/rrT. These accelerators can be used in a suitable solvent (
Alcohols such as HtO1 methanol and ethanol,
It is dissolved in acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A plurality of types of these additives may be used in combination.

The sensitizing dyes used in the present invention include various sensitizing dyes known in the field of photographic materials, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemicyanine dyes. Included are oxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon is fused to these nuclei, that is, Indolenine nucleus, henzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be placed 1 m above the carbon atom.

Merocyanine dyes or complex merocyania dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.080;
U.S. Patent No. 2,231.658, U.S. Patent No. 2,493.748
No. 2.503.776, No. 2.519.001, No. 2,912.329, No. 3.656,959,
No. 3,672,897, No. 3,694,217, British Patent No. 1,242.588, Japanese Patent Publication No. 14030/1973
No., JP-A-53-137133, JP-A-55-450
15, as described in Japanese Patent Application No. 61-79533.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes 11 Combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are listed in Research Disclosure in addition to the above.
Volume 176 17643 (Published December 1978) No. 23
It is described in sections A-J on page 2.

Here, the sensitizing dye and the like can be added at any step in the manufacturing process of the photographic emulsion, or can be added at any stage after the manufacturing of the emulsion up to just before coating.

Examples of the former include particle formation, physical ripening, and chemical ripening.

The sensitizing dye used in the present invention is added to the silver halide emulsion as a solution dissolved in 1 volume of water or a water-miscible organic solvent such as methanol, ethanol, propyl alcohol, methyl cellosolve, or pyridine. .

The timing of adding the aggravating dye used in the present invention to the emulsion is as follows:
-C is carried out before the emulsion is coated on a suitable support, but it may also be carried out in a chemical ripening step or in a silver halide grain forming step.

In the present invention, the sensitizing dye is preferably added in an amount of 1 O-h-10-' mol per 1 mol, preferably lo-4 to 1 O-2 mol.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used especially for the purpose of supersensitization.

The light-sensitive material used in the present invention contains dyes for use as filter dyes, irradiation prevention, and other purposes.
May contain water-soluble dyes. Such dyes include oxonol dyes, benzylidene dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and benzylidene dyes are useful. Specific examples of dyes that can be used include British Patent No. 58
No. 4.609, No. 1,177.429, Japanese Unexamined Patent Publication No. 1977-
No. 85130, No. 49-99620, No. 49-114
No. 420, No. 52-20822, No. 59-154439
, No. 59-2085/I8, U.S. Patent No. 2,274,78
No. 2, No. 2,533,472, No. 2.95 (i, 87
No. 9, No. 3.148187, No. 3,177.078, No. 3,247.127, No. 3,540.887,
No. 3゜575.704-, No. 3.653,905,
It is described in No. 3.718.427.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as henzthiazolium salts, nitroindazoles, chlorohenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, penzothiazoles, nitrohencitriazoles, etc. ; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy Z-substituted (1,3,3a,7) tetrazaindenes); ), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as henzene thiosulfonic acid, henzene sulfinic acid, henzene sulfonic acid amide, hydroquinone derivatives, etc. . Among these, preferred are benzotriazoles (eg, 5-methyl-hensitriazole), nitroindazoles (eg, 5-nitroindazole), and hydroquinone derivatives (eg, hydroquinone, methylhydroquinone).

Further, these compounds may be included in the treatment liquid.

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, active vinyl compounds (1,35-triacryloyl-hexahydro-5-triazine, 3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (24-dichloro-6-hydroxy-s-triazine, etc.) , mucohalogen acids, etc. can be used alone or in combination. Among them, JP-A-53-4122
1, 53-57257, 59-162546, 6
The active vinyl compounds described in US Pat. No. 0-80846 and the active halides described in US Pat. No. 3,325,287 are preferred.

The photographic emulsion layer or the hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photo1'L property improvement (for example, development acceleration). , contrast enhancement, sensitization), etc., and may contain various surfactants.

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

When used as an antistatic agent here, surfactants containing fluorine fluorine (for example, US Pat. No. 4,201,586, JP-A-60-80849) are particularly preferred.

The light-sensitive material used in the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates alone or in combination, or combinations of these with acrylic acid, methacrylic acid, etc. - polymers containing u as an "Ii m" component can be used.

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

The photosensitive material used in the present invention includes, for the purpose of promoting development,
It may contain quaternary onium salts or amine compounds described in Japanese Patent Application No. 124830/1983.

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 compounds having acid groups include polymers or copolymers having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, Japanese Patent Application No. 60-56179 and No. 60-
No. 68873, No. 60-163856, and No. 60-
The description in the specification of No. 195655 can be referred to. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, acid salts such as acrylic acid and crosslinkable compounds having two or more unsaturated groups such as divinylhenzene are particularly preferred. It is a water-dispersible latex, a copolymer consisting of monomers.

As the binder or protective colloid used in the photosensitive material, it is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used. Specifically, Research Disclosure 1--(RIiSEAflCHDI
SCLO5IJRE) Volume 176, No. 17643
(December 1978) (7) Described in Section IX.

In addition to the silver halide emulsion 1n, the photosensitive material used in the present invention includes a surface protective layer, an intermediate layer, a filter layer,
A hydrophilic colloid layer such as an antihalation+fx layer can be provided.

In addition, the photosensitive material used in the present invention has 1'll of front and back sides.
A back layer (hereinafter referred to as a back layer) may be provided for the purpose of different properties, curling properties, prevention of halation, etc.

The back layer used in the present invention preferably contains a matting agent having a relatively large average particle size, especially from the viewpoint of adhesion resistance. The preferred average particle size is 1.0μmm-
1OI1, particularly preferably from 2.0 μm to 5.0 μm.

The surface protective layer also contains a homopolymer of polymethyl methacrylate, a copolymer of methyl methacrylate and methacrylic acid, magnesium oxide as a matting agent, and U.S. Pat.
Silicone compound described in No. 8, Japanese Patent Publication No. 56-2313
In addition to the colloidal silica described in No. 9, paraffin wax, higher fatty acid esters, denso, etc. can be used.

Further, polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer.

In order to obtain ultra-high contrast and high-sensitivity photographic l'L characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a high It is not necessary to use an alkaline developer, and any stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at 0.15 mol/jI! Including the above,
pH 9.5 to 12.0, especially when it contains a compound of formula (1), pH 1.0 to 12.0. When it depends on p
By using a developer of H9.5 to H12.0, photographic characteristics of sufficiently high contrast and high sensitivity can be obtained.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes since it is easy to obtain good halftone quality, and furthermore, it is preferable to contain dihydroxybenzenes in terms of developing ability. -Combination of phenyl-3-pyrazolidones or dihydroxybenzenes and ρ-
Combinations of aminophenols are preferred.

Dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc.
Hydroquinone is particularly preferred.

As the developing agent for I-phenyl-3-pyrazolidone or its derivative used in the present invention, l-phenyl-3-virapritone, ■-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4methyl-4-hydroxymethyl -3-pyrazolidone and the like.

Examples of the ρ-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, ρ-aminephenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. Among them, N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/2 to 0.8 mol/l. Furthermore, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols, the former should be 0.
05 mol/l -0.5 mol/1, 0.06 mol/l
It is preferable to use it at a maximum of mol/l or less.

Preservatives for sulfite used in the present invention include 11: sodium sulfate, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite, and the like.

Sulfite is at least 0.255 mol/1, especially 0.3 mol/1
However, if too much is added, it will precipitate in the developer and cause Wllη staining, so the upper limit is preferably 1.2 mol/l.

As the alkaline agent used for setting the pH, ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, sodium carbonate, etc.) can be used.

In the developing solution used in the present invention, a buffering agent is added.
Boric acid described in No. 1-28708, JP-A No. 60-9343
The saccharides (e.g. sucrose), oximes (
For example, acetoxime), phenolic surface (for example, 5-sulfosalicyl), tertiary phosphate (for example, sodium salt, potassium salt), etc. are used, and boric acid is preferably used.

to the developer (preferably I
A buffering agent (having an acid dissociation constant of -12) can be added at least 0.1 mol/P, particularly from 0.2 mol/e to 1 mol/r. By adding these compounds, it is possible to stably obtain the effects of ultra-high contrast and increased sensitivity caused by hydrazines, even when using an automatic processor, regardless of the silver content or blackening rate of the photosensitive material being developed. become. Incidentally, the acid dissociation constant herein means a compound having an acid dissociation constant of 1X10" to 3X10-", regardless of the first, second, third, etc.

Additives used in addition to the above components include ρ11 regulators such as potassium hydroxide and sodium carbonate; development inhibitors such as sodium bromide and potassium bromide; and ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide. fa solvents; development accelerators such as alkanolamine dazoles or derivatives thereof such as jetanolamine and triethanolamine'; ■mercapto compounds such as phenyl-5-mercaptotetrazole, indazole compounds such as 5-nitroindazole, 5- A benz-1-riazole compound such as methylbenz-triazole is mixed with an antifoggant or a black bottle.
pepper) as an inhibitor, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc., if necessary.

The fixing agent contains a thiosulfate such as sodium thiosulfate or ammonium thiosulfate as an essential component, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0.1 to
It is about 5 mol/l.

Examples of acidic hardeners in the fixing solution in the present invention include water-soluble aluminum salts, chromium salts, and ethylenediaminetetraacetic acid complexes using trivalent iron compounds as oxidizing agents. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate, and potassium alum.

A preferred additive is O, Of mol to 0.2 mol/i! , more preferably 0.03 to 0.08 mol/l.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. These compounds are the fixer
It is effective to contain 0.005 mol or more, especially 0.0
Particularly effective is 1 mol/2 to 0.03 mol/l.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, aluminum potassium tartrate, antimonyl potassium tartrate, antimonyl sodium tartrate, lithium hydrogen tartrate, Examples include lithium tartrate, magnesium hydrogen tartrate, potassium boron tartrate, and potassium lithium tartrate.

Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain preservatives (e.g. sulfite, bisulfite), buffers (e.g. acetic acid, boric acid).
, p 1+ modifiers (eg, sulfuric acid), and chelating agents (described above). Since the pH of the developer is high, the p[lll buffering agent is used in an amount of about 10 to 40 g/l, more preferably about 18 to 25 g/l.

The fixing temperature and time are the same as for development, approximately 0°C.
~50°C for 10 seconds to 1 minute is preferred.

Next, the present invention will be explained with reference to examples.

In addition, the following formulation was used as a developer.

Treatment liquid prescription (1) Hydroquinone 50.0 gN
Methyl-p-aminophenol 0.3 g2 Sulfate Sodium hydroxide 18.0 g5
-Sulfosalicylic acid 55. Og potassium sulfite 110.0 g ethylenediaminetetraacetic acid disodium 1. Potassium bromide 5-methylbenzotriazole 2-mercaptopenzimidazole 5-sulfonic acid 3-(5-mercaptotetrazole)benzenesulfonic acid sodium 10.0 g 0.4 g 0.3 g 0.2 g Um N- n-Butyljetanolamine 15.0 g Add sodium toluenesulfonate water to 8.0 g PH 11,6 Treatment liquid prescription (1) Hydroquinone 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone sulfite Potassium ethylenediaminetetraacetic acid disodium 25.0 g 0.5 g 90.0 g 2.0 g Potassium bromide 5.0 g 5-methylbenzotriazole 0.2 g 2-mercaptohenreimidazole = 5-sulfonic acid 0.3 g Sodium carbonate 50 .0 g (Add sodium hydroxide to adjust pH to 10.6) Add water 11 Preparation of emulsion A Add 7 g of gelatin and 4 g of KBr to water 12, and add p I
While adjusting the I6.0 and keeping the solution temperature at 25°C, Ag
NO3 aqueous solution (A g N 0.32.6g) and KB
r aqueous solution (K B r 24.08 g) was added at the same time over 4 minutes, then 25 g of gelatin was added and p
Adjust H to 6.5, raise to 60°C, and at this temperature
After aging for 0 min, AgN0. Aqueous solution (A g NOs
26g) and KBr aqueous solution (KBr 18.94g)
were added at the same time over 25 minutes. During this time, the silver potential of the solution was maintained at -20 mV.

After leaving it for 5 minutes, AgN0. Aqueous solution (A g
NOx 39g) and KBr water-soluble? &(KBr28
．． 0 g) was simultaneously added over 25 minutes so that the silver potential was -20 mV.

After the addition was completed, the mixture was precipitated and washed with water, followed by dispersion, by a conventional method. The resulting emulsion had an average grain size of 0.42 μm, an average thickness of 0.076 μm, an average aspect ratio of 5.5, and a coefficient of variation of projected grain size of 22%.

Preparation of emulsion B In the preparation of emulsion A, the third AgNO3 aqueous solution and K
The same procedure was carried out except that the addition of the Br aqueous solution was omitted, and the average particle size was 0.
．． 32μ, average thickness 0.076μ, average aspect ratio 4
．． 2. An emulsion with a coefficient of variation of 19% was prepared.

Preparation of emulsion C In 11 parts of water, 12.5 g of gelatin, 5 g of KB r,
was added to adjust the pH to 6.0, and while maintaining the solution temperature at 25°C, AgN0. Aqueous solution (AgNCh 32.6g)
and a KBr aqueous solution (24.45 g of KBr) were added simultaneously over a period of 4 minutes. Thereafter, in the same manner as Emulsion A, an emulsion having an average grain size of 0.48 .mu.m, an average thickness of 0.08 .mu.m, an average aspect ratio of 6.0, and a coefficient of variation of 19.3% was prepared.

Preparation of emulsion: Emulsion A was prepared in the same manner except that the temperature during grain formation in the first stage was changed from 25°C to 35°C, and the average grain size was 0.5.
6μ, average J:lmi 0.094, average aspect ratio 6
．． An emulsion with a 01 coefficient of variation of 16.0% was prepared.

Emulsion tone! ! ! E When preparing emulsion A, the third stage halogen aqueous solution is KL'
AgBr1 (11 mol%)
was prepared.

The obtained emulsion had an average grain size of 0.40μ and an average thickness of 0.0
75μ, average aspect ratio 5.3, and coefficient of variation 21%.

Preparation of Comparative Emulsion (Emulsion F) The same procedure was used as in Emulsion A except that the temperature at the time of grain formation in the first stage was changed to 43°C, and the average grain size was o, 62μ, the average thickness was 0.087μ, and the aspect ratio was 7. .1, coefficient of variation 16.
Emulsion No. 8 was prepared.

(Emulsion G) In the presence of ammonia, AgNO3 solution and KBr solution were added simultaneously for 60 minutes to a gelatin aqueous solution kept at 50°C, and by keeping PAg at 7.8 during that time, an average particle size of 0.35 μm was obtained. A cubic monodisperse emulsion (emulsion G) was prepared.

Also, by adjusting the amount of ammonia, 0.27μ
A cubic monodisperse emulsion (emulsion II) was prepared.

After forming grains, each emulsion was washed with water and dispersed.

Example 1 1-hydroxyethoxyethyl-3-(2-pyridyl)-5-(3-(4-sulfobutyl)-5chloropenzoxazolidenethylidene) was added as a sensitizing dye to emulsions A-G. Adding 5X10-' mol of ethoxyethylthiohydantoin potassium salt per mol of Ag;
Others 4-hydroxy-6-methyl 1,3.3a, 7-
Chitrazaindene, polyethyl acrylate dispersion,
Ascorbic acid, 1,3-divinylsulfonyl-2propatur was added. Furthermore, 8 mg/ni of hydrazine compound 1-15 of the present invention was added to the polyethylene terephthalate film so that the amount was 1 lurt and 3.4 g/rd, and a geladine protective layer was applied thereon to prepare samples a to g. .

In order to examine the exposure latitude of the character manuscript of each sample,
After photographing a grade 7 Mincho font (Tsukasa) and Gothic font (Ren) 5-character manuscript with a Dainippon Screen camera (DSC351), it was developed for 30 seconds at 34°C using the developer recipe (1) above. , fixed, washed and dried.

The shooting conditions were that the fine lines in a certain area of the Mincho typeface were 40 μm.
The quality of the Gothic font (the clarity of the letters) was evaluated.

Evaluation is performed on a five-level scale, with "5" representing the best quality and rlj representing the worst quality. r5j, "4" is practical, r
3. Although it is poor quality, it is barely practical. rl,
is not practical.

Example 2 When preparing samples a to e of Example 1, the compound U-15 was added to give 50 mg/r4 to prepare samples a' to e'.

Photographs were taken to examine the exposure latitude in the same manner as in Example 1, developed for 3Q seconds at 38° C. using the developer formulation (2), fixed, washed with water, dried, and evaluated in the same manner.

Example 3 When preparing samples a-e of Example 1, 1-38 was used instead of ■-15, and samples a# to e# were prepared by using 1-38 in place of ■-15 to give 40 ■/nT. It was developed and evaluated in the same manner as 1.

Example 4: When preparing samples a to e' of Example 2, 1-41 was used instead of I-15 so that the image quality was 10+ng/+Tf. Samples a1 to e'' were prepared and developed in the same manner as in Example 2 using the developer (2) and evaluated.

Procedural amendment

Claims (1)

[Claims] In a negative-working silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer, halogenation of the emulsion layer A silver halide photosensitive material characterized in that the silver grains are tabular grains with a projected area diameter of 0.6 to 0.2 μm.