JPH07104420A - Silver halide photographic material and image formation - Google Patents

Abstract

PURPOSE:To obtain the photographic characteristics having hard negative gradation and always stable photograph characteristics (sensitivity, gamma, image quality), and eliminate dispersion, by allowing hydrazine derivatives and the nucleus formation accelerating agent to be contained in different layers. CONSTITUTION:A negative type silver halide emulsion layer is formed on a supporting body, and the silver halide emulsion preferably consists of the silver halide particles having a silver chloride content of 50mol% or more, and hydrazine derivatives are contained in the emulsifier layer and/or other hydrophilic colloid layer, and the nucleus formation accelerating agents are contained in the layer different from the layer containing hydrazine derivatives. The nucleus formation accelerating agent is perferably the compound represented by the formula. In the formula, each of R1-R3 is an alkyl group, cycloalkyl group, aryl group, alkenyl group, cycloalkenyl group, or a hetero ring residual, and (m) is 1 or 2, and L represents an (m) valence organic group which is juined with a P atom by carbon atoms, and (n) is an integer of 1-3, and X is an (n) valence anionic ion. and X represents an acid anion. Each of n, p and m is 1 or 2 indepently.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material, and in particular, a silver halide capable of obtaining a high contrast negative image useful in a photomechanical process by using a processing solution having a pH of less than 11.0. It relates to a photosensitive material.

[0002]

Various additives have been proposed for the purpose of improving the photographic characteristics (sensitivity, fog, rapid developability, etc.) of silver halide light-sensitive materials.

Addition of a hydrazine compound to a silver halide photographic emulsion or a developing solution is disclosed in US Pat. No. 3,73.
No. 0,727 (developing solution in which ascorbic acid and hydrazine are combined), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image),
No. 3,386,831 (containing β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitizers), No. 2,419,975 and Mees.
By The Theory of Photographic Process 3rd Edition (1
966), page 281 etc. Among these,
In particular, U.S. Pat. No. 2,419,975 discloses that addition of a hydrazine compound gives a high contrast negative image. According to the patent specification, when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH of 12.8, a gamma (γ) of more than 10 and extremely high photographic characteristics are obtained. Is listed. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use. A silver halide light-sensitive material containing a hydrazine compound,
An attempt has been made to develop a high contrast image by developing with a developer having a lower pH. In JP-A-1-179939 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group was used to obtain a pH of 11 .0
The processing method of developing with the following developing solution is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit, the photosensitivity may be impaired, the development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient contrast cannot be exhibited. JP-A-60-14
No. 0340 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the contrast. However, in the case of developing with a developer having a pH of less than 11.0, sufficient contrast cannot be expressed. JP-A-56-106244 discloses adding an amino compound to a developer having a pH of 10 to 12 to promote contrast. However, when amines are used by adding them to a developing solution, there are problems such as odor of the solution and stains due to adhesion to equipment used, or environmental pollution due to waste solution, and it is desired to incorporate it into a light-sensitive material. It has not yet been found that it can be added to a light-sensitive material to obtain sufficient performance.

JP-A-61-167939, JP-A-4-6
2544, JP-A-62-250439, and JP-A-62-250439.
-280733 discloses that a hydrazine derivative and a quaternary onium salt compound are used for processing with a developer having a pH of 11 or more to form a high contrast image. Further, JP-A-61-47945, JP-A-61-47924 and JP-A-1-1-1
79930 and 2-2542, it is possible to form a high-contrast image by developing with a developer having a pH of 11 or more using an emulsion of silver bromide of 50 mol% or more, a specific hydrazine derivative and a quaternary onium salt compound. , Which are disclosed, but both are p
Since the developing solution having H11 or more is used, it is easily oxidized by air, and the performance tends to change due to fatigue of the developing solution over time. JP-A-4-51143, JP-A-4-56949, and JP-A-4-62554.
In 4, the specific hydrazine derivative and amine, hydrazine,
A photosensitive material containing a quaternary onium compound has a pH of 10.4 to 1
Processing with a developer of 0.8 is disclosed. The patent specification describes that a high contrast image of γ10 or more can be obtained by using a specific hydrazine derivative and a specific accelerator in a silver iodobromide emulsion system. However, with such a photosensitive material structure, the development progresses slowly, and the gradation of the gradation becomes soft, the sensitivity changes, and Dm due to the change of the liquid composition due to the fatigue of the developing liquid.
However, it has not yet been possible to obtain sufficient photographic performance after a lapse of time with the developing solution, such as a decrease in the image quality. Further, in the development process, the dye is not sufficiently flowed out or decomposed and remains in the treated sample, so-called residual color is often present, and a practical product cannot be obtained.

US 4998604 and US 499
No. 4365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is clear from these examples, the contrast is not sufficient,
It is difficult to obtain the high contrast and the required Dmax under practical development processing conditions.

In order to obtain a sufficiently high-contrast image using a stable developing solution having a pH of 11 or less, it is necessary to incorporate a highly reactive hydrazine derivative or an accelerator into the light-sensitive material, which is under study. Thus, when highly activated, the hydrazine derivative tends to be unstable in the coating solution during the production of the light-sensitive material or in the light-sensitive material (decrease in γ, increase in fog, etc.), and a stabilizing means is desired. , The direction of sufficient solution has not been found.

[0007]

SUMMARY OF THE INVENTION Therefore, firstly, the object of the present invention is to obtain a very hard negative gradation photographic property with a gamma of more than 10 by using a stable processing solution having a pH of 11 or less, Another object of the present invention is to provide a silver halide photographic light-sensitive material having photographic characteristics (sensitivity, gamma, image quality) that are always stable and substantially free of variations.

[0008]

The object of the present invention is to have at least one negative working silver halide emulsion layer on a support, the silver halide emulsion preferably having a silver chloride content of 5%.
It is composed of 0 mol% or more of silver halide grains, contains at least one hydrazine derivative in at least one of the emulsion layer and / or other hydrophilic colloid layer, and is different from a layer containing the hydrazine derivative. Achieved by a silver halide photographic light-sensitive material characterized by containing a nucleation accelerator in the layer.

In the present invention, the hydrazine derivative and the nucleation accelerator are added to separate layers located on the side of the support where the silver halide emulsion layer is present. Specifically, the hydrazine derivative is added to the emulsion layer and the nucleation accelerator is added to the overcoat layer of the emulsion layer or the layer between the emulsion layer and the support, or vice versa. When two or more emulsion layers are provided, the hydrazine derivative and the nucleation accelerator may be added to separate emulsion layers.

The nucleation accelerator preferably used in the present invention is a compound represented by the following general formula (I), (II) or (III).

[0011]

[Chemical 5]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents 1 or 2, L represents an m-valent organic group bonded to the P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents L. May be linked with.

[0013]

[Chemical 6]

In the formula, A is a compound for completing the heterocycle.
Represents a machine. B and C are alkylene and aryl, respectively.
Len, alkenylene, -SO₂-, -SO-, -O-,
-S-, -N (R_Five) -Is used alone or in combination.
Represents something. However, R _FiveIs an alkyl group, aryl
Represents a hydrogen atom. R₁, R₂Are each an alkyl group
Represent, R₃, R_FourEach represents a substituent. X is anio
X is not necessary in the case of an inner salt.

The general formula (I) will be described in more detail.
It R in the formula₁, R₂, R₃Is an alkyl group, cycloalkyl
Group, aryl group, alkenyl group, cycloalkenyl
Group, a heterocyclic residue, which further has a substituent.
You may have. m represents an integer, L is a P atom and its
Represents an m-valent organic group bonded by a carbon atom, n is not 1
Represents an integer of 3, X represents an n-valent anion, X represents
May be linked to L. R₁, R₂, R₃Represented by
Examples of groups that may be mentioned include methyl, ethyl, propyl
Group, isopropyl group, butyl group, isobutyl group, sec
-Butyl group, tert-butyl group, octyl group, 2-ethyl
Hexyl group, dodecyl group, hexadecyl group, octadecyl group
A linear or branched alkyl group such as a chloro group;
Groups such as phenyl, cyclopentyl, and cyclohexyl groups.
Chloroalkyl group, phenyl group, naphthyl group, phenanthate
Aryl group such as ryl group; allyl group, vinyl group, 5-hexyl group
Alkenyl groups such as xenyl group; cyclopentenyl
Group, cycloalkenyl group such as cyclohexenyl group;
Lysyl group, quinolyl group, furyl group, imidazolyl group, thiyl group
Azolyl group, thiadiazolyl group, benzotriazolyl
Group, benzothiazolyl group, morpholyl group, pyrimidyl
And heterocyclic residues such as a pyrrolidyl group. This
Examples of substituents substituted on these groups are R₁,
R₂, R₃In addition to the groups represented by
Child, halogen atom such as bromine atom, iodine atom, nitro
Groups, 1, 2, 3 amino groups, alkyl or aryl ethers
Ter group, alkyl or aryl thioether group, carbo
Amide group, carbamoyl group, sulfonamide group,
Famoyl group, hydroxyl group, sulfoxy group, sulfo
Nyl group, carboxyl group, sulfonic acid group, cyano group or
A carbonyl group. Examples of groups represented by L and
Then R₁, R₂, R₃In addition to the group synonymous with
Group, tetramethylene group, hexamethylene group, pentamene group
Such as tylene group, octamethylene group, dodecamethylene group, etc.
Polymethylene group, phenylene group, biphenylene group, naphth
Divalent aromatic group such as tylene group, trimethylenemethyl group,
Polyvalent aliphatic groups such as tetramethylenemethyl group, phenyle
1,3,5-toluyl group, phenylene-1,2,
Examples include polyvalent aromatic groups such as 4,5-tetrayl group.
Be done. An example of an anion represented by X is chlorine ion.
, Halogen ions such as bromide and iodine,
Acetate ion, oxalate ion, fumarate toy
Carboxylate ions such as on and benzoate ions
, P-toluene sulfonate, methane sulfonate,
Sulfur such as butane sulfonate and benzene sulfonate
Honate ion, sulfate ion, perchlorate ion, carbonate ion
On, nitrate ions can be mentioned. Smell of general formula (I)
And R₁, R₂, R₃Is preferably a group having 20 or less carbon atoms
And an aryl group having 15 or less carbon atoms is particularly preferable.
m is preferably 1 or 2, and when m represents 1, L is preferably
It is preferably a group having 20 or less carbon atoms, and a total carbon number of 15 or less
The alkyl group or aryl group of is particularly preferable. m is 2
When L represents, the divalent organic group represented by L is preferably
An alkylene group, an arylene group or a combination of these groups
Formed divalent group, and further, these groups and -CO-
Group, -O- group, -NR_Four-Group (however R_FourIs a hydrogen atom
Or R₁, R₂, R₃Represents a group synonymous with
Number R_FourWhen present, they are the same or different
May be attached to each other).
-S- group, -SO- group, -SO ₂− Combined shape
It is a divalent group formed. When m represents 2, L is
A divalent group having a total carbon number of 20 or less that is bonded to a P atom by a carbon atom.
Is particularly preferable. m represents an integer of 2 or more
Sometimes R in the molecule₁, R₂, R₃There are multiple
But the multiple R₁, R₂, R₃Are the same
Or they may be different. n is preferably 1 or 2,
X is R₁, R₂, R₃, Or L to form an inner salt
You may form. The compound represented by the general formula (I) of the present invention
Many compounds are known and commercially available as reagents
Is. The general synthetic method is to use phosphinic acids
Alkyl Genates, Sulfonates, etc.
Method of reacting with agent: or pair of phosphonium salts
There is a method of exchanging anions by a conventional method. General formula
Specific examples of the compound represented by (I) are shown below. However
However, the present invention is not limited to the following compounds.

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

The amount of the compound of formula (I) of the present invention to be added is not particularly limited, but it is preferably 1 × 10 ^-5 to 2 × 10 ^-2 mol per mol of silver halide. Particularly, the addition amount is preferably in the range of 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol. When the compound represented by the general formula (I) of the present invention is contained in a photographic light-sensitive material,
When it is water-soluble, it is used as an aqueous solution, and when it is water-insoluble, it is used as a solution of alcohols (eg methanol, ethanol), esters (eg ethyl acetate), ketones (eg acetone) and other water-miscible organic solvents. It may be added to the silver halide emulsion solution or the hydrophilic colloid solution.

The general formulas (II) and (III) will be described in more detail.

[0027]

[Chemical 16]

In the formula, A represents an organic group for completing the heterocycle, which may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and may further have a condensed benzene ring. . As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B and C are alkylene,
Arylene, _{alkenylene, -SO 2 -, - SO -} , -
O -, - S -, - N (R 5) - the meanings that are configured either alone or in combination. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. As a preferred example, B,
Examples of C include alkylene, arylene, -O-, and -S-, which may be used alone or in combination. R
₁ and R ₂ represent an alkyl group having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), a substitution or Unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p
-Bromobenzoyl group, acetyl group, etc.), sulfo group,
Carboxy group, hydroxy group, alkoxy group (for example,
Methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group,
It represents a nitro group, an alkylthio group, or an arylthio group.
As a preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ and R ₄ each represent a substituent, and examples of the substituent are the same as the substituents mentioned for R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anion group, but X is not necessary in the case of an inner salt.
Examples of X include chlorine ion, bromine ion, iodine ion,
It represents nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention will be described, but the present invention is not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful.
(See Quart. Rev., 16, 163 (1962).)

Specific compounds of the general formulas (II) and (III) are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

The amount of the compounds represented by the general formulas (II) and (III) to be added is not particularly limited as long as it is added in a necessary amount depending on the characteristics of the photosensitive material. When used in the present invention, the preferable addition amount is 1 × 10 ⁻⁶ to 1 × 10 ^−3.
mol / m ² , more preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mo
l / m ² .

The compounds of the general formulas (II) and (III) of the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide,
It can be used by dissolving it in methyl cellosolve or the like.
Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, the powders represented by the general formulas (II) and (III) can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The hydrazine derivative used in the present invention includes RESERCH DISCLOSURE Item 23516 (1
November 983, p.346) and the references cited therein, as well as U.S. Pat. Nos. 4,080,207 and 4,26.
9,929, 4,276,364, 4,27
8,748, 4,385,108, 4,45
9,347, 4,560,638, 4,47
8,928, British Patent 2,011,391B, JP-A-60-179,734, 62-270,948,
63-29,751, 61-170,733,
61-270,744, 62-270,948.
No., EP217,310, EP356,898, U
S4,686,167, JP-A-62-178,246
63, 32, 538, 63-104, 047.
63, 121-838, 63-129, 33.
No. 7, No. 63-223,744, No. 63-234,2
44, 63-234, 245, 63-234,
246, 63-294, 552, 63-30
6,438, JP-A-1-100,530, 1-1.
05,941, 1-105,943, JP-A-64
-10,233, JP-A-1-90,439, JP-A-1-276,128, 1-280,747, 1
-283,548, 1-283,549, 1-
285,940, JP-A-63-147,339, 63-179,760, 63-229,163,
Japanese Patent Application Nos. 1-18,377, 1-18,378, 1-18,379, 1-15,755, 1-1
6,814, 1-40,792, 1-42,6
No. 15, No. 1-42,616, No. 1-123,693
Nos. 1-126,284 may be used.

Particularly preferred in the present invention is a hydrazine derivative represented by the following general formula (IV).

[0037]

[Chemical 20]

In the general formula (IV), the aliphatic group represented by R ¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ¹ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The hetero ring of R ¹ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, a benzthiazolyl group. Those are preferable. Preferred as R ¹ are aromatic groups, nitrogen-containing heterocycles and groups represented by the general formula (b). General formula (b)

[0039]

[Chemical 21]

(Where X is_bIs an aromatic group or nitrogen-containing complex
Represents a ring group, R_b ¹~ R_b ^FourAre hydrogen atom and halogen
Represents an alkyl atom or an alkyl group, X_bAnd R_b ¹
~ R _b ^FourMay have a substituent if possible.
r and s represent 0 or 1. ) R¹Is more preferably an aromatic group, especially aryl.
Group is preferred. R¹May be substituted with a substituent
Yes. Examples of the substituent include, for example, an alkyl group and aralkyl.
Group, alkenyl group, alkynyl group, alkoxy group,
Reel group, substituted amino group, aryloxy group, sulfa
Moyl group, carbamoyl group, alkylthio group, aryl
Thio group, sulfonyl group, sulfinyl group, hydroxy
Groups, halogen atoms, cyano groups, sulfo groups and carboxyls
Groups, alkyl and aryloxycarbonyl groups, acyl
Group, alkoxycarbonyl group, acyloxy group, cal
Bonamide group, sulfonamide group, nitro group, alkyl
In addition to a thio group, an arylthio group, etc., the following general formula (c)
And a group represented by. General formula (c)

[0041]

[Chemical formula 22]

In the formula (c), Y _c is --CO-- or --SO.
_2- , -P (O) ( _Rc3 )-(wherein _Rc3 is an alkoxy group,
Alternatively, it represents an aryloxy group. ) Or -OP
(O) (R _c3 )-, L is a single bond, -O-, -S-.
Or —NR _c4 — (wherein R _c4 is a hydrogen atom, an alkyl group,
Represents an aryl group. ) Is represented. R _c1 and R _c2 represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
They may be the same or different and may be bonded to each other to form a ring. R ¹ may include one or more of general formula (c).

In the general formula (c), the aliphatic group represented by R _c1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _c1 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocycle of R _c1 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, and S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R _c1 may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, alkyl group, aralkyl group, alkenyl group,
Alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group , Halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group. When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R _c2 in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _c2 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _c2 may be substituted with a substituent. Examples of the substituent include those listed as R _c1 in the general formula (c) and the substituent. If possible, R _c1 and R _c2 may be linked to each other to form a ring. R _c2 is more preferably a hydrogen atom.
Y _c in the general formula (c) is —CO—, —SO _2
-Is particularly preferable, L is preferably a single bond and -NR _c4- .

The aliphatic group represented by R _c4 in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _c4 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _c4 may be substituted with a substituent. Examples of the substituent include those listed as the substituent of R _c1 in the general formula (c). R
_A hydrogen atom is more preferable as _c4 .

Most preferably, G in the general formula (IV) is a -CO- group. R ^{2 in the} general formula (IV) represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, and preferably a substituted alkyl group with two electron withdrawing groups is substituted. Represent. The electron withdrawing group for substituting the carbon atom substituted by G of R ² preferably has a σ _p value of 0.2 or more and a σ _m value of 0.3 or more, and examples thereof include halogen, cyano, nitro and nitrosopolyhaloalkyl. ,
Polyhaloaryl, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, It represents a phosphino group, a phosphine oxide group, a phosphonic acid ester group, a phosphonic acid amide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, and an electron-deficient heterocyclic group. R ^{2 in the} general formula (IV) particularly preferably represents a trifluoromethyl group.

R ¹ and R ^{2 in} the general formula (IV) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-00533
Those described in No. 0 are mentioned. R ^{1 of} the general formula (IV),
R ² may be one in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, triazole group and the like, and US Pat.
5,108, 4,459,347, JP-A-59-
195, 233, 59-200, 231 and 59.
-201, 045, 59-201, 046, 5
9-201, 047, 59-201, 048, 59-201, 049, 61-170, 733,
61-270,744, 62-948, 63.
-234, 244, 63-234, 245, 6
The groups described in 3-234,246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

[0050]

[Chemical 25]

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

[0053]

[Chemical 28]

[0054]

[Chemical 29]

[0055]

[Chemical 30]

[0056]

[Chemical 31]

[0057]

[Chemical 32]

The compound used in the present invention is the hydrazine derivative of the present invention in which the corresponding hydrazine is reacted with the corresponding carboxylic acid in the presence of a condensing agent such as dicyclohexylcarbodiimide, or an acid halide such as sulfonyl chloride or acyl chloride. Alternatively, it was synthesized by reacting with an acid anhydride, an active ester or the like. Further, when EWG is R ₃ SO ₂ —, a method of reacting the corresponding haloacetylhydrazide derivative with R ₃ SO ₂ H in the presence of a base was also used. A specific example is shown below.

Synthesis Example: Synthesis of Exemplified Compound IV-16 Under a nitrogen atmosphere, triethylamine (15.3 ml) was added to a mixed solution of the starting compound A (63.2 g) and tetrahydrofuran (200 ml), and the mixed solution was heated to 5 ° C. Cool down
Trifluoroacetic anhydride (16.9 ml) was added and stirred overnight at room temperature. The reaction solution was poured into 0.1N HCl aqueous solution and extracted with ethyl acetate, and the organic layer was washed with saturated saline. It was dried over anhydrous magnesium sulfate, ethyl acetate was distilled off, and the product was isolated and purified by silica gel chromatography to obtain the desired product (52.1 g). The structure of the compound was confirmed by nmr spectrum and ir spectrum. The structure of the raw material compound A is shown below.

[0060]

[Chemical 33]

The amount of the hydrazine derivative of the present invention added is 1 × 10 ⁻⁶ to 5 × 10 5 per mol of silver halide.
^It is preferably contained in an amount of ^-2 mol, particularly preferably in the range of 1 x 10 ^-5 mol to 2 x 10 ^-2 mol.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cell. It can be used by dissolving it in sorb or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The halogen composition of the silver halide emulsion used in the present invention preferably has a silver chloride content of 50 mol% or more and is composed of any one of silver chlorobromide, silver iodochloride and silver iodochlorobromide. The silver iodide content is 3 mol% or less, more preferably 0.
It is 5 mol% or less. As a method for preparing the silver halide emulsion used in the present invention, various methods known in the field of silver halide photographic light-sensitive materials are used. For example, P. Glafkidea's "Chimie et Physique Photographique"
(Published by Paul Montel, 1967
), GF Dufin, "Photographic Emory Chemistry (Photogra
phic Emulsion Chemistry) (The Focal Press)
(TheForcal Press), 1966), V.L.
Making of VLZelikman et al
And Coating Photographic Emulsion "
(Published by The Focal Press, 19
64) and the like. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 20% or less, particularly preferably 15% or less.

The average grain size of the grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.
It is 1 μm to 0.4 μm. As a method for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Further, it is preferable to form grains by using a so-called silver halide emulsion such as ammonia, thioether or tetra-substituted thiourea. Tetrasubstituted thiourea compounds are more preferred, and JP-A-53-82408 and JP-A-55-77 are preferred.
No. 737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The control double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool. Monodisperse emulsion is a cube,
It preferably has a regular crystal form such as an octahedron or a tetradecahedron, and a cube is particularly preferable. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Even if a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof are allowed to coexist in the silver halide emulsion used in the present invention in the process of formation or physical ripening of silver halide grains. Good.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is silver 1
It is an emulsion produced in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol. In the above, it is desirable to add the above-mentioned amount of iridium salt before the physical ripening in the production process of the silver halide emulsion, especially at the time of grain formation. The iridium salt used here is a water-soluble iridium salt or iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), and hexachloroiridium (I
V) Potassium acid, ammonium hexachloroiridium (III) acid, and the like.

The monodisperse emulsion of the present invention is chemically sensitized
Known methods such as sulfur sensitization, reduction sensitization and gold sensitization can be used, and they can be used alone or in combination. The preferred chemical sensitization method is gold sulfur sensitization. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are U.S. Pat. Nos. 1,574,944 and 2,278,94.
No. 7, No. 2,410,689, No. 2,728,668
Nos. 3,501,313 and 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg during chemical sensitization is preferably 8.3 or less, more preferably 7.3 to.
The range is 8.0. Also Moisar, Klein Gelatine.
Proc. Syme. 2nd, 301-309 (1976) et al. Also use polyvinylpyrrolidone in combination with thiosulfate to give good results. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are US Pat. No. 2,448,060,
It is described in British Patent No. 618,061 and the like.

In the present invention, a silver halide emulsion particularly suitable as a reversing light-sensitive material is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, and silver bromide in an amount of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

The silver halide emulsion of the present invention preferably contains a transition metal complex. As the transition metal, R
h, Ru, Re, Os, Ir, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, seleno Cyanate ligands, tellurocyanate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in an arbitrary form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium halogen complex compound, for example, hexachlororhodium (III) acid or a salt thereof. (Ammonium salt, sodium salt, potassium salt, etc.).
The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.
0 × 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-3 15 [Re (NO) Cl ₅ ] ^-1 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, as for A) an argon laser light source, JP-A-60-1
No. 62247, JP-A-2-48653, US Pat.
161,331, West German Patent 936,071, and Japanese Patent Application No. 3-189532, simple merocyanines,
B) For helium-neon laser light sources, JP-A-50-62425, 54-18726, and 59-
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398.
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
32, the tricarbocyanines described in JP-A-60-80841, and the compounds represented by the general formula (IIIa) and the general formula (IIIb) in JP-A-59-192242 and JP-A-3-67242. -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
Monthly publication) It is described on page 23, IV, section J. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifoggant compound, and the like. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art. Usually, preferably 10 ^-7 to 1 × 10 ^-2 mol, particularly 10 ^-6 to 5 × 10 ^-3 mol per mol of silver halide.
Used in the molar range.

For the argon laser light source, V-1 to V-13 described in Japanese Patent Application No. 5-123273 are particularly preferably used.

For a helium-neon light source, in addition to the above, it is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to top. Particularly preferred are sensitizing dyes. Specific compounds include:
Dyes VI-1 to VI-described in Japanese Patent Application No. 5-123273
8, in addition to these, all of those described in Japanese Patent Application No. 4-228745 and general formula (I) are preferably used.

Regarding the LED light source and the infrared semiconductor laser, the dye VII-1 described in Japanese Patent Application No. 5-123273 is used.
~ VII-8 is preferably used.

For infrared semiconductor laser light sources, dyes VIII-1 to VIII-9 described in Japanese Patent Application No. 5-123273.
Is preferably used.

For a white light source, Japanese Patent Application No. 5-1232
No. 73 described in formula (IV), and as specific compounds, dyes IV-1 to IV-20 listed in the same application are preferably used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or a highly alkaline developer close to pH 13 described in US Pat. No. 2,419,975 is used. It is not necessary to use, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / liter or more of sulfite ion as a preservative, and can obtain a sufficiently superhigh contrast negative image with a developer having a pH of 9.0 to 11.0. You can

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl are preferable. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

As the developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone and 1-phenyl-4- Methyl-4-
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone,
1-p-tolyl-4,4-dimethyl-3-pyrazolidone and the like.

As the p-aminophenol type developing agent used in the present invention, N-methyl-p-aminophenol, p
-Aminophenol, N- (β-hydroxyethyl)-
p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol, etc., but among them N-
Methyl-p-aminophenol is preferred.

The developing agent is usually from 0.05 mol / liter to
It is preferably used in an amount of 0.8 mol / l.
When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / liter to 0.5.
It is preferable to use the latter in an amount of 0.06 mol / liter or less.

In the present invention, in particular, the compound (preservative) represented by the following general formula (V) has a concentration ratio (the concentration of the compound of the general formula (V) in the developing solution to that of the dihydroxybenzene type developing agent. The value obtained by dividing the concentration of the dihydroxybenzene-based developing agent in the developing solution) is 0.03 to 0.12.
A developer having a pH of 9.0 to 11.0 is preferably used.

[0083]

[Chemical 34]

In the general formula (V), R ₁ and R ₂ are each a hydroxy group or an amino group (having 1 carbon as a substituent).
-10 alkyl groups such as methyl, ethyl, n-
Those having a butyl group, a hydroxyethyl group or the like as a substituent are included. ), An acylamino group (acetylamino group, benzoylamino group, etc.), an alkylsulfonylamino group (methanesulfonylamino group, etc.), an arylsulfonylamino group (benzenesulfonylamino group, p-
A toluenesulfonylamino group), an alkoxysulfonylamino group (methoxycarbonylamino group, etc.), a mercapto group, an alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

P and Q represent a hydroxy group, a hydroxyalkyl group, a carboxyl group, a carboxylalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group, an alkoxy group, a mercapto group, or P and Q represents an atomic group necessary for bonding to form a 5- to 7-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Specific examples of the ring structure, -O -, - C- (R 4) (R 5) -,
_{-C (R 6) =, -} C (= O) -, - N (R 7) -, - N
=, Combined. However, R ₄ , R ₅ , R
₆ , R ₇ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, a sulfo group can be mentioned as the substituent), and 6 to 15 carbon atoms
Represents an aryl group (which may be an alkyl group, a halogen atom, a hydroxy group, a carboxy group or a sulfo group), a hydroxy group or a carboxyl group which may be substituted. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexequin ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. And the like, and as an example of a preferred 5- to 7-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is composed of = O or = N-R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl group, ethyl group), an acyl group (eg, acetyl group), a hydroxyalkyl group (eg, hydroxymethyl group, hydroxyethyl group), a sulfoalkyl group (eg, sulfomethyl group). Group, sulfoethyl group) and carboxyalkyl group (eg carboxymethyl group, carboxyethyl group).

Specific examples of the compound of the present invention are shown below.
The present invention is not limited to this.

[0089]

[Chemical 35]

[0090]

[Chemical 36]

[0091]

[Chemical 37]

Among these, ascorbic acid or erythorbic acid (cubic isomer) (V-1) is preferable. As a general range of the amount of the compound of the general formula (V) used, 5 × 10 ⁻³ mol to 1 mol, and particularly preferably 10 ⁻² mol to 0.5 mol per liter of the developer, This is the amount that is the concentration ratio with the above-mentioned dihydroxybenzene type developing agent.

Examples of the sulfite-based preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is 0.15 mol / liter or more,
Particularly, 0.3 mol / liter or more is preferable. The upper limit is preferably 2.5 mol / liter. Sodium hydroxide is used as the alkaline agent to set the pH.
It contains a pH adjusting agent and a buffering agent such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. The pH of the developer is set between 9.6 and 11.0.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, toluethylene glycol, Organic solvents such as dimethylformamide, methylcellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 5-
An indazole compound such as nitroindazole, an antifoggant such as 5-methylbenztriazole or a benztriazole compound such as a benztriazole compound or a black pepper inhibitor: may be contained, and if necessary, a toning agent and a surfactant. , Antifoaming agent, water softener, hardener, JP-A-56-10
The amino compound described in No. 6244 may be included.

The compounds described in JP-A-56-24347 can be used in the developer of the present invention as a silver stain preventing agent. Japanese Patent Application No. Sho 6 as a dissolution aid added to the developer.
The compounds described in 0-109,743 can be used. Further, as a pH buffering agent used in a developing solution, Japanese Patent Laid-Open No.
No. 0-93,433 or Japanese Patent Application No.
The compounds described in -28708 can be used.
As the fixing agent, those having a generally used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, light vane, etc.) as a hardening agent. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al / liter. Furthermore, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent. The developing treatment temperature is usually selected from 18 ° C to 50 ° C, more preferably 25 ° C to 43 ° C.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and the additives described in the following sections can be preferably used. Item This section 1) Spectroscopy that may be used in combination JP-A-2-12236, page 8, lower left column, line 13 From sensitizing dye to lower right column, line 4; JP-A-2-103536, page 16, lower right Column 3, line to page 17, lower left column, line 20, further JP-A Nos. 1-112235, 2-124 560, 3-7928, and Japanese Patent Application Nos. 3-189532 and 3-411064. The spectral sensitizing dye described in 1. 2) Surfactants JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to fourth. Lower right column, line 18 3) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A-1-237538 Thiosulfinic acid compounds described in the public notice. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 6) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 8) Dyes Dyes in the lower right column, lines 1 to 18 of page 17 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Monomethine compound Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 13) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12 lower left column, and EP452772A.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0098]

EXAMPLES First, a method of making a silver halide emulsion used in the following examples will be described. Emulsion-A 0.37 mol of silver nitrate aqueous solution, and (NH ₄ ) ₃ RhCl ₆ and 2x corresponding to 1.0 × 10 ^-7 mol per mol of silver in the finished emulsion.
Gelatin containing 10 ^-7 mol of K ₃ IrCl ₆ , 0.11 mol of potassium bromide and 0.27 mol of sodium chloride in an aqueous solution of halogen salt, sodium chloride and 1,3-dimethyl-2-imidazolidinethione. Add to the aqueous solution with stirring by the double jet method at 45 ° C for 12 minutes,
Average grain size 0.20 μm, silver chloride content 70 mol%
Nucleation was carried out by obtaining silver chlorobromide grains of Then, similarly, an aqueous solution of halogen salt containing 0.63 mol of silver nitrate aqueous solution, 0.19 mol of potassium bromide and 0.47 mol of sodium chloride was similarly added by a double jet method to give 20
Added over minutes. Then 1 × 10 ^-3 per 1 mol of silver
A molar KI solution was added for conversion, followed by washing with water by a flocculation method according to a conventional method, and gelatin 4
The pH was adjusted to 6.5 and pAg to 7.5 by adding 0 g, and sodium benzenethiosulfonate 7 was added per mol of silver.
mg, sodium thiosulfate 5 mg, and chloroauric acid 8 mg were added, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization, and 4-hydroxy-6-methyl-1,3,3 as a stabilizer.
150 mg of a, 7-tetrazaindene and proxel as preservative were added. The resulting grains were silver chlorobromide cubes having an average grain size of 0.28 μm and a silver chloride content of 60 mol%. (Coefficient of variation 9%)

Example 1 (Preparation of coating sample) UL / EM / ML / PC on a support
The following formulation was applied in the order of. (UL) Gelatin was dissolved at 40 ° C., and then compound (g) was added so as to be 5 mg / m ² , compound (e) was 30 wt% with respect to gelatin, methyl acrylate and 2-acrylamido-2-methylpropanesulfone. A latex copolymer of sodium acid salt and acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7) was added to gelatin to 2 parts.
0% by weight, 3% by weight of compound (f) as a hardening agent to gelatin and 2% by weight of bisvinylsulfonylmethane to gelatin were added. The pH of the solution was adjusted to 5.8 and gelatin was applied at 0.5 g / m ² . (EM) 40 parts of the silver halide emulsion together with gelatin
After dissolving at ℃, IV-9 was used as a sensitizing dye at 4.0 × 10.
^-4 mol / mol Ag was added. Then compound (a) 1.0 ×
10 ⁻⁵ mol / m ² , compound (b) 5.0 × 10 ⁻⁶ mol / m
m ² , compound (c) 7.0 × 10 ⁻⁶ mol / m ² , hydroquinone 40 mg / m ² , and general formula (I) to general formula (I
V) compound, compound (d) 2 mg / m ² , compound (g) 1
0 mg / m ² , water-soluble latex of compound (e) 500 mg /
m ² , a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, and acetoacetoxyethyl methacrylate (polymerization ratio 88: 5: 7) 300 mg / m ² , and a compound (f 3% by weight to gelatin and 1% by weight of bis-vinylsulfonylmethane to gelatin.
The pH of the solution was adjusted to 5.8. The liquid prepared in this manner was used as an undercoat layer (0.
It was coated on a polyethylene terephthalate film (thickness: 150 μm) support having 5 μm) so that the amount of silver was 3.2 g / m ² and gelatin was 1.6 g / m ² .

[0100]

[Chemical 38]

After dissolving (ML) gelatin, 30 mg / m ^{2 of} the compound (g), compounds of the general formulas (I) to (IV) shown in Table 1, and 30 wt% of the compound (e) with respect to gelatin (e) ) And gelatin in an amount of 3 wt% (f) to adjust the pH to 5.8, and gelatin 0.5 g / m ²
Was applied.

(PC) Gelatin 0.5 mg / m ² as a protective layer on these emulsion layers, 40 mg / m ^{2 of} amorphous silicon dioxide matting agent having an average particle size of 3.5 μm, and 0.1 g / m of methanol silica. ² , polyacrylamide 100 mg / m ² ,
Hydroquinone 150 mg / m ² , silicone oil 20 mg
/ M ² and a coating solution containing 5 mg / m ² of the compound (g) as a coating aid and 25 mg / m ^{2 of} sodium dodecylbenzenesulfonate were coated to prepare samples as shown in Table 1.

The coating layer on the back surface of the support was as shown below. (Back layer formulation) Gelatin 3 g / m ² Polyethyl acrylate latex 2 g / m ² Sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound (f) 3 wt% SnO ₂ / Sb (weight ratio 90/10) to gelatin , Average particle size 0.20 μm) 200 mg / m ² dye (a) 50 mg / m ² dye (b) 100 mg / m ² dye (c) 50 mg / m ²

[0104]

[Chemical Formula 39]

(Back protective layer) Gelatin 0.8 mg / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate Na salt 15 mg / m ² p-dodecylbenzene sulfonate sodium 15 mg / M ² Sodium acetate 40mg / m ²

The developer formulation is shown below. Developer Formulation Developer (A) Developer (B) Potassium hydroxide 35.0 g 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g 2.0 g Sodium metabisulfite 40.0 g 40.0 g Potassium carbonate 12.0 g 12.0 g Potassium bromide 3.0 g 3.0 g 5 -Methylbenzotriazole 0.06 g 0.06 g 2,3,5,6,7,8-hexahydro 0.04 g 0.04 g-2-thioxo-4- (1H) -quinazolinone 2-mercaptobenzimidazole-5 0.15 g 0.15 g-sulfone Sodium acid hydroquinone 25.0 g 25.0 g 4-hydroxymethyl-4-methyl-1 0.45 g 0.45 g phenyl-3-pyrazoline sodium erythorbate 3.00 g 3.00 g Add water to make 1 liter pH10.5 pH10.8

Development processing and photographic performance evaluation were carried out as follows. (Fresh processing) Color temperature 320 using tungsten sensitometer
After exposure through a 0 ° K filter and a step wedge, FG-460A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) was used to develop with a developing solution (A) at 35 ° C for 30 ″, followed by fixing and washing with water. Then, the fixing solution was
GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used. (Photographic performance evaluation) γ (gradation) γ = optical density (3.0-0.3) ÷ Δlog E ΔlogE in the formula is O. D. The exposure dose (log E3.0) required to give 3.0 and O.I. D. It means the difference in exposure dose (log E0.3) required to give 0.3. 2. D1504 O.D. D. O.V. when the exposure was increased by 0.4 in log E from the exposure required to give 1.5. D. Value 3. Performance of coating solution over time A photosensitive material (Fresh) applied immediately after preparation of the preparation solutions of EM and PC and a photosensitive material (40 ° C for 6 hours) after application for 6 hours after preparation were simultaneously developed. And compared the photographic performance.

The results obtained in this way are shown in Table 1.

[0109]

[Table 1]

From the results of Table 1, sample Nos. 101 to 103
Then, γ and D1504 in Fresh are high, but both γ and D1504 decrease with time. Sample No. 104 ~
In 106, γ and D1504 in Fresh are slightly low, and further decrease with time. On the other hand, sample No. 107 of the present invention
At ~ 115, both γ and D15 are high both in Fresh and after aging.
I keep 04. Among them, in Sample Nos. 107 to 110, good performance was obtained.

Example 2 The following formulation was applied on a support in the order of UL / EMU / EMO / ML / PC. (UL) It was prepared by the same formulation as UL of Example-1 and coated so as to be 0.5 g / m ^{2 of} gelatin. (EMU) General formula (I) to general formula (I) of EM of Example 1
It was prepared in the same manner as in EM of Example 1 except that the compound of V) was changed as shown in Table 2, and applied so that the amount of Ag was 2.4 g / m ² . (EMO) EMU was prepared in the same manner as EMU except that the compounds represented by the general formulas (I) to (IV) were replaced as shown in Table 2, and the Ag amount was 0.8 g / m ² . And applied.
However, the addition amount of the chemical agent of EM of Example 1 is
It was adjusted to be proportional to the amount. (ML) A gelatin was prepared in the same manner as in ML of Example 1 except that the compounds of the general formulas (I) to (IV) of Example 1 were not added, and the amount of gelatin was 0.3 g / m ^2. Applied. P
The C and bag formulations were applied in exactly the same way as in Example 1. The results are shown in Table 2.

[0112]

[Table 2]

From the results of Table 2, Nos. 204 to 2 of the present invention
In No. 18, all have a high contrast and a high D _m , and the performance of the coating solution after aging is also good. Especially sample Nos. 204-207 and N
o. 216 to 218, γ and D1504 in Fresh are high, which is preferable.

[0114]

According to the present invention, gamma due coating solution over time, the variation of D _m is small, always provide a photosensitive material with stable photographic characteristics.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

In the present invention, the hydrazine derivative and the nucleation accelerator are added to separate layers located on the side of the support where the silver halide emulsion layer is present. Specifically, the hydrazine derivative is added to the emulsion layer and the nucleation accelerator is added to the overcoat layer of the emulsion layer or the layer between the emulsion layer and the support, or vice versa. When two or more emulsion layers are provided, the hydrazine derivative and the nucleation accelerator may be added to separate emulsion layers, or the nucleation accelerator may be added to the emulsion layer and the hydrazine derivative is added to the upper and lower layers of the emulsion layer. You may add it separately.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Most preferably, G in the general formula (IV) is a -CO- group. R ^{2 in the} general formula (IV) represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, preferably a substituted alkyl group with two or more electron withdrawing groups. Represents a group. The electron withdrawing group for substituting the carbon atom substituted by G in R ² is preferably σ
_{having a p} value of 0.2 or more and a σ _m value of 0.3 or more, for example, halogen, cyano, nitro, nitrosopolyhaloalkyl, polyhaloaryl, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group , Alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or aryl sulfonyl group, alkyl or aryl sulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate ester group, phosphonate amide group, arylazo group , Amidino group, ammonio group, sulfonio group, electron-deficient heterocyclic group. R ^{2 in the} general formula (IV) particularly preferably represents a trifluoromethyl group.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

[0052]

[Chemical 27]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0099

[Correction method] Change

[Correction content]

Example 1 (Preparation of coating sample) UL / EM / ML / PC on a support
The following formulation was applied in the order of. (UL) Gelatin was dissolved at 40 ° C., and then compound (g) was added so as to be 5 mg / m ² , compound (e) was 30 wt% with respect to gelatin, methyl acrylate and 2-acrylamido-2-methylpropanesulfone. A latex copolymer of sodium acid salt and acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7) was added to gelatin to 2 parts.
0% by weight, 3% by weight of compound (f) as a hardening agent to gelatin and 2% by weight of bisvinylsulfonylmethane to gelatin were added. The pH of the solution was adjusted to 5.8 and gelatin was applied at 0.5 g / m ² . (EM) 40 parts of the silver halide emulsion together with gelatin
After dissolving at ℃, as a sensitizing dye, Japanese Patent Application No. 5-12327
4 of the specific compound example IV-9 of the general formula (IV) of 3
0 ⁻⁴ mol / mol Ag was added. Then compound (a) 1.0
× 10 ^-5 mol / m ² , compound (b) 5.0 × 10 ^-6 mol / m
m ² , compound (c) 7.0 × 10 ⁻⁶ mol / m ² , hydroquinone 40 mg / m ² , and general formula (I) to general formula (I
V) compound, compound (d) 2 mg / m ² , compound (g) 1
0 mg / m ² , water-soluble latex of compound (e) 500 mg /
m ² , a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt, and acetoacetoxyethyl methacrylate (polymerization ratio 88: 5: 7) 300 mg / m ² , and a compound (f 3% by weight to gelatin and 1% by weight of bis-vinylsulfonylmethane to gelatin.
The pH of the solution was adjusted to 5.8. The liquid prepared in this manner was used as an undercoat layer (0.
It was coated on a polyethylene terephthalate film (thickness: 150 μm) support having 5 μm) so that the amount of silver was 3.2 g / m ² and gelatin was 1.6 g / m ² .

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

The developer formulation is shown below. Developer Formulation Developer (A) Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium metabisulfite 40.0 g Potassium carbonate 12.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.06 g 2,3,5,6,7 , 8-Hexahydro 0.04 g-2-thioxo-4- (1H) -quinazolinone 2-mercaptobenzimidazole-5 0.15 g-sodium sulfonate hydroquinone 25.0 g 4-hydroxymethyl-4-methyl-1 0.45 g phenyl-3- Pyrazoline sodium erythorbate 3.00 g Add 1 liter of water to adjust pH pH10.5

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0109

[Correction method] Change

[Correction content]

[0109]

[Table 1]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0112

[Correction method] Change

[Correction content]

[0112]

[Table 2]

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material having at least one negative type silver halide emulsion layer on a support, wherein a hydrazine derivative and a nucleation accelerator are contained in different layers. Silver photographic light-sensitive material. 2. The silver halide emulsion has a silver chloride content of 50.
The silver halide photographic light-sensitive material according to claim 1, comprising silver halide grains in an amount of at least mol%. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the nucleation accelerator is at least one compound represented by the following general formula (I). [Chemical 1] In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may further have a substituent. m represents 1 or 2, L represents an m-valent organic group bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion,
X may be linked to L. 4. The nucleation accelerator is represented by the following general formula (II) or
Is at least one compound represented by general formula (III)
A silver halide photographic light-sensitive material according to claim 1, characterized in that
Fee. [Chemical 2]In the formula, A represents an organic group for completing the heterocycle.
You B and C are alkylene, arylene and ar, respectively.
Kenylene, -SO₂-, -SO-, -O-, -S-,-
N (R_Five) -Tables that are configured alone or in combination
Forget However, R _FiveIs an alkyl group, aryl group, hydrogen source
Represents a child. R₁, R₂Each represents an alkyl group, R
₃, R_FourEach represents a substituent. X represents an anion group
However, X is not necessary in the case of an inner salt. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine derivative is at least one compound represented by the following general formula (IV). General formula (IV): R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G is -CO- group, -SO ₂ - group,
Represents a —SO— group, a —COCO— group, a thiocarbonyl group, an iminomethylene group or a —P (O) (R ⁴ ) — group, and R ²
Represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group. R ⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group. 6. A silver halide photographic light-sensitive material according to claim 1
An image forming method, which comprises performing development processing using a developing solution of H 9.0 to 11.0. 7. A silver halide photographic light-sensitive material according to claim 1
Compound represented by general formula (V) and dihydroxybenzene system
The concentration ratio of the developing agent is 0.03 to 0.12, and the pH is
It is characterized in that it is processed with a developing solution of 9.0 to 11.0.
Image forming method. General formula (V):In the general formula (V), R₁, R₂Are each
Si group, amino group, acylamino group, alkylsulfonyl
Amino group, arylsulfonylamino group, alkoxy
Represents a sulfonylamino group, a mercapto group, and an alkylthio group.
Forget P and Q are hydroxy group, hydroxyalkyl group,
Carboxyl group, carboxyalkyl group, sulfo group, sulfur
Rufoalkyl group, amino group, aminoalkyl group, alkyl group
Group, an alkoxy group, a mercapto group, or
P and Q combine to form R ₁, R₂Are replaced by
5 to 7 together with the carbon atom substituted by the Nyl carbon atom and Y
Represents the atomic group necessary to form a member ring. Y is = O,
Or = NR₃Composed of. Where R₂Is a hydrogen atom,
Hydroxyl group, alkyl group, acyl group, hydroxy group
Alkyl group, sulfoalkyl group, carboxyalkyl group
Represent.