JP2699207B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast negative image using the same, and particularly to a silver halide photographic material used in a photomechanical process. The present invention relates to a super-high contrast negative type photographic light-sensitive material suitable for a light-sensitive material.

(Prior Art) In the field of photoengraving, there is a demand for a photographic photosensitive material having good original reproducibility, a stable processing solution, or a simple replenishment in order to cope with the variety and complexity of printed matter.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, images having different densities and line widths are mixed in an original, and a plate-making camera, a photographic photosensitive material, or an image forming method for finishing these originals with good reproducibility is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred. Shooting. In reduction, the number of lines / ink is larger than that of the original, and a thin point is photographed. Therefore, there is a demand for an image forming method having a wider latitude in order to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain a photographic sensitivity with respect to these light sources, a photographic light-sensitive material is usually subjected to orthosensitization. However, it has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

The lith-type silver halide photographic material composed of silver chlorobromide (with a silver chloride content of at least 50%) has a very low effective concentration of sulfite ions (usually 0.1 mol / or less). There is known a method of obtaining a line image or a halftone image having a high contrast and a high blackening density in which an image area and a non-image area are clearly distinguished by processing with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, development is extremely unstable against air oxidation, and various efforts and efforts have been made to keep the solution activity stable. Was extremely slow, and the work efficiency was reduced.

For this reason, an image forming system that eliminates instability of image formation by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857,
4,224,401, 4,243,739, 4,272,606, 4,31
As shown in No. 1,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound has been added contains 0.15 mol / or more of a sulfite preservative at pH 11.0 to 12.3 and has good storage stability. Is treated with a developer having
Systems have been proposed for forming over 10 ultra-high contrast negative images. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is.

Although the above imaging system shows excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, the original reproducibility has been further improved to cope with the recent variety of printed matter. A system is desired.

JP-A-56-153,336, JP-A-61-156,043, JP-A-61-230,
Nos. 135 and 62-296,138 show photosensitive materials containing a redox compound which releases a photographically useful group by oxidation, and show an attempt to extend the gradation reproduction range. However,
In a super-high contrast processing system using a hydrazine derivative, these redox compounds have a problem of inhibiting high contrast,
The characteristics could not be utilized.

(Object of the Invention) An object of the present invention is to provide a plate-making photosensitive material having a wide halftone reproduction range in a method for producing a high-contrast image with high stability.

A second object is to provide a plate-making photosensitive material having a wide halftone reproduction range and a high contrast.

(Constitution of the Invention) The object of the present invention is to provide a first silver halide emulsion layer containing at least one silver halide emulsion on a support, wherein the first emulsion layer contains a hydrazine derivative. And a second silver halide emulsion layer, wherein the second emulsion layer contains a compound represented by formula (I).

General formula [I] In the formula (I), R ₁ is R ₃ represents an alkyl group, an aryl group or a heterocyclic group, R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group, and R ₂ has a Hammett's substituent constant σ _p value.
Represents a substituent of 0.3 or less, n represents 0, 1 or 2, and when n is 2, two R ₂ may be the same or different, and B represents PUG after leaving from the hydroquinone mother nucleic acid. Represents a releasing group, PUG represents a development inhibitor, l represents an integer, A and A 'represent a group which can be removed by a hydrogen atom or an alkali, R ₁ and R ₂ , R ₁ and A or A or A ', R ₂ and A or A', and two R _{2 s} may together form a ring.

As a result of a more detailed study, they have found that, among the compounds represented by the formula [I], particularly the compound represented by the formula [II] exhibits excellent properties even when used in a small amount.

General formula (II) In the formula [II], R ₁ , R ₂ , B, PUG, A, A ′, n
And 1 have the same meaning as in formula [I].

Formulas [I] and [II] of the present invention will be described in more detail.

R ₁ is Wherein R ₃ is a substituted or unsubstituted alkyl (C 1-30, for example, methyl, ethyl, iso-propyl, n
-Decyl, n-hexadecyl, etc.), substituted or unsubstituted aryl groups (e.g., having 6 to 30 carbon atoms, such as phenyl, naphthyl, m-dodecylamidophenyl, m-hexadecylsulfonamidophenyl, p-dodecyloxyphenyl), Or a heterocyclic group (eg, 2-pyridyl, 4
-Pyridyl, 3-pyridyl, 2-furyl, etc.), and the substituent on R ₃ is an alkyl group, an aryl group,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxamide group, sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, An acyl group, a carboxyl group, a sulfo group, a nitro group, a heterocyclic residue or the like is mentioned, R ₄ and R ₅ may be the same or different, and a hydrogen atom or a substituent represented by R ₃ Express.

Preferred R ₄ in the formulas [I] and [II] is a hydrogen atom.

In the formulas [I] and [II], R ₂ represents a substituent having a Hammett's substituent constant σp value of 0.3 or less, and examples thereof include a substituted or unsubstituted alkyl group (having 1 to 1 carbon atoms).
30, for example, methyl, ethyl, iso-propyl, n-decyl, n-hexadecyl, etc., and substituted or unsubstituted aryl groups (C6-C30, for example, phenyl, naphthyl,
m-dodecylamidophenyl, m-hexadecylsulfonamidophenyl, p-dodecyloxyphenyl, etc.), alkoxy group (1 to 30 carbon atoms, for example, methoxy,
Ethoxy, n-hexyloxy, n-hexadecyloxy, etc., an aryloxy group (C6-30, for example, phenoxy, naphthyl, etc.), an alkylthio group (C1)
To 30, for example, methylthio, n-butylthio, n-decylthio, etc., arylthio (for example, having 6 to 30 carbon atoms, for example, phenylthio, 2-n-butyloxy-5-tert-octylphenylthio), an acylamino group (for example, acetylamide, n-decanoic acid amide, benzoic acid amide, etc.),
Examples include sulfonic acid amide groups (methanesulfonic acid amide, n-butanesulfonic acid amide, etc.), and halogen atoms (chlorine, bromine, fluorine) and the like.

In the formulas (I) and (II), R ₁ and R ₂ , R ₁ and A or A ′, R ₂ and A or A ′, and two R
₂ may form a ring together, in which case the number of ring members is preferably 5 to 7.

In the formulas [I] and [II], l preferably represents 0, 1 or 2.

Among the compounds represented by the formula [I], a preferred compound is a compound represented by the formula [II], and a more preferred compound is represented by the formula [III].

General formula (III) R ₁ , B, PUG, A, A ′ and 1 in the formula [III] have the same meaning as in the formulas [I] and [II].

In formulas (I), (II) and (III), A,
A ', B and PUG will be described in detail.

In the formulas [I], [II], and [III], when A and A ′ represent a group that can be removed by an alkali (hereinafter, referred to as a precursor group), preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Hydrolyzable groups such as carbamoyl group, imidoyl group, oxazolyl group, sulfonyl group, U.S. Pat.
No. 029, a precursor group of the type utilizing the reverse Michael reaction, U.S. Pat.No. 4,310,612, a precursor group of the type utilizing an anion generated after the ring cleavage reaction as an intramolecular nucleophilic group, U.S. Pat. No. 3,932,480
No. 3,993,661, a precursor group in which an anion is electron-transferred through a conjugated system and thereby causes a cleavage reaction, and a cleavage reaction is caused by electron transfer of an anion reacted after ring opening described in U.S. Pat.No.4,335,200. Precursor groups or U.S. Pat.
No. 10,618, a precursor group utilizing an imidomethyl group.

 In formulas [I], [II] and [III], represented by B
Is that the hydroquinone nucleus oxidizes the developing agent during development.
After being oxidized by the body to a quinone body, B_lPUG
Represents a divalent group capable of releasing and then releasing PUG
And may have a timing adjustment function.
Acid that releases PUG by reacting with oxidized developing agent of one molecule
It may be a redox group. If l is 0, PUG
Is directly bonded to the hydroquinone nucleus
However, when l is 2 or more, 2 of the same or different B
Represents one or more combinations.

When B is a divalent linking group having a timing control function, examples thereof include the following.

(1) A group utilizing a cleavage reaction of hemiacetal A group described in, for example, U.S. Pat. No. 4,146,396, JP-A-60-249148 and JP-A-60-249149, and represented by the following general formula. Here, the asterisks indicate the formulas (I), (II) and (II)
In [I], the position bonding to the left side is indicated. In the formulas [I], [II] and [III], the position bonding to the right side is shown.

General formula (T-1) Wherein W is an oxygen atom, a sulfur atom or R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t represents 1 or 2. When t is 2, two Represents the same or different. R ₆₅ and R ₆₆
Is a substituent, and representative examples of R ₆₇ are each R ₆₉
R ₆₉ CO- group, R ₆₉ SO ₂ -group, And the like. Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group, and may be linked to form a cyclic structure. Specific examples of the group represented by formula (T-1) include the following groups.

(2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, a timing group described in US Pat. No. 4,248,962 may be mentioned. It can be represented by the following general formula.

General formula (T-2) * -Nu-Link-E-** In the formula, the symbol * represents the position bonded to the left side in the formulas [I], [II] and [III], and the symbol ** represents the formula [I ] [II]
And (III) represents the position bonded to the right side,
u represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and is a group capable of undergoing a nucleophilic attack from Nu to cleave a bond with the ** mark Link Is Nu
And E represent a linking group which sterically relates so that an intramolecular nucleophilic substitution reaction can take place. Specific examples of the group represented by the general formula (T-2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, they are described in U.S. Pat. No. 4,409,323 or 4,421,845 and are groups represented by the following general formula.

General formula (I-3) In the formula, *, **, W, R ₆₅ , R ₆₆ , and t are (T
-1) has the same meaning as described above. Specific examples include the following groups.

(4) A group utilizing a cleavage reaction due to hydrolysis of an ester.

For example, the linking group described in West German Patent Publication No. 2,626,315 includes the following groups. In the formulas, * and ** have the same meaning as described for the general formula (T-1).

(5) A group that utilizes the cleavage reaction of imino ketal.

For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following general formula.

General formula (T-6) In the formula, *, ** and W have the same meaning as described in formula (T-1), and R ₆₈ has the same meaning as R ₆₇ . Specific examples of the group represented by the general formula (T-6) include the following groups.

In the general formulas [I], [II] and [III], when the group represented by B represents a group which is cleaved from the hydroquinone nucleus to become a redox group, preferably the following general formula (R-
It is represented by 1).

Formula (R-1) * -P- (X = Y) _n -QA In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n X and Y At least one represents a methine group having -PUG as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents 1 to 3
(N X's and n Y's represent the same or different), A represents a hydrogen atom or a group which can be removed by an alkali, and has the same meaning as A in formula (I). Here, the case where any two substituents of P, X, Y, Q and A are linked as a divalent group to form a cyclic structure is also included. For example, (X = Y) _n forms a benzene ring, a pyridine ring, and the like.

When P and Q represent a substituted or unsubstituted imino group, it is preferably a sulfonyl group or an imino group substituted with an acyl group.

 At this time, P and Q are represented as follows.

Here, the * mark indicates the position where it bonds to A, and the ** mark indicates-
(X = Y) represents a position where it is bonded to one of _n − free bonds.

In the formula, a group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32, preferably 1 to 22 carbon atoms (eg, methyl,
Ethyl, benzyl, phenoxybutyl, isopropyl), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (eg, phenyl, 4-methylphenyl, 1-naphthyl, 4-dodecyloxyphenyl, etc.), or A 4- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom (for example, a 2-pyridyl group, a 1-phenyl-4-imidazolyl group, a 2-furyl group, a benzothienyl group, etc.) Is a preferred example.

In the general formula (R-1), P and Q are preferably each independently an oxygen atom or a group represented by the general formula (N-1).

In the general formula (R-1), it is preferable that P represents an oxygen atom and A represents a hydrogen atom.

More preferably, in the general formula (R-1), X and Y are each a substituted or unsubstituted methine group except when X and Y are methine groups having PUG as a substituent.

Particularly preferred groups among the groups represented by formula (R-1) are those represented by the following formula (R-2) or (R-3).

General formula (R-2) General formula (R-3) In the formula, an asterisk indicates a position bonding to the hydroquinone nucleus, and an asterisk indicates a position bonding to PUG.

R ₆₄ represents a substituent, and q represents an integer of 0, 1 to 3. q is may be two or more R ₆₄ when two or more the same or different, also the linked cyclic structural each a divalent group when two R ₆₄ are substituents on adjacent carbons The case where it expresses is also included. In that case, it becomes a benzene condensed ring, for example, naphthalenes, benzonorbornenes, chromans, indoles, benzothiophenes,
Ring structures such as quinolines, benzofurans, 2,3-dihydrobenzofurans, indanes, and indenes, which may further have one or more substituents. Examples of preferred substituents when these fused rings have a substituent, and R when R ₆₄ does not form a fused ring
Preferred examples of ₆₄ are as follows.

That is, an alkoxy group (eg, methoxy group, ethoxy group, etc.), an acylamino group (eg, acetamido group,
Benzamide group), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), carbamoyl group (eg, N-propylcarbamoyl group, Nt-butylcarbamoyl) Group, Ni-
Propylcarbamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, propoxycarbonyl group, etc.), aliphatic group (eg, methyl group, t-butyl group, etc.), halogen atom (eg, fluoro group, chloro group, etc.), sulfamoyl Groups (eg, N-propylsulfamoyl group, sulfamoyl group, etc.), acyl groups (eg, acetyl group, benzoyl group, etc.), hydroxyl group,
Examples thereof include a carboxyl group and a heterocyclic thio group (for example, a 1-phenyltetrazolyl-5-thio group, a 1-ethyltetrazolyl-5-thio group, and a group represented by PUG described below). A typical example of the case where two R ₆₄ are linked to form a cyclic structure is (* And ** have the same meaning as described in formula (R-3)).

In the general formulas [I], [II] and [III], the group represented by PUG represents a development inhibitor. For details, tetrazolylthio group, benzimidazolylthio group, benzothiadiazolylthio group, benzoxazolylthio group, benzotriazolyl group, benzoindazolyl group, triazolylthio group, oxadiazolylthio group, imidazolylthio group, thiadiazolylthio group Group, a thioether-substituted triazolyl group (for example, a development inhibitor described in U.S. Pat. No. 4,579,816) or an oxazolylthio group, which may optionally have a substituent, and preferable substituents include the following. Can be That is, R ₇₇ group, R ₇₈ O- group, R
₇₇ S- group, R ₇₇ OCO- group, R ₇₇ OSO ₂ - group, a halogen atom, a cyano group, a nitro group, R ₇₇ SO ₂ - group, R ₇₈ CO- groups, R ₇₇ COO-
Group, Is mentioned. Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. In one molecule
When there are two or more of R ₇₇ , R ₇₈ , R ₇₉ and R _80, these may be linked to form a ring (for example, a benzene ring). Here, the aliphatic group is a saturated or unsaturated, branched or linear, chain or cyclic, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms. The aromatic group is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. The heterocyclic group has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and is selected from a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom. It is a saturated or unsaturated, substituted or unsubstituted heterocyclic group, preferably a 4- to 8-membered heterocyclic group. When these aliphatic group, aromatic group and heterocyclic group have a substituent, examples of the substituent may include a heterocyclic thio group or a substituted or unsubstituted heterocyclic group described as examples of the development inhibitor. The substituents listed as the groups are exemplified.

Particularly preferred development inhibitors in the general formulas (I), (II) and (III) are compounds having a development inhibiting property when cleaved, but after they have flowed into the color developing solution, they are substantially It is a development inhibitor having the property of being decomposed (or changed) into a compound that does not affect photographic properties.

For example, U.S. Pat.No.4,477,563, JP-A-60-218644
No. 60-221750, No. 60-233650 or No. 61-11
No. 743.

In the formula (III), preferred R ₁ is R ₃ and R ₅ have the same meaning as described above.

In the formula [III], preferred A and A 'are a hydrogen atom.

In the formula [III], preferred 1 is 0 or 1.

Hereinafter, specific examples of the compound used in the present invention are listed, but the present invention is not limited thereto.

Specific examples of the synthesis of compounds are shown below. The compounds used in the present invention can be easily synthesized by the same method.

1) Synthesis of 1-A 400 g of acetonitrile was added to 50 g of 2,5-dimethoxyaniline.
l, 26 ml of pyridine were added, and 46 g of phenylchloroformate was added dropwise, followed by stirring at room temperature for 3 hours. After completion of the reaction, an aqueous hydrochloric acid solution was added to the reaction mixture, extracted with ethyl acetate, washed with water, dried and concentrated to obtain 50 g of the title compound.

2) Synthesis of 1-B 300 ml of acetonitrile was added to 25 g of 1-A obtained above.
-22 g of hexadecylamine was added, and the mixture was heated under reflux for 5 hours. After completion of the reaction, an aqueous hydrochloric acid solution was added to the reaction mixture, and the precipitated crystals were separated by filtration, washed with acetonitrile, and dried.
35 g of the title compound were obtained.

3) Synthesis of 1-C To 16 g of 1-B obtained above, 250 ml of 47% hydrobromic acid was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, water was added to the reaction mixture, and the precipitated crystals were separated by filtration, washed with acetonitrile, and dried to obtain 11 g of the title compound.

4) Synthesis of 1-D To 1.5 g of 1-C obtained above, 50 ml of ethanol and 0.9 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were added, and the mixture was stirred at room temperature for 30 minutes. . After the completion of the reaction, the precipitated crystals were separated by filtration and dried to obtain 1.3 g of the title compound.

5) Synthesis of Exemplified Compound (1) 150 g of ethyl acetate was added to 1.3 g of 1-D obtained above.
2.0 g of 5-mercapto-1- (4-nitrophenyl) -tetrazole and 0.1 g of p-toluenesulfonic acid monohydrate were added, and the mixture was stirred at 50 ° C. for 1 hour. After completion of the reaction, the precipitated insolubles were removed by filtration, and the filtrate was concentrated. The residue was crystallized from acetonitrile, separated by filtration, and dried to obtain 1.7 g of the title compound.

1) Synthesis of 2-A To 80 g of 2,5-dimethoxyaniline was added 450 g of 47% hydrobromic acid, which was heated under reflux for 6 hours. After completion of the reaction, the reaction mixture was concentrated, and the precipitated crystals were separated by filtration, washed with acetonitrile, and dried to obtain 87 g of the title compound.

2) Synthesis of 2-B 300 ml of acetonitrile was added to 30 g of 2-A obtained above, and 28 ml of pyridine was added thereto under a nitrogen stream, and the mixture was added at room temperature.
Stir for 15 minutes. Further, under a nitrogen gas stream, n-hexadecyl chloroformate 48 g was N, N-dimethylacetamide 150 m
After the solution dissolved in l was added dropwise, the mixture was stirred at room temperature for 3 hours.
After completion of the reaction, a hydrochloric acid / hydroxyl solution was added to the reaction mixture, and the precipitated crystals were separated by filtration, washed with acetonitrile, and dried to obtain 54 g of the title compound.

3) Synthesis of 2-C To 30 g of 2-B obtained above, 500 ml of ethyl acetate and 45 g of manganese dioxide were added, and the mixture was stirred at 45 ° C for 3 hours. After completion of the reaction, insolubles were removed by filtration, and the filtrate was concentrated to obtain 23 g of the title compound.

4) Synthesis of Exemplified Compound (2) To 2.0 g of 2-C obtained above, 600 ml of methylene chloride, 9.2 g of 2-mercapto-5-methylthio-1,3,4-thiadiazole, 9.2 g of p-toluenesulfonic acid. 0.5 g of monohydrate
Was added and the mixture was refluxed at room temperature for 2 hours. After the completion of the reaction, the precipitated crystals were separated by filtration and dried to obtain 27.8 g of the title compound. (Mp: from 135.8 to 136.0 ° C.) a compound of the general formula (I) of the present invention, 1.0 × 10 ^-7 ~1.0 ×
It is used in the range of 10 ⁻³ mol / m ² , preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻⁴ mol / m ² .

The compound of the present invention is dissolved in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve, etc. Can be used.

Also, by the well-known emulsification dispersion method, it is dissolved in an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified. A dispersion can also be prepared and used. Alternatively, the compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (IV).

General formula (IV) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group,
G ₁ -SO ₂ -group, -SO- group, Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (IV), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. This alkyl group may have a substituent.

In formula (IV), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with the aryl group.

Preferred as R ₁ is an aryl group, particularly preferably a group containing a benzene ring.

The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group,
Aryl group, substituted amino group, ureido group, urethane group,
Aryloxy, sulfamoyl, carbomoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl An acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, And the like. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), and an alkoxy group (preferably having 1 to 20 carbon atoms). ), A substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms),
Examples thereof include a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), and a phosphoric amide group (preferably having 1 to 30 carbon atoms).

In formula (IV), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). .

G ₁ In the case of, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group and the like). ), Aralkyl groups (eg, o-hydroxybenzyl group), aryl groups (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl) And the like), and a hydrogen atom is particularly preferable.

R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

As G in the general formula (IV), Is most preferred.

Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
-R ₂ moiety of atoms may be such as to occur a cyclic structure cyclization reaction to form a containing, include those described in, for example, JP 63-29751 as an example.

A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (IV) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (IV) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Patent Nos. 4,385,108 and 4,459,347;
-195,233, 59-200,231, 59-201,045, 5
Nos. 9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
And the groups described in JP-A-62-67,510.

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

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No. 4,278,748, No. 4,385,108, No. 4,459,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
Nos. 61-170,733, 61-270,744, 62-948
No., EP217,310, EP356,898, or US4,686,167
No., JP-A-62-178,246, JP-A-63-32,538, JP-A-63-10
No. 4,047, No. 63-121,838, No. 63-129,337, No. 63-2
No. 23,744, No. 63-234,244, No. 63-234,245, No. 63-
No. 234,246, No. 63-294,552, No. 63-306,438, JP-A No. 1-100,530, No. 1,105,941, No. 1-105,943,
JP-A-64-10,233, JP-A-1-90,439, Japanese Patent Application No. 63-90
No. 105,682, No. 63-114,118, No. 63-110,051, No. 63
-114,119, 63-116,239, 63-147,339, 6
3-179,760, 63-229,163, Japanese Patent Application No. 1-18,377
Nos. 1-18,378, 1-18,379, 1-15,755
Nos. 1-16,814, 1-40,792, 1-42,615
Nos. 1-42,616, 1-123,693, 1-126,284
Those described in the item can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1.times.10.sup.- ⁶ mol to 5.times.10.sup.- ² mol, more preferably 1.times.10.sup.- ⁵ mol to 2.times.10.sup.- ⁵ mol per mol of silver halide.
A range of × 10 ^-2 mol is a preferable addition amount.

The first and second silver halide emulsion layers may be coated on the support in any order. For example, a second silver halide emulsion layer, a first silver halide emulsion layer, and vice versa may be arranged in this order on a support. Further, another hydrophilic colloid layer may be provided between these layers.

The first emulsion layer preferably has a coated silver amount of 0.01 to 2.0 g.
In / m ^2, preferably, 0.05 to 1.0 g / m ^2, coated silver amount of the second emulsion layer, 0.5~7.5g / m ^2, and preferably is 1.0~6.0g / m ² suitably.

The above-mentioned hydrophilic colloid layer contains gelatin or a synthetic polymer (polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc.) in a range of 0.1 to 5.0 μm, preferably 0.2 to 5.0 μm.
~ 4.0μ is appropriate.

The silver halide emulsion used in the first and second silver halide emulsion layers of the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide and silver bromide. .

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly 0.5 μm.
The following is preferred. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic and octahedral, and irregular such as spherical and tabular.
It may be one having a suitable crystal or one having a complex form of these crystal forms.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A dye may be contained as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the range of 350 nm to 600 nm are used to increase the light absorption.

These dyes are added to the emulsion layer depending on the purpose,
Alternatively, it is preferable to add and fix a non-photosensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with the mordant before use.

Different by the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ² ~
It is added in the range of 1 g / m ² . Preferably 50mg~500mg / m ²
It is.

The dyes used are disclosed in various known patents. For example, JP-A-55-155,350; JP-A-55-155,351;
-92716, 56-12639, 63-27838, U.S. Pat.
3, WO 88/04794.

Known water-soluble dyes can also be used. Some examples follow.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein: cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives, polyvinyl alcohol, acetal of polyvinyl alcohol portion, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylidazole, etc. Can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in British Patent 618,061 and the like.

As the sulfur sensitizer, various sulfur compounds such as thiosulfate, thiourea, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin.

As the reduction sensitizer, a stannous salt, an amine salt, formamidinesulfinic acid, a silane compound and the like can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindene) ), Pentaazaindenes, etc .; and many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. Rukoto can. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, etc.), aldehydes, glutaraldehyde, etc., N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine) , 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4
-Dichloro-6-hydroxy-s-triazine, etc.),
Mucohalogen acids and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), and alkyl esters such as fatty acid esters of polyhydric alcohols. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group or a phosphate group, such as acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or phosphoric acid Amphoteric surfactants such as esters, alkyl betaines, and amine oxides; alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Examples of development accelerators suitable for use in the present invention or accelerators for nucleation transmission development include JP-A-53-77616 and JP-A-54-377.
In addition to the compounds disclosed in Nos. 32, 53-137, 133, 60-140,340, and 60-14959, various compounds containing an N or S atom are effective.

 Next, specific examples are listed.

n-C ₄ H ₉ N (C ₂ H ₄ OH) ₂ These accelerators have an optimum addition amount depending on the kind of the compound, but 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
It is desirable to use it in the range of 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (H ₂ O), such as alcohols such as methanol and ethanol, acetone, dimethylformamide, and methylcellosolve, and added to the coating solution.

 A plurality of these additives may be used in combination.

To obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use a high alkali developer close to pH 13 described in JP-A-975, and a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / or more of sulfite ion as a preservative, and has a pH of 10.5
With a developer having a pH of from 12.3 to 12.3, particularly from 11.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-). 3-pyrazolidone), aminophenols (for example, N
-Methyl-p-aminophenol) or the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent and 3
-Suitable for processing with a developer containing pyrazolidones or aminophenols. Preferably, the developer contains 0.05 to 0.5 mol / dihydroxybenzenes / mol.
, 3-pyrazolidones or aminophenols are 0.
It is used in the range of 06 mol / or less.

Further, as described in U.S. Pat. No. 4,269,929, the development speed can be increased by adding amines to a developer to shorten the development time.

Other developers include pH buffers such as sulfites, carbonates, borates and phosphates of alkali metals, bromides,
It may contain an iodide and a development inhibitor such as an organic antifoggant (especially nitroindazoles or benzotriazoles) or an antifoggant. Also, if necessary, a water softener, a dissolution aid, a color tone agent,
It may contain a development accelerator, a surfactant (especially preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, and a silver stain inhibitor (for example, 2-mercaptobenzimidazole sulfonic acids) of the film.

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C.

Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is set to 60 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained.

The developing solution of the present invention is disclosed in JP-A-56-2 as a silver stain inhibitor.
The compounds described in 4,347 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Further, compounds described in JP-A-60-93,433 or compounds described in Japanese Patent Application No. 62-186259 can be used as a pH buffer used in the developer.

 Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 (Preparation of photosensitive emulsion) Emulsion-A 4 × 10 ⁻⁷ per mol of silver was added to an aqueous gelatin solution kept at 50 ° C.
An aqueous silver nitrate solution and an aqueous solution of potassium iodide and potassium bromide were added simultaneously over 60 minutes in the presence of moles of potassium iridium (III) chloride and ammonia, and the pAg between them was kept at 7.8 to obtain an average particle size of 0.28 μm. A cubic monodispersed emulsion having an average silver iodide content of 0.3 mol% was prepared. The emulsion was desalted by flocculation, and after adding 40 g of inert gelatin per mol of silver,
C. and 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine as a sensitizing dye and ^10-3 moles per mole of silver in a KI solution, Fifteen
After aged for minutes, the temperature was lowered.

Emulsion-B 1.4 × 10 ^-7 mol of rhodium (III) hexachloride and 4 × 10 ^-7 mol of hexachloride per mol of silver nitrate and 1 mol of silver nitrate in aqueous gelatin solution at pH = 4.0 kept at 50 ° C. A mixed aqueous solution of sodium chloride and potassium bromide containing potassium iridate (III) is simultaneously added at a constant rate for 30 minutes to obtain a silver chlorobromide monodispersed emulsion (Cl composition 70 mol%) having an average particle size of 0.23 μm. Prepared.

This emulsion was washed with water according to a conventional method to remove soluble salts, and then chemically sensitized by adding sodium thiosulfate and potassium chloroaurate. In addition, 0.
A potassium iodide solution corresponding to 1 mol% was added to convert the particle surface.

Further, after that, the following compound as a sensitizing dye was added at 2.7 × 10 ⁻⁴ mol / Ag mol while the temperature was kept at 50 ° C., and the mixture was aged for 15 minutes and then stored at a lower temperature.

(Preparation of coating sample) Support: Undercoat layer (0. 1) made of vinylidene chloride copolymer
5 μ) polyethylene terephthalate film (1
50μ) On the support, coating was performed in order from the support side to form a layer structure of UL, ML, OL, and PC. The preparation method and coating amount of each layer are shown below.

(UL) After dissolving Emulsion-B together with gelatin at 40 ° C,
5-methyl benzotriazole, 85mg / m ^2, 6- methyl-4-hydroxy-1,3,3a, 7- tetrazaindene 12 mg / m
^2. 30 wt% of polyethyl acrylate and the following compound (d) as a gelatin hardener were added to the following compounds (a), (b) and (c) and gelatin, and Ag3.6 g / m ² , Table 1 The hydrazine compound was applied so as to have a density of 2.8 × 10 ⁻⁵ mol / m ² and gelatin of 1.9 g / m ² .

(ML) 10 g of gelatin, the above compound (d) was added to gelatin
2.0 wt% was added, and water was added so as to obtain a final volume of 250 ml, and the mixture was applied so that gelatin became 1.5 g / m ² .

(OL) The above-mentioned emulsion-A was dissolved at 40 ° C., and 5-methylbenztriazole 3 mg / m ² , 6-methyl-4-hydroxy-1,
3,3a, 7-tetrazaindene, 4.3 × 10 ⁻⁵ mol / m ^{2 of} the compound of the general formula (I) of the present invention shown in Table 1, 0.4 mg of the compound (a)
/ m ^2, (b) 1.5 mg / m ^2, prepared by adding 2 wt% relative to (c) 15 mg / m ² and the compound as a 30 wt% of poly ethyl acrylate and a gelatin hardening agent to gelatin (d) Gelatin did. It was applied so as to have an Ag of 0.4 g / m ² .

(PC) Polymethyl methacrylate dispersion (average particle size: 5.0μ) and the following surfactants were added to the gelatin solution and coated to 1.5 g / m ^{2 of} gelatin and 0.3 g / m ^{2 of} polymethyl methacrylate. did.

(Evaluation of performance) After exposing these samples with 3200 ク K tungsten light through an optical wedge or an optical wedge and a contact screen (Fujifilm, 150L chain dot type), develop at 34 ° C for 30 seconds with the next developer. Fixing, washing and drying.

As the fixing solution, GR-GR manufactured by Fuji Photo Film Co., Ltd.
F1 was used.

 The halftone was expressed by the following equation.

* Halftone = Exposure to give 95% halftone dot area ratio (logE95%)-Exposure to give 5% halftone dot area ratio (logE5%) Halftone dot quality was visually evaluated on a 5-point scale. In the five-point evaluation, "5" indicates the best quality and "1" indicates the worst quality.
"5" and "4" are practically usable as the halftone dot masters for plate making, "3" is a practically usable limit level, "2",
"1" is a quality that cannot be used.

Table 1 shows the obtained results.

The gradation (γ) is the slope of a straight line connecting the points of density 0.3 and 3.0 in the characteristic curve.

From the results in Table 1, the sample of the present invention has a high γ,
It can be seen that an image having a wide halftone and a good halftone quality is provided.

Example 2 (Preparation of Photosensitive Emulsion C) An aqueous solution of gelatin kept at 50 ° C. was added in an amount of 3.0 × 10 3 per mol of silver.
^An aqueous solution of silver nitrate and an aqueous solution of sodium chloride are simultaneously mixed in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , and then soluble salts are removed by a method well known in the art. 6-methyl-4 as stabilizer without aging
-Hydroxy-1,3,3a, 7-tetrazaindene was added. This emulsion was a cubic monodispersed emulsion having an average size of 0.15 μm.

(Coating of Photosensitive Emulsion Layer) The hydrazine compound IV-8 (25 mg /
m ² ), 5-methylbenzotriazole (5 × 10 ⁻³ mol / Ag
mol), polyethyl acrylate latex (30 wt% vs. gelatin), and 1,3-divinylsulfonyl-2-propanol (2.0 wt% vs. gelatin). The amount of silver applied was 3.5 g / m ² .

Second layer gelatin (1.0 g / m ² ) Third layer Same as photosensitive emulsion C, except that 6.0 × 10 ^-6 mol of (NH ₄ ) ₃ RhC
emulsion prepared in the presence of l ₆ D (coated silver amount 0.4 g /
m ² ), 5-methylbenzotriazole (5 × 10 ⁻³ mol / Ag
mol), polyethyl acrylate latex (30 wt% to gelatin), 1,3-divinylsulfonyl-2-propanol (2 wt% to gelatin), and the compound of the general formula (I) of the present invention shown in Table 2 did.

Fourth layer (protective layer) Gelatin 1.5 g / m ² , polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g / m ² as a matting agent, and the following surfactants and stabilizers as coating aids, And a protective layer containing a UV absorbing dye was applied and dried.

The sample was exposed to an image as shown in FIG. 1 through a document as shown in FIG. 1, developed at 38.degree. C. for 20 seconds, fixed, washed with water, dried, and then printed to obtain the image quality of the printed characters. An evaluation was performed.

Character extraction quality 5 means that a 30 μm wide character is reproduced when an appropriate exposure is performed so that a halftone dot area of 50% becomes 50% halftone dot area on a return photosensitive material using an original as shown in FIG. The image quality is very good and the image quality is very good. On the other hand, the extracted character image quality 1 is an image quality that can only reproduce characters having a width of 150 μm or more when the same appropriate exposure is given. Rank was set. Three or more is a practical level.

The results are shown in Table 2. The sample of the present invention is excellent in the character extraction image quality.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a configuration at the time of exposure in the case where a character extraction image is formed by repetition, and the reference numerals indicate the following. (A) Transparent or translucent pasted base (b) Line drawing original (black part shows line drawing) (c) Transparent or translucent pasted base (d) Halftone original (black part is halftone (Shown) (f) Photosensitive material for return (note that the shaded area indicates the photosensitive layer)

Claims (2)

(57) [Claims] 1. A support comprising a first silver halide emulsion layer containing at least one silver halide emulsion on a support, said first emulsion layer containing a hydrazine derivative, and a second halide layer. A silver halide photographic material having a silver emulsion layer, wherein the second emulsion layer contains a compound represented by formula (I). General formula (I) Where R ₁ is R ₃ represents an alkyl group, an aryl group or a heterocyclic group, R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group, and R ₂ is a substituent having a Hammett's substituent constant σp of 0.3 or less. And n represents 0, 1 or 2, and n is 2
In the above case, two R ₂ may be the same or different, B represents a group that releases PUG after elimination from the hydroquinone mother nucleic acid derivative, PUG represents a development inhibitor, and l represents an integer. ,
A and A 'represent a hydrogen atom or a group which can be removed by an alkali, and R ₁ and R ₂ , R ₁ and A or A', R ₂ and A or A ', and two R ₂ together A ring may be formed. " 2. The silver halide photographic material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (IV). General formula (IV) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, Represents a thiocarbonyl group or an iminomethylene group; A ₁ , A ₂
Represents a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.