JP3038457B2 - Silver halide photographic light-sensitive material and photographic image forming method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and, more particularly, to a super-high contrast silver halide photographic material used for photolithography.

[0002]

BACKGROUND OF THE INVENTION The addition of hydrazine compounds to silver halide photographic emulsions and developers is disclosed in U.S. Pat.
No. 727 (a developing solution combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color image), No. 3,386,831 (silver halide) (Containing β-mono-phenylhydrazide of an aliphatic carboxylic acid as a stabilizer for a light-sensitive material), 2,419,975, and Mees, The Theory of Photographic Process
(The Theory of Photographic Process) Third Edition (196
6) 281 pages. Among them, in particular, US Pat. No. 2,419,975 discloses that a high contrast negative image can be obtained by adding a hydrazine compound.
It has been disclosed. The patent discloses that when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH such as 12.8, extremely hard photographic characteristics with a gamma (γ) exceeding 10 can be obtained. Is described. However, a strong alkaline developer having a pH close to 13 is liable to be oxidized by air and is unstable, and cannot withstand long-term storage or use. Silver halide photosensitive materials containing hydrazine compounds
There have been attempts to develop a high-contrast image by developing with a pH developer.

[0003] JP-A-1-179939 and JP-A-Hei-1
No. 179940, a process of developing with a developer having a pH of 11.0 or less using a sensitizing material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group. A method is described. However,
When a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit amount, it may impair photosensitivity, inhibit development, or hinder the action of other useful adsorptive additives. Therefore, the amount used is limited, and sufficient high contrast cannot be exhibited.

US Pat. Nos. 4,998,604 and 4,994
No. 365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is apparent from these examples, the high contrast is not sufficient, and it is difficult to obtain the high contrast and the necessary Dmax under practical development conditions. The nucleation hard contrast material using a hydrazine derivative has a large change in photographic properties due to a change in pH of a developer. The pH of the developer greatly varies due to an increase due to air oxidation of the developer and concentration due to evaporation of water, or a decrease due to absorption of carbon dioxide in the air. Therefore,
Attempts have been made to reduce the developer pH dependence of photographic performance. As described above, in the prior art, even when processed with a developer having a pH of less than 11, it was not possible to obtain a light-sensitive material exhibiting sufficient contrast and having a small dependence of photographic performance on the pH of the developer.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is firstly to provide a silver halide photographic material capable of obtaining extremely hard negative gradation photographic properties having a gamma exceeding 10 using a stable developing solution. It is to provide a photosensitive material. A second object of the present invention is to provide a silver halide photographic light-sensitive material in which the photographic performance has little dependence on the developer pH. A third object of the present invention is to provide a silver halide photographic material which can be hardened with a developer having a pH of 11 or less.

[0006]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
At least one photosensitive silver halide emulsion layer is provided on a support, and at least one hydrazine derivative represented by the general formula (I) and a general formula (I) II), (III), (IV), (V)
And at least one compound selected from the compounds represented by (VI).

[0007]

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R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G is a -CO- group,
—SO ₂ — group, —SO— group, —COCO— group, thiocarbonyl group, iminomethylene group or —P (O) (R ⁴ )
R ² represents a substituted alkyl group in which a carbon atom substituted by G is substituted by 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.

[0009]

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In the formula, Y represents a group adsorbed on silver halide. X represents a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom,
It represents a divalent linking group consisting of an atom or an atom group selected from sulfur atoms. A represents a divalent linking group. B represents an amino group, an ammonium group and a nitrogen-containing heterocycle,
The amino group may be substituted. m represents 1, 2 or 3, and n represents 0 or 1.

[0011]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom or an aliphatic residue. R ₁ and R ₂ may combine with each other to form a ring. R ₃ represents a divalent aliphatic group. X ₁ represents a divalent hetero ring containing a nitrogen, oxygen or sulfur atom. n represents 0 or 1. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group.

[0013]

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In the formula, R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 3 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. However, when R ₁₁ and R ₁₂ simultaneously represent an alkyl group, R ₁₁ +
R ₁₂ represents 10 or more carbon atoms. R ₁₁ and R ₁₂ do not represent a hydrogen atom at the same time, and may combine with each other to form a ring. n represents an integer of 2 to 50. R ₁₃ ,
R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom or a carbon atom
4 represents an alkyl group.

[0015]

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R ₁₁ and R ₁₂ are the same as those in formula (IV), and R ₁₁ ′ and R ₁₂ ′ have the same meaning as R ₁₁ and R ₁₂ .

[0017]

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X, Y and B are the same as those in formula (II), and A ₀ represents a divalent linking group having at least two alkyleneoxy units. m represents 1, 2 or 3, and n represents 0 or 1.

Next, the compound represented by formula (I) will be described in more detail. In the general formula (I), R
^The aliphatic group represented by ¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. R ¹
The aromatic group represented by is a monocyclic or bicyclic aryl group, for example, 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, and S atoms, which may be a single ring, 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 thiazoline group, and a benzothiazolyl group. Are preferred. R
Preferred as ¹ is an aromatic group, a nitrogen-containing heterocyclic ring and a group represented by the general formula (b).

[0020]

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[0021] (wherein ,, X _b represents an aromatic group or a nitrogen-containing heterocyclic group, R _b ¹ to R _b ⁴ each represent a hydrogen atom, a halogen atom or an alkyl group,, X _b and R _b
May have a substituent in the case ¹ to R _b ⁴ is possible. r and s represent 0 or 1. ) R ¹ is more preferably an aromatic group, particularly preferably an aryl group. R ¹ may be substituted with a substituent. Examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, and a sulfinyl. Group, hydroxy group, halogen atom, cyano group, sulfo group or carboxyl group, alkyl and aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group,
In addition to a sulfonamide group, a nitro group, an alkylthio group, an arylthio group and the like, a group represented by the following general formula (c) can be mentioned.

[0022]

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In the formula (c), Y _c is -CO-, -SO
_2- , -P (O) (R _c3 )-(where R _c3 represents an alkoxy group or an aryloxy group) or -OP
(O) (R _c3 )-, where L is a single bond, -O-, -S
— Or —NR _c4 — (wherein R _c4 represents a hydrogen atom, an alkyl group, or an aryl group). R _c1 and R _c2
Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, which 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 the general formula (c).

In the general formula (c), the aliphatic group represented by R _c1 is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c1 is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group. The hetero ring of R _c1 is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, and S atoms, which may be a single ring, or other ring. A condensed ring may be formed with an aromatic or hetero ring. The heterocyclic ring 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 thiazolyl group, and a benzothiazolyl group. Are preferred. R _c1 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted. For example, an alkyl group, an aralkyl group, an alkenyl group,
Alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy , Halogen atom, cyano group, sulfo group or carboxyl group, alkyl and aryloxycarbonyl group, acyl group,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido 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, alkenyl or alkynyl group. The aromatic group represented by R _c2 is a monocyclic or bicyclic aryl group, such as a phenyl group. R _c2 may be substituted with a substituent. Examples of the substituent include those listed as R _c1 and the substituent in the general formula (c). R _c1 and R _c2 may be linked to each other to form a ring, if possible. R _c2 is more preferably a hydrogen atom.
In formula (c), Y _c represents —CO— or —SO ₂
Is particularly preferred, and L is preferably a single bond or -NR _c4- .

The aliphatic group represented by R _c4 in the general formula (c) is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c4 is a monocyclic or bicyclic aryl group, such as 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 _c4 is more preferably a hydrogen atom.

The G in the general formula (I) is most preferably a -CO- group. R ^{2 in the} general formula (I) represents a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, preferably two electron-withdrawing groups, and particularly preferably three electron-withdrawing groups. Represents a substituted alkyl group substituted with a suction group. The electron withdrawing group for substituting the carbon atom substituted with G in R ² preferably has a σp value of 0.2 or more,
σm 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 arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate ester group, phosphonamide group, arylazo group, It represents an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group. R ^{2 in the} general formula (I) particularly preferably represents a trifluoromethyl group.

R ¹ and R ^{2 in} the general formula (I) may have a ballast group or a 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, an alkylphenoxy group, and the like. Can be. Further, as a polymer, for example,
No. 0.

R ¹ and R ^{2 in} the general formula (I) may have a group in which a group for enhancing the adsorption to the surface of the silver halide grain is incorporated. Examples of such an adsorbing group include thiourea group, heterocyclic thioamide group, mercapto heterocyclic group, triazole group and the like, US Pat. Nos. 4,385,108 and 4,459,347, and JP-A-59-195,233.
Nos. 59-200, 231 and 59-201, 04
No. 5, 59-201, 046, 59-201, 0
No. 47, 59-201, 048, 59-201,
Nos. 049, 61-170, 733, 61-27
Nos. 0,744, 62-948, 63-234,2
No. 44, No. 63-234, No. 245, No. 63-234,
No. 246. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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

The following is a specific example. Synthesis Example: Synthesis of Exemplified Compound 16 Under a nitrogen atmosphere, triethylamine (15.3 ml) was added to a mixed solution of raw material compound A (63.2 g) and tetrahydrofuran (200 ml), and the mixed solution was cooled to 5 ° C.
Trifluoroacetic anhydride (16.9 ml) was added and stirred at room temperature overnight. The reaction solution was poured into 0.1N HCl aqueous solution, 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 residue was isolated and purified by silica gel chromatography to obtain the desired product (52.1 g). The structure of the compound was confirmed by an nmr spectrum and an ir spectrum. The structure of the starting compound A is shown below.

[0041]

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Next, the compound represented by formula (II) will be described in more detail. Examples of the group adsorbed on silver halide represented by Y include a nitrogen-containing heterocyclic compound.
When Y represents a nitrogen-containing heterocyclic compound, the compound of the general formula (II) is represented by the following general formula (II-a).

[0043]

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In the formula, 1 represents 0 or 1, m represents 1,
Represents 2 or 3, and n represents 0 or 1.
[(X) _n -AB] _m has the same meaning as that in formula (II), and Q represents a carbon atom, a nitrogen atom, an oxygen atom,
A group of atoms necessary to form a 5- or 6-membered heterocyclic ring composed of at least one kind of sulfur atom.
This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring.

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

M represents a hydrogen atom, an alkali metal atom (for example, sodium atom, potassium atom, etc.), an ammonium group (for example, trimethylammonium group, dimethylbenzylammonium group, etc.), or M = H or an alkali metal atom under alkaline conditions. (For example, acetyl, cyanoethyl, methanesulfonylethyl, etc.). These heterocycles may be nitro group, halogen atom (eg, chlorine atom, bromine atom, etc.), mercapto group, cyano group, and substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, t-group). Butyl group,
Cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.), aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group,
3,4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group,
Etc.), an alkoxy group (for example, a methoxy group, an ethoxy group,
Etc.), an aryloxy group (for example, phenoxy group, 4-methoxyphenoxy group, etc.), an alkylthio group (for example, methylthio group, ethylthio group, methoxyethylthio group),
Arylthio group (for example, phenylthio group), sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group,
a carbamoyl group (eg, an unsubstituted carbamoyl group, a methylcarbamoyl group, a phenylcarbamoyl group, etc.), a sulfamoyl group (eg, an unsubstituted sulfamoyl group, a methylsulfamoyl group,
Phenylsulfamoyl group, etc.), carbonamide group (eg, acetamido group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group,
), Acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, etc.), ureido group (eg, unsubstituted ureido group, methylureido group, ethylureido group, phenyl) Ureido group, etc.), thioureido group (for example, unsubstituted thioureido group, methylthioureido group,
Etc.), acyl group (for example, acetyl group, benzoyl group,
Heterocyclic group (eg, 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-
Tetrahydrofuryl group, tetrahydrothienyl group,
Oxycarbonyl group (eg, methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), amino group (eg, Unsubstituted amino group, dimethylamino group, methoxyethylamino group, anilino group, etc.), carboxylic acid or a salt thereof, sulfonic acid or a salt thereof, and hydroxy group.

Examples of the divalent linking group represented by X include -S-, -O-, -N (R ₁ )-, -C (O) O-,
-OC (O) -, - C (O) N (R 2) -, - N (R 3) C
_{(O) -, - SO 2} N (R 4) -, - N (R 5) SO 2 -,
_{-N (R 6) C (O} ) N (R 7) -, - N (R 8) C (S) N
_{(R 9) -, - N} (R 10) C (O) O -, - SO 2 -, -
C (O)-,-(O) S (O) O-, -O (O) S
(O) —, and the like, and these linking groups are linear or branched alkylene groups (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group) , Etc.). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
₇ , R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a propyl group, an n-butyl group, etc.), a substituted or unsubstituted aryl group (eg, Phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.) ).

A represents a divalent linking group. As the divalent linking group, a linear or branched alkylene group (for example, methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene, Etc.), linear or branched alkenylene groups (eg, vinylene group, 1-methylvinylene group, etc.), linear or branched aralkylene groups (eg, benzylidene group, etc.), arylene groups (eg, phenylene, naphthylene, etc.), etc. Is mentioned. In the above group represented by A, X and A may be further substituted in any combination. The substituted or unsubstituted amino group of B is represented by the general formula (II-b).

[0049]

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In the formula, R ¹¹ and R ¹² may be the same or different and each represent a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aralkyl group having 1 to 30 carbon atoms. The group may be straight-chain (for example, methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl, benzyl, 1-naphthylmethyl, etc.), branched (for example, iso propyl group, t
-Octyl group, etc.) or cyclic (eg, cyclohexyl group, etc.).

Further, R ¹¹ and R ¹² may be linked to each other to form a ring, and a saturated ring containing one or more hetero atoms (eg, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) therein. It may be cyclized to form a heterocycle, and examples thereof include a pyrrolidyl group, a piperidyl group, and a morpholino group. Examples of the substituent of R ¹¹ and R ¹² include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl having 20 or less carbon atoms. Group (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group having 20 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group,
Phenethyloxy group), monocyclic aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy group having 20 or less carbon atoms (eg, acetyloxy group, propionyloxy group, etc.), carbon An acyl group (eg, an acetyl group, a propionyl group, a benzoyl group, a mesyl group, etc.), a carbamoyl group (eg, a carbamoyl group, an N, N-dimethylcarbamoyl group, a morpholinocarbonyl group, a piperidinocarbonyl group, etc.), and sulfamoyl Group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), having 2 carbon atoms
0 or less acylamino group (for example, acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, p-toluenesulfonamide group, etc.), carbon number 20
Examples thereof include the following carbonamide groups (eg, a methylcarbonamide group, a phenylcarbonamide group, etc.), ureido groups having 20 or less carbon atoms (eg, a methylureido group, a phenylureido group, etc.), and amino groups. The ammonium group of B is represented by the general formula (II-c).

[0052]

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In the formula, R ¹³ , R ¹⁴ and R ¹⁵ are the same groups as R ¹¹ and R ¹² in the above formula (II-b),
Z ⁻ represents an anion, for example, a halide ion (eg, Cl ⁻ , Br ⁻ , I ^−, etc.), a sulfonate ion (eg, trifluoromethanesulfonate, paratoluenesulfonate, benzenesulfonate, parachlorobenzenesulfonate, etc.), sulfonate Fat ion (for example, ethyl sulfate, methyl sulfate, etc.), perchlorate, tetrafluoroborate and the like can be mentioned. p represents 0 or 1, and is 0 when the compound forms an internal salt.

The nitrogen-containing heterocyclic ring of B is a 5- or 6-membered ring containing at least one or more nitrogen atoms, and these rings may have a substituent and may be condensed with another ring. May be. Examples of the nitrogen-containing hetero ring include an imidazolyl group, a pyridyl group, and a thiazolyl group.

Preferred examples of the general formula (II) include compounds represented by the following general formulas (II-m), (II-n), (II-o) and (II-p).

[0056]

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In the formula,-(X) _n -AB, M, and m have the same meanings as those in formula (II-a). Z ₁ , Z ₂ and Z ₃ are each represented by — (X) _n -A in formula (II-a).
Has the same meaning as -B, or represents a halogen atom, an alkoxy group having 20 or less carbon atoms (eg, a methoxy group), a hydroxy group, a hydroxyamino group, a substituted or unsubstituted amino group, and the substituent is represented by the general formula It can be selected from the substituents of R ¹¹ and R ¹² in (II-b).
Provided that at least one of Z ₁ , Z ₂ and Z ₃ is-
(X) Synonymous with _n- AB. Further, these heterocycles may be substituted with a substituent applied to the heterocycle of the formula (II). Next, examples of the compound represented by the general formula (II) are shown, but the present invention is not limited thereto.

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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In the formula, R ¹ and R ² each represent a hydrogen atom or an aliphatic residue. R ¹ and R ² may combine with each other to form a ring. R ³ represents a divalent aliphatic group. X is nitrogen,
Represents a divalent hetero ring containing an oxygen or sulfur atom.
n represents 0 or 1. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group. As the aliphatic residue of R ¹ and R ² , an alkyl group, an alkenyl group and an alkynyl group each having 1 to 12 carbon atoms are preferable, and each may be substituted with an appropriate group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group, an isopropyl group and a sec-
Butyl group, cyclohexyl group and the like. Examples of the alkenyl group include an allyl group, a 2-butenyl group, a 2-hexenyl group, and a 2-octenyl group. Examples of the alkyl group include a propargyl group and a 2-pentynyl group. Examples of the substituent include a phenyl group, a substituted phenyl group, an alkoxy group, an alkylthio group, a hydroxy group, a carboxyl group, a sulfo group, an alkylamino group, and an amide group.

In the case where R ¹ and R ² form a ring, a 5- or 6-membered carbon or heterocyclic ring composed of carbon or a combination of nitrogen and oxygen, particularly a saturated ring is preferable. Piperidyl, morpholyl, piperazyl, 4-methyl-piperazyl and the like. R ¹
And R ² are particularly preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group.

[0065] As the divalent aliphatic group of R ³ -R ⁴ - or -R ⁴ S- are preferred. Here, R ⁴ is a divalent aliphatic residue, preferably a saturated or unsaturated one having 1 to 6 carbon atoms, for example, —CH ₂ —, —CH ₂ CH ₂ —, — (CH ₂ )
_{3 -, - (CH 2)} 4 -, - (CH 2) 6 -, - CH 2 CH
_{= CHCH 2 -, - CH 2} C = CCH 2 -, - CH 2 C
H (CH ₃ ) CH ₂ — and the like.

R ₄ has preferably 2 to 4 carbon atoms, and more preferably R ⁴ is —CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ . Note that _n of (X) _n is 0
R ³ in the formula represents only —R ⁴ —.

As the hetero ring of X, a 5- or 6-membered hetero ring containing nitrogen, oxygen or sulfur may be fused to the benzene ring. Heterocycles are preferably aromatic and include, for example, tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole,
Benzoxazole and the like. Of these, tetrazole and thiadiazole are particularly preferred.

As the alkali metal of M, Na ⁺ ,
K ⁺ , Li ⁺ and the like. As alkaline earth metals,
Ca ⁺⁺ , Mg ⁺⁺ , and the like. Examples of the quaternary ammonium salt of M include those having 4 to 30 carbon atoms, such as (C
^{_{H 3) 4 N +, (}} C 2 H 5) 4 N +, (C 4 H 9) 4 N +, C
^{_{6 H 5 CH 2 N + (}} CH 3) 3, C 16 H 33 N + (CH 3) 3
And so on. As the quaternary phosphonium salt, (C ₄ H ₉ )
₄ P ⁺ , C ₁₆ H ₃ P ⁺ (CH ₃ ) ₃ , C ₆ H ₃ CH ₂ P ⁺
(CH ₃ ).

The inorganic acid salt of the compound represented by the general formula (III) includes, for example, hydrochloride, sulfate, phosphate and the like, and the organic acid salt includes acetate, propionate, methanesulfonate, benzene and the like. Sulfonates, p-toluenesulfonates and the like. Specific examples of the compound represented by the general formula (III) are shown below.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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Next, the compounds represented by formulas (IV) and (V) will be described in more detail.

R ₁ and R ₂ may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms (including those having a substituent, for example, a methyl group, an ethyl group, -Butyl group, n-hexyl group, n-octyl group,
2-ethylhexyl group, methoxyethyl group, ethylthioethyl group, dimethylaminoethyl group, n-decyl group, n
-Dodecyl group, phenoxyethyl group, 2,4-di-t-
Amylphenoxyethyl group, n-octadecyl group, etc.)
An alkenyl group having 3 to 30 carbon atoms (including those having a substituent; for example, an allyl group, a butenyl group, a pentenyl group,
Etc.) or an aralkyl group having 7 to 30 carbon atoms (including those having a substituent. For example, a phenethyl group, a benzyl group,
-Methoxybenzyl group, 4-t-butylbenzyl group,
2,4-di-t-amylphenethyl group, etc.).

Further, R ₁ and R ₂ may be unified as alkylene which may be substituted, and may form a ring together with a nitrogen atom. (For example, pyrrolidine ring, piperidine ring, 2
-Methyl piperidine ring, hexamethylene imine ring,
etc). R ₃ , R ₄ , R ₅ and R ₆ may be the same or different, and each may be a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms (preferably a lower alkyl group having no substituent.
For example, a methyl group, an ethyl group, an n-butyl group, etc.).

When R ₁ and R ₂ have a substituent, examples of the substituent include a halogen atom (eg, a chlorine atom and a bromine atom), a cyano group, a nitro group, a hydroxy group, and an alkoxy group (eg, a methoxy group) ), An aryloxy group (eg, a phenoxy group, a 2,4-di-t-amylphenoxy group, etc.), an alkylthio group (eg, a methylthio group, etc.), an arylthio group (eg, a phenylthio group, etc.), an acyloxy group ( For example, an acetyloxy group,
Benzoyloxy group, etc.), amino group (eg, unsubstituted amino group, dimethylamino group, etc.), carbonamide group (eg, acetamido group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.) ), An oxycarbonylamino group (eg, methoxycarbonylamino group, etc.), a ureido group (eg, unsubstituted ureido, 3,3-dimethylureide group, etc.), a thioureido group (eg, unsubstituted thioureido group, 3-phenylthioureido group) , Etc.), an acyl group (for example, an acetyl group,
Benzoyl group, etc.) oxycarbonyl group (eg, methoxycarbonyl group, etc.), carbamoyl group (eg, methylcarbamoyl group, 4-methylphenylcarbamoyl group,
Etc.), a sulfonyl group (for example, a methanesulfonyl group,
And the like, a sulfamoyl group (eg, a methylsulfamoyl group, a 4-methoxyphenylsulfamoyl group, and the like), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, and the like.

In formulas (IV) and (V), preferably, R ₁
And R ₂ each represents an alkyl group having 1 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and R ₃ , R ₄ , R
₅ and R ₆ represent a hydrogen atom, and n represents an integer of 3 to 20. In the general formulas (IV) and (V), more preferably R
₁ and R ₂ each represent an alkyl group having 5 to 20 carbon atoms. Specific examples of the compounds represented by formulas (IV) and (V) are shown below, but the compounds of the present invention are not limited thereto.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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Next, the compound of the formula (VI) will be described. In the formula, the description other than A ₀ is the same as the description of the general formula (II). A ₀ represents a divalent linking group having at least two alkyleneoxy units, but is preferably

[0089]

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Represents the following. R ₁ ′, R ₂ ′, R ₃ ′ and R ₄ ′ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.). , Q represents an integer of 2 to 50. Specific examples of the compound represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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These general formulas (II), (III), (IV),
Although the optimum amount of (V) and (VI) varies depending on the type of the compound, it is 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^{−3 to} 0.3 g. / M ² is desirably used. These accelerators can be used in suitable solvents (H ₂ O, alcohols such as methanol and ethanol, acetone,
Dimethylformamide, methylcellosolve, etc.) and added to the coating solution. A plurality of these additives may be used in combination.

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 pH 1
It is not necessary to use one or more high alkali developing solutions, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / L or more of sulfite ion as a preservative and has a pH of 11.0 to 9.0.
By using the developing solution, a negative image having a sufficiently high contrast can be obtained. By using a developer having a pH of preferably 10.7 to 9.2, a stable processing system can be constructed. 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 (eg, N-methyl-p-aminophenol) and the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developing solution containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, in this developer, dihydroxy and benzene are contained in an amount of 0.05 to 0.05%.
0.5 mol / l, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / l or less.

As described in US Pat. No. 4,269,929, the development speed can be increased by adding amines to the developer to shorten the development time. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates,
Bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles)
And an antifoggant or the like. If necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, a silver stain preventing agent for a film. (For example, 2-mercaptobenzimidazolesulfonic acids). 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 method of the present invention is usually 18
Between 50 ° 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 to when it comes out is set to 90 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained. In the developer of the present invention, compounds described in JP-A-56-24347 can be used as silver stain inhibitors. Compounds described in JP-A-61-267759 can be used as a dissolution aid to be added to the developer. Further, the compounds described in JP-A-60-93,433 or the compounds described in JP-A-62-186259 can be used as a pH buffer used in the developer.

The halogen composition of the silver halide emulsion used in the present invention is arbitrary. However, the photosensitive material for line drawing and halftone dot production which requires high photographic sensitivity has a silver chloride content of 80 mol% or less. It is preferred that

As a method for preparing a silver halide emulsion used in the present invention, various methods known in the field of silver halide photographic materials are used. For example, P. Glaf
Chiides et Physique Photographique, by Paul Montel (1967), G.F.
GFDuffin, Photographic Emulsion Chemistry
emistry) (The Focal Pres)
s) 1966), V. El-Zelikmann (VLZe)
Making and Coating Photographic Emulsion (Making and Coa) by likman et al)
ting Photographic Emulsion "(The Focal Press, 1964) and the like.

The emulsion of the present invention is preferably a monodispersed emulsion, and the coefficient of variation is preferably 20% or less, particularly preferably 15% or less.
Here, the variation coefficient is defined as (Equation 1) below.

[0106]

(Equation 1)

The average grain size of the grains in the monodispersed silver halide emulsion is 0.5 μm or less. As a method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a control double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonium, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds, described in JP-A-53-82408 and JP-A-55-82408.
-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-dimethyl-2
-Imidazolidinethione. According to the control double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool. The monodispersed emulsion preferably has a regular crystal form such as a cubic, octahedral, or tetradecahedral, and particularly preferably a cubic. 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. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof may coexist in the process of forming silver halide grains or physical ripening. 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 emulsion.
It is an emulsion prepared 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 amount of iridium salt before the completion of physical ripening in the production process of the silver halide emulsion, particularly at the time of grain formation. The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, for example, iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), hexachloroiridium (I
V) potassium and ammonium hexachloroiridium (III)).

The monodispersed emulsion of the present invention can be used as a chemical sensitizer.
Known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and they are used alone or in combination. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are described in U.S. Pat.
No. 78,947, No. 2,410,689, No. 2,72
8,668, 3,501,313, 3,65
No. 6,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Moisar, Klei
n Gelatine. Proc. Syme. 2nd, 301-309 (197
The method of using polyvinylpyrrolidone and thiosulfate in combination, as reported by 6), also gives good results. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Precious metals other than gold,
For example, complex salts such as platinum, palladium, and iridium may be contained. A specific example is described in US Pat. No. 2,448,
060, British Patent 618,061 and the like. There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following places can be preferably used. Item Applicable part 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4, JP-A-2-103536, page 16, lower right column, line 3, line 3 to line 4 Spectral sensitizing dyes described in page 17, lower left column, line 20, further described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, JP-A-3-18932 and JP-A-3-41164. . 2) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to line 4 Line 18 in the lower right column of the page. 3) Antifoggants 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, furthermore, JP-A-1-237538. Thiosulfinic acid compounds described in the official bulletin. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 6) Matting agent, slip agent JP-A-2-103536, page 19, upper left column, line 15 plasticizer to line, page 19, upper right column, line 15; 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17. 8) Dyes Dyes described in JP-A-2-103536, page 17, lower right column, lines 1 to 18 and solid dyes described in JP-A-2-29438 and Japanese Patent Application No. 3-185773. 9) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 10) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 11) Redox compound A compound represented by the general formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50), and a compound represented by the general formula (3) of JP-A-3-174143, pp. 3 to 20: (R-1), (R-2) and (R-3), compounds described in Compound Examples 1 to 75, and further described in Japanese Patent Application Nos. 3-69466 and 3-15648. 12) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 13) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column to benzenes, page 12, lower left column, and EP 452772A.

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

[0111]

【Example】

Example 1 (Emulsion preparation) Emulsion A: 0.13 M aqueous silver nitrate solution and 0.04 M potassium bromide containing 0.04 M potassium bromide containing (NH ₄ ) ₃ RhCl ₆ corresponding to 1 × 10 ⁻⁷ mol per mol of silver. An aqueous solution of a halogen salt containing 09 M sodium chloride was mixed with sodium chloride,
To a gelatin aqueous solution containing 3-dimethyl-2-imidazolidinethione was added by a double jet method at 38 ° C. for 12 minutes with stirring, and the average particle size was 0.15 μm.
nucleation was performed by obtaining silver chlorobromide grains having a silver chloride content of 70 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, 0.26 M potassium bromide, 0.65 M
A halogen salt aqueous solution containing M sodium chloride was added by a double jet method over 20 minutes. Then 1 ×
Conversion was carried out by adding 10 ^-3 mol of KI solution, washed with water by a flocculation method in accordance with a conventional method, adjusted to pH 6.5 and pAg 7.5 by adding 40 g of gelatin, and further adjusted to 5 mg of sodium thiosulfate per 1 mol of silver. 8 mg of chloroauric acid was added, the mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl-
150 mg of 1,3,3a, 7-tetrazaindene were added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.27 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

(Preparation of Coated Samples) The compounds of the present invention were added to these emulsions as shown in Table 1. The following compounds were used as comparative compounds of the hydrazine derivative of the present invention.

[0113]

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[0114]

[Table 1]

Further, a sensitizing dye represented by the following structural formula (S ₁ ) was added in an amount of 3.4 × 10 ^-4 mol / mol of silver, and 1-phenyl-5-mol.
2 × 10 ⁻⁴ mol of mercaptotetrazole, 5 × 10 ⁻⁴ mol of short-wave cyanine dye represented by the following structural formula (a), water-soluble latex represented by (b) (200 mg /
m ² ), a dispersion of polyethyl acrylate (200 mg /
m ² ) and 1,3-divinylsulfonyl-2-propanol (200 mg / m ² ) as a hardener.

[0116]

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As a protective layer, 1.0 g / m ² of gelatin, 40 mg of an amorphous SiO ₂ matting agent having a particle size of about 3.5 μm /
m ^2, including methanol silica 0.1 g / m ^2, polyacrylamides 100 mg / m ^2, hydroquinone 200 mg / m ^2, a fluorine surfactant and sodium dodecyl benzene sulfonate represented by the following structural formula as a silicone oil and a coating aid The layers were coated simultaneously with the emulsion layers.

[0118]

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The back layer and the back layer protective layer were applied according to the following formulation.

[Formation of Back Layer] Gelatin 3 g / m ² Latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Gelatin hardener

[0121]

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Dye Mixture of dyes [a], [b] and [c]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethyl methacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² dihexyl-α-sulfosacnate sodium salt 15 mg / m ² dodecylbenzenesulfonic acid sodium salt 15 mg / m ² sodium acetate 40 mg / m ²

(Evaluation of photographic characteristics)
After being exposed through an optical wedge with tungsten light of 00 ° K, the film was developed with the following developer 1 at 34 ° C for 25 seconds, fixed, washed with water, and dried. GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used as the fixing solution.

Developer 1 Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-Methylbenzo Triazole 0.4 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Sodium toluenesulfonate 8.0 Add water to 1 liter to pH 10.3 Match

Similarly, the developing treatment was carried out using a developing solution 2 adjusted to pH 10.6 by adding a potassium hydroxide solution to the developing solution 1 and a developing solution 3 adjusted to pH 10.0 by adding acetic acid to the developing solution 1. went.

Table 2 shows the obtained photographic characteristics. Where G
Is defined by Equation 2.

[0129]

(Equation 2)

S _1.5 representing the sensitivity is a logarithmic value of the exposure amount giving a density of 1.5.

[0131]

[Table 2]

As shown in Table 2, the samples of the present invention have pH values
It can be seen that even when processed with a developing solution of less than 11, a high-contrast image is obtained, and the change in photographic sensitivity with respect to a change in pH of the developing solution is small.

Example 2 The coating sample shown in Table 1 was used instead of the following developer 1 in a developer 4
Except that the developing process was carried out.

Developer 4 Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Disodium ethylenediaminetetraacetate 1.0 Potassium bromide 10.0 5-Methylbenzo Triazole 0.4 2-Mercaptobenzimidazole-5-sulfonate 0.3 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Sodium toluenesulfonate 8.0 N-dimethyl-n-hexanolamine 15. 0 Add water to adjust to 1 liter pH 9.8

Table 3 shows the obtained photographic characteristics.

[0136]

[Table 3]

As shown in Table 3, by adding an amine compound to the developer, the pH of the developer can be further lowered to obtain a high contrast photographic performance.

Example 3 Using an emulsion prepared as described below, using a compound of the following (S ₂ ) as a sensitizing dye, and adding a compound of the present invention as shown in Table 4 Was carried out in the same manner as in Example 1 except that the time was changed to 45 seconds.

[0139]

[Table 4]

(Emulsion Adjustment) A cubic monodispersed silver iodobromide emulsion having a grain size of 0.25 μm (coefficient of variation: 0.15, silver iodide: 1.0 mol%, iodine distribution uniform) was obtained by the control double jet method. Prepared. The silver iodobromide emulsion contains K ₃
IrCl ₆ was added to contain 4 × 10 ⁻⁷ mol / Ag mol. The emulsion was desalted by flocculation and kept at 50 DEG C., followed by 10 ^{@ -3} mol of potassium iodide solution per mol of silver and 4-hydroxy-6 as a stabilizer.
-Methyl-1,3,3a, 7-tetrazaindene was converted to silver 1
5 × 10 ^-4 mol was added per mol.

[0141]

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Table 5 shows the obtained photographic characteristics.

[0143]

[Table 5]

As shown in Table 5, the samples of the present invention have pH values
It can be seen that even when processed with a developing solution of less than 11, a high-contrast image is obtained, and the change in photographic sensitivity with respect to a change in pH of the developing solution is small.

Example 4 (Emulsion preparation) A silver nitrate aqueous solution and a sodium chloride aqueous solution were simultaneously mixed in an aqueous gelatin solution kept at 30 ° C. in the presence of 5.0 × 10 ⁻⁶ mol (NH ₄ ) ₃ RhCl ₆ per mol of silver. After that, a soluble salt was removed by a method well known in the art, and gelatin was added. As a stabilizer, 2-methyl-4-hydroxy-1,3,3a, 7- was used without chemical ripening.
Tetraazaindene was added. This emulsion was a cubic monodispersed emulsion having an average grain size of 0.08 μm.

(Preparation of Coated Samples) The compounds of the present invention were added to these emulsions as shown in Table 6. Next, polyethyl acrylate latex is used as a solid content with respect to gelatin at 30 wt%.
1,3-vinylsulfonyl-2 as a hardening agent
-Add propanol, 3.8 on polyester support
It was applied so that the amount of Ag was g / m ² . Gelatin is 1.8
g / m ² . Gelatin 1.5 as a protective layer on this
g / m ² , 2.5 μm particle size polymethyl methacrylate
A layer of 3 g / m ² was applied.

(Evaluation of Photographic Properties) These samples were exposed through an optical wedge by a light room printer P-607 manufactured by Dainippon Screen Co., Ltd.
Using 2 and 3, development processing was performed at 38 ° C. for 40 seconds, followed by fixing, washing and drying. Table 7 shows the obtained photographic characteristics. Here, G is defined by Equation 3.

[0148]

(Equation 3)

Further, S _1.5 representing the sensitivity is a logarithmic value of the exposure amount giving a density of 1.5.

[0150]

[Table 6]

[0151]

[Table 7]

As shown in Table 7, the sample of the present invention has a pH of
It can be seen that even when processed with a developing solution of less than 11, a high-contrast image is obtained, and the change in photographic sensitivity with respect to a change in pH of the developing solution is small.

Continuation of the front page (56) References JP-A-2-103536 (JP, A) JP-A-4-76530 (JP, A) JP-A-4-141651 (JP, A) JP-A-2-294638 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/06 501 G03C 1/295

Claims (3)

(57) [Claims] 1. A hydrazine derivative represented by the general formula (I) having at least one light-sensitive silver halide emulsion layer on a support, and adding the emulsion layer and / or a hydrophilic colloid layer adjacent thereto to a hydrophilic colloid layer. At least one of the general formula (I
A silver halide photographic material containing at least one compound selected from the compounds represented by I), (III), (IV), (V) and (VI). Embedded image R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group,
It may be substituted. G is -CO- group, -SO ₂ -
Group, -SO- group, -COCO- group, thiocarbonyl group,
Represents an iminomethylene group or a —P (O) (R ⁴ ) — group, and R ² represents a substituted alkyl group in which a carbon atom substituted by G is substituted by 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. Embedded image In the formula, Y represents a group adsorbed on silver halide. X represents a divalent linking group consisting of an atom or an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. A represents a divalent linking group. B represents an amino group, an ammonium group and a nitrogen-containing heterocyclic ring, and the amino group may be substituted. m represents 1, 2 or 3, and n represents 0 or 1. Embedded image In the formula, R ₁ and R ₂ each represent a hydrogen atom or an aliphatic residue. R ₁ and R ₂ may combine with each other to form a ring. R
₃ represents a divalent aliphatic group. X ₁ represents a divalent hetero ring containing a nitrogen, oxygen or sulfur atom. n represents 0 or 1. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group. Embedded image In the formula, each of R ₁₁ and R ₁₂ is a hydrogen atom, and has 1 to 30 carbon atoms.
An alkenyl group having 3 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. However, R ₁₁ and R ₁₂
And when simultaneously represents an alkyl group, the carbon number of R ₁₁ + R ₁₂ represents 10 or more. R ₁₁ and R ₁₂ do not represent a hydrogen atom at the same time, and may combine with each other to form a ring. n represents an integer of 2 to 50. R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Embedded image R ₁₁ and R ₁₂ are the same as in general formula (IV),
R ₁₁ ′ and R ₁₂ ′ have the same meaning as R ₁₁ and R ₁₂ . Embedded image X, Y and B are the same as those in the general formula (II), and A ₀
Represents a divalent linking group having at least two alkyleneoxy units. m represents 1, 2 or 3, and n
Represents 0 or 1. 2. The silver halide photographic material according to claim 1, wherein the material has at least one photosensitive layer containing a silver halide emulsion containing 80 mol% or less of silver chloride. 3. A method of forming a photographic image, comprising developing the silver halide photographic material of claim 1 using a developing solution having a pH of at least 9.0 and less than 11.0.