JP2887367B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a silver halide photographic light-sensitive material used in the field of photoengraving, which is capable of rapidly forming an ultra-high contrast image with a highly stable processing solution. Especially negative).

(Prior Art) It is known that a photographic image having a very high contrast can be formed using a certain kind of silver halide, and such a method of forming a photographic image is used in the field of photolithography.

Conventionally, a special developer called a lith developer has been used for this purpose. The squirrel developer contains only hydroquinone as a developing agent, and uses a sulfite as a preservative in the form of an adduct with formaldehyde so as not to impair its infectious developability, so that the concentration of free sulfite ions is extremely low (usually 0.1%). Mol / or less). Therefore, the squirrel developer has a serious disadvantage that it is extremely susceptible to air oxidation and cannot withstand storage for more than three days.

U.S. Pat. Nos. 4,224,401 and 4,168,977 for obtaining high contrast photographic characteristics using a stable developer.
No. 4,166,742, No. 4,311,781, No. 4,272,60
No. 6,411,857, 4,243,739 and the like using a hydrazine derivative. According to this method, photographic characteristics with ultra-high contrast and high sensitivity are obtained, and the addition of a high concentration of sulfite to the developer is allowed. Dramatically improved.

However, the ultra-high-contrast image forming method using these hydrazine compounds strongly promotes infectious development,
A high sensitivity and high blackening density can be obtained, but when photographing low-contrast character originals (especially Mincho-type thin lines), the blackening of the part that should become a thin white background causes the problem that the line width tends to be thin. Was.

In particular, the manuscript in the line drawing photographing process is created by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, originals contain images having different densities and line widths, and a plate-making camera, a photographic material, or an image forming method for finishing these originals with good reproduction 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 the reduction, the number of lines / inch 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 halftones.

The method of suppressing the infectious developability is to lower the amount of the nucleating agent added or to lower the pH of the developing solution, but this makes the gradation soft, the sharpness of the image is lost, and the method is practical. Had a problem.

In the present invention, by using an accelerator for nucleation development in combination
Even with a developing solution having a pH of 11.2 or less, the gradation could be made sufficiently high, and the exposure latitude for line drawing could be improved by using a dye having an absorption maximum at 300 nm to 420 nm.

If the wavelength of the dye is shorter than 300 nm, the effect of improving the image quality cannot be obtained, and if it is longer than 420 nm, the sensitivity is significantly reduced.

(Object of the Invention) A first object of the present invention is to provide a silver halide photographic material having good reproducibility of image lines and halftone dots (wide exposure latitude).

A second object is to provide an ultra-high-contrast image forming method capable of maintaining stable performance with a stable developer in a system using a hydrazine compound.

(Disclosure of the Invention) The object of the present invention is to provide at least one silver halide emulsion layer on a support, and to have the hydrazine derivative of the general formula (I) in the emulsion layer or another hydrophilic colloid layer. In a method of processing a negative photosensitive material with a developer having a pH of 11.2 or less to form a hard black-and-white image having a gamma of 8 or more,
The image forming method, wherein the silver halide photographic material contains at least one dye having an absorption maximum at 300 nm to 420 nm, and the silver halide emulsion is spectrally sensitized to a longer wavelength than 420 nm. Was achieved.

First, the hydrazine derivative of the general formula (I) used in the present invention will be described.

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

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, a carbamoyl group or an oxycarbonyl group, and G ₁ represents a carbonyl group. Group, sulfonyl group,
Sulfoxy group, Or A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl Represents a group.

In the general formula (I), 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. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

In the general formula (I), 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 a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and an acylamino group. Group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group,
Examples include 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. As a preferable substituent, a linear, branched or cyclic alkyl group (preferably having 1 carbon atom) To 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), 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)
), A sulfonamide group (preferably having 1 carbon atom)
Ureido group (preferably having 1 to 30 carbon atoms)
A phosphoric acid amide group (preferably having 1 carbon atom)
~ 30).

The alkyl group represented by R ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group, and a sulfonyl group.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, a sulfonyl group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

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

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R ₂ , when G ₁ is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl) Group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o
-Hydroxybenzyl group), an aryl group (for example,
Phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyl) and the like, and a hydrogen atom is particularly preferable.

When G ₁ is a sulfonyl group, R ₂ represents an alkyl group (eg, a methyl group), an aralkyl group (eg, o
-Hydroxyphenylmethyl group), an aryl group (eg, a phenyl group) or a substituted amino group (eg,
And a dimethylamino group.

When G ₁ is a sulfoxy group, preferred R ₂ is a cyanobenzyl group, a methylthiobenzyl group, and the like, In the case of R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group,
Phenoxy groups are preferred.

When G ₁ is an N-substituted or unsubstituted iminomethylene group,
Preferred R ₂ is a methyl group, an ethyl group, a substituted or unsubstituted phenyl group.

As the substituent for R _2, the substituents listed for R ₁ can be applied.

G in the general formula (I) is most preferably a carbonyl group.

Further, R ₂ disrupts the G ₁ -R ₂ moiety from the remainder molecule, -G ₁ -
It may be one that causes a cyclization reaction to generate a cyclic structure containing an atom of the R ₂ moiety, and specifically, it can be represented by the general formula (a).

In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, is a group capable of splitting the G ₁ -R ₃ -Z ₁ moiety from the remainder molecule, R ₃ than that removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, G _1, R
₃ , Z ₁ can form a cyclic structure.

More specifically, Z ₁ is easily prepared when the hydrazine compound of the general formula (I) produces the next reaction intermediate by oxidation or the like.
G ₁ and nucleophilic reaction with _{R 1 -N = N-G 1} -R 3 -Z 1 R 1 -N = N group is a group capable of splitting from G _1, in particular OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ , or —SO ₂ R ₅ , and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), COOH, etc. It may be filed with a functional group which reacts directly with G ₁ to _{(wherein, OH, SH, NHR 4,} -COOH is be temporarily protected so as to generate these groups by hydrolysis such as an alkali Good) or (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group capable of performing the above.

The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c).

Wherein, R _b ¹ ~R _b ⁴ is a hydrogen atom, (preferably those having 1 to 12 carbon atoms) alkyl groups, (those of preferably 2 to 12 carbon atoms) alkenyl group, an aryl group (preferably having a carbon number of 6 ~
12) and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n
+ M) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
A cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₁ has the same meaning as in formula (a).

In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or the like, and may be the same or different.

R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

 p represents 0 or 1, and q represents 1-4.

R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on G ₁ .

R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, p is 0 or 1 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is 2 Or 3 for CR _c ¹ R _c
² may be the same or different.

Z ₁ has the same meaning as in formula (a).

A ₁ and A _{2 each} represent a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably phenylsulfonyl group or phenylsulfonyl substituted such that the sum of the substituent constants of Hammett is -0.5 or more; Group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; or a straight-chain, branched or cyclic unsubstituted group; Substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group). A ₁ and A ₂ are most preferably hydrogen atoms. preferable.

R ₁ or R _{2 in} the general formula (I) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from.

R ₁ or R _{2 in} the general formula (I) 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 (I) 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 those described 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
No., JP-A-61-170,733, JP-A-61-270,744, JP-A-62-94
No. 8, EP 217,310, Japanese Patent Application No. 61-175,234, No. 61-251,4
No. 82, No. 61-268,249, No. 61-276,283, No. 62-6752
No. 8, No. 62-67,509, No. 62-67,510, No. 62-58,513
No., 62-130,819, 62-143,467, 62-166,11
No. 7, or US 4,686,167, JP-A-62-178,246, JP-A-63-234,244, JP-A-63-234,245, JP-A-63-234,246.
No. 63-294,552, No. 63-306,438, Japanese Patent Application No. 62-16
No. 6,117, No. 62-247,478, No. 63-105,682, No. 63-1
No. 14,118, No. 63-110,051, No. 63-114,119, No. 63-
No. 116,239, No. 63-147,339, No. 63-179,760, No. 63
No. 229,163, Japanese Patent Application No. 1-18,377, No. 1-18,378,
〃1-18,379, 〃1-15,755, 〃1-16,814, 〃
Nos. 1-40,792, # 1-42,615 and # 1-42,616 can be used.

The compound represented by the general formula (I) is
It is preferable to add 1 × 10 ⁻⁶ mol to 5 × 10 ⁻² mol per mol, and the range of 1 × 10 ⁻⁵ mol to 2 × 10 ⁻² mol is a preferable addition amount.

When the compound of the general formula (I) is contained in a photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and it is an alcohol (for example, methanol or ethanol) ester (for example, ethyl acetate) ketone (for example, when it is insoluble in water). Acetone) as a water-miscible organic solvent solution
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution.

When added to the silver halide emulsion solution, the addition can be performed at any time from the start of chemical ripening to coating, but is preferably performed after the completion of chemical ripening, especially the coating prepared for coating. It is preferably added to the solution.

 Next, the dye used in the present invention will be described.

The dye used in the present invention is a dye having a peak at 300 to 420 nm, more preferably a dye having a peak at 350 to 410 nm (including an ultraviolet absorber). Specific examples include JP-A-62-210458, JP-A-63-104046, JP-A-63-103235, Japanese Patent Application No. 62-43704, JP-A-62-218648, and JP-A-63-306436.
And No. 63-314535.

Compounds having an absorption peak at 300 to 420 nm preferably used in the present invention include, for example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and ultraviolet light. Absorbing polymers can be used.

More particularly preferably used dyes include the following formulas (Da), (Db), (Dc) or (Dd)
And a compound having an absorption maximum of 300 to 420 nm.

General formula [Da] Wherein R ₁ ″ is —OX or Wherein X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, a halogenated alkyl group, an alkyl group which may be substituted or R ₂ ″ and R ₃ ″ represent a hydrogen atom,
H represents a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or a group similar to the aforementioned -OX group, and Q represents at least one halogen atom, a carboxy group, a sulfo group, a sulfoalkyl group, or a sodium salt thereof. A phenyl group or a sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoalkylthioalkyl group substituted with a potassium salt, and L represents a methine group which may be substituted. R ₄ ″ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group or an acyl-substituted or unsubstituted amino group; m is an integer 1 or 2;
Are respectively shown.

General formula [D-b] In the formula, R ₅ ″, R ₆ ″, R ₈ ″, R ₉ ″ and R ₁₀ ″ are a hydrogen atom,
Represents a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group or a sodium / potassium salt thereof,
R ₇ represents an alkyl group or a carboxyl group.

General formula [D-c] In the formula, R ₁₁ ″ and R ₁₂ ″ represent an alkyl group, a substituted alkyl group,
R ₁₃ ″ and R ₁₄ ″ represent an aryl group, an alkoxycarbonyl group or a carboxyl group; R ₁₃ ″ and R ₁₄ ″ represent an alkyl group substituted with a sulfonic acid group or a carboxyl group, or an aryl group substituted with a sulfonic acid group or a carboxyl group or a sulfonic acid group; Represents a sodium / potassium salt thereof, and L represents a substituted or unsubstituted methine chain. M represents a sodium, potassium or hydrogen atom, and l represents 0 or 1.

General formula [D-d] In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group and a sulfoalkyl group. R ₅ and R ₆ represent a sulfonic acid group or an alkylsulfonic acid group.

The specific examples of the dyes preferably used in the invention are shown below, but the invention is not limited thereto.

These dyes may be added to any of the emulsion layer, intermediate layer, protective layer and other hydrophilic colloid layers. Also, these compounds may be substantially immobilized on any layer.
In this case, it is preferably present in the emulsion layer or a layer outside the emulsion. As mordants for immobilizing these dyes, JP-B-43-10254, US-2,548,564, US-2,882,
No. 156 and US Pat. No. 3,444,138 are used.

Further, fine solid crystal dispersions of dye solid particles described in US-73256 and WO-8804794 can also be used.

Further, as a dye useful in the present invention, Japanese Patent Application No. 62-43704.
And functional dyes capable of being decolorized in a developer described in JP-A-62-218648. Next, specific examples of these functional dyes will be shown.

These dyes differ depending on the molar extinction coefficient, but usually 10
^-2 is added in a range of ^{g / m 2 ~1g / m 2} . Preferably 50mg-5
00 mg / m ² .

The dye is dissolved in an appropriate solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof), and is dissolved in the hydrophilic colloid layer coating solution of the present invention. Can be added.

These UV absorbers can be used in combination of two or more.

Next, the general formula (II) or (III) used in the present invention
Will be described.

In order to adjust the pH from 11.0 or lower to 8 or higher, it is preferable to include a compound represented by the general formula (II) and / or (III) in the light-sensitive material.

The measurement of this value indicates that the pH of the developer is pH 11.2 or less.
Any B / W developer can be used.
Performed at 8 ° C for 30 seconds. Is expressed as a density difference with respect to a difference (ΔlogE) between exposure amounts giving densities of 0.1 and 3.0.

(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 heterocycle, and the amino group may be substituted, m represents 1, 2 or 3, and n represents 0 or 1. The group adsorbed on the silver halide represented by Y includes a nitrogen-containing heterocyclic compound.

When Y represents a nitrogen-containing heterocyclic compound, the compound represented by the general formula (II)
Is represented by the following general formula (II-a).

In the formula, 1 represents 0 or 1, m represents 1, 2 or 3, and n represents 0 or 1.

[(X _n A-B) _m has the same meaning as that in the general formula (II), and Q represents 5 or 6 composed of at least one atom of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom.
Represents the atoms necessary to form a membered heterocycle. 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, tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, quinolines and the like.

M represents a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, etc.), a group which can be 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.), alkoxy group (eg, methoxy group, 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), an arylthio group (for example, phenylthio group), a sulfonyl group (for example, methanesulfonyl) Group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group) , Phenylsulfamoyl group ), A carbonamide group (eg, an acetamido group, a benzamide group, etc.), a sulfonamide group (eg, a methanesulfonamide group, a benzenesulfonamide group, a p-toluenesulfonamide group, etc.), an acyloxy group (eg, an acetyloxy group, Benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, etc.), ureido group (eg, unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido group (eg, unsubstituted) Thioureido group, methylthioureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), 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, etc.), oxycarbonyl group (for example, methoxycarbonyl group, phenoxycarbonyl group) , Etc.), oxycarbonylamino group (for example, methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group,
And the like, an amino group (eg, an unsubstituted amino group, a dimethylamino group, a methoxyethylamino group, an anilino group, etc.), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxy group, and the like.

Examples of the divalent linking group represented by X include: These linking groups are linked to Q via a linear or branched alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.). May be combined.
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) Group, n-butyl group,
Etc.), a substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.), a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or a substituted or unsubstituted group. Represents an aralkyl group (eg, benzyl group, phenethyl group, etc.).

A represents a divalent linking group, wherein the divalent linking group is a linear or branched alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group,
-Methylethylene group, etc.), linear or branched alkenylene group (for example, vinylene group, 1-methylvinylene group,
And the like, linear or branched aralkylene groups (eg, benzylidene groups, etc.), and arylene groups (eg, phenylene, naphthylene, etc.). 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).

(Wherein, R ¹¹ and R ¹² may be the same or different and each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group, or an aralkyl group. Straight chain (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3
-Butenyl group, benzyl group, 1-naphthylmethyl group,
Etc.), branched (eg, isopropyl group, t-octyl group, etc.), or cyclic (eg, cyclohexyl group, etc.).

R ¹¹ and R ¹² may be linked to form a ring, in which one or more heteroatoms (eg, an oxygen atom,
Cyclized to form a saturated heterocyclic ring containing a sulfur atom, a hydrogen atom and the like, 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, an alkoxy group having 20 or less carbon atoms. Carbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.),
An alkoxy group having 20 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), a monocyclic aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, etc.), carbon Number 20
The following acyloxy groups (eg, acetyloxy group, propionyloxy group, etc.), acyl groups having 20 or less carbon atoms (eg, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl groups (eg, carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc., sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon An acylamino group having a number of 20 or less (eg, acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), a sulfonamide group (an ethylsulfonamide group, a p-toluenesulfonamide group, etc.), a carbonamide having 20 or less carbon atoms Groups (eg, methylcarbonamide group, phenylcarbonamide group, etc.), ureido groups having 20 or less carbon atoms (eg, methylureido group, phenylureido group, etc.), amino groups and the like.

The ammonium group of B is represented by the general formula (II-c).

(Where R¹³, R¹⁴, R^FifteenIs represented by the above general formula (II-b)
R¹¹And R¹²Is the same group as Represents an anion
Represents, for example, a halide ion (eg, Cl , Br , I
), Sulfonate ion (for example,
Tansulfonate, paratoluenesulfonate, benze
Sulfonate, parachlorobenzene sulfonate
), Sulfite ions (eg, ethyl sulfite
, Methyl sulfite, etc.), perchlorate, tet
Lafluoroborate and the like. p is 0 or 1
And 0 when the compound forms an inner salt.
You. ) The nitrogen-containing heterocyclic ring of B has at least one nitrogen atom.
A 5- or 6-membered ring containing
May be condensed with another ring
No. Examples of the nitrogen-containing hetero ring include an imidazolyl group,
Examples include a lysyl group and a thiazolyl group.

Among the general formulas (II), preferred are those represented by the following general formulas (II-m), (II-n), (II-o) or (II-o).
and the compounds represented by p).

(Wherein, X _n AB, M, and m have the same meanings as those of the general formula (III). Z ₁ , Z _2, and Z ₃ represent the general formula (II
Is the same as X _n AB in I), or represents a halogen atom, an alkoxy group having 20 or less carbon atoms (for example, a methoxy group), a hydroxy group, a hydroxyamino group, a substituted or unsubstituted amino group, The group can be selected from the substituents of R ¹¹ and R ¹² in the general formula (III-b). However, at least one of Z ₁ , Z ₂ and Z ₃
One is synonymous with X _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.

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 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.

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 a suitable 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, a sec-butyl group, and a cyclohexyl group.
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 provalgyl group and a 2-pentynyl group. As the substituent, 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,
Amide group and the like.

When R ¹ and R ² form a ring, a 5- or 6-membered carbon or heterocyclic ring composed of a combination of carbon or nitrogen and oxygen, particularly a saturated ring, is preferred. And so on.

Particularly preferred as R ¹ and R ² are alkyl groups having 1 to 3 carbon atoms, more preferably an ethyl group.

As the divalent aliphatic group for R ³ , —R ⁴ — or —R ⁴ S— is preferable. 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- , And so on.

R ₄ preferably has 2 to 4 carbon atoms, and R ⁴ is more preferably —CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ . R ³ when the Note _{(X) n} n of 0 is -R ⁴ - represents only.

X is a heterocyclic ring containing nitrogen, oxygen or sulfur;
And a 6-membered heterocycle fused to a benzene ring. As a heterocyclic ring preferably aromatic, for example,
Examples include tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole, and benzoxazole. Of these, tetrazole and thiadiazole are particularly preferred.

Examples of the alkali metal of M include Na ⁺ , K ⁺ , and Li ⁺ .

Examples of the alkaline earth metal include Ca ⁺⁺ and Mg ⁺⁺ .

The quaternary ammonium salt of M, made of 4 to 30 carbon atoms, for example _{(CH 3) 4 N, (} C 2 H 5) 4 N, (C 4 H
_{9) 4 H, C 6 H} 5 CH 2 N (CH 3) 3, C 16 H 33 N (CH 3) 3 and the like. As the quaternary phosphonium salt, (C ₄ H ₉ ) ₄ P
, C ₁₆ H ₃ P (CH ₃ ) ₃ and C ₆ H ₅ CH ₂ P (CH ₃ ).

Examples of the inorganic acid salt of the compound represented by the general formula (III) include hydrochloride, sulfate and phosphate, and examples of the organic acid salt include acetate, propionate, methanesulfonate and benzenesulfonate. , P-toluenesulfonate and the like.

Specific examples of the compound represented by the general formula (III) are shown below.

Optimum amounts of the accelerators represented by the general formulas [II] and [III] differ depending on the kind of the compound, but the amount is 1.0
It is desirably used in the range of × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^{−3 to} 0.3 g / m ² . These accelerators are suitable solvents (H ₂ O, alcohols such as methanol and ethanol,
Dissolved in acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A method for preparing a silver halide emulsion used in the present invention is described in Chimie et Physique Photograph by P. Glafkides.
ique "(Paul Montel, 1967), GFDuffin's" Pho
tographic Emulsion Chemistry "(The Focal Press
Publishing, 1966), Making and Coati by VLZelikman et al.
ng Photographic Emulsion ”(The Focal Press, 1964)
US Patent No. 2,592,250)
No. 4,075,020 and the like, and the core / shell emulsion preparation method described in British Patent No. 1,027,146 and the like.

As a method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt, any one 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.

Grains can also be formed using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea.

In 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.

Silver halide grains in the photographic emulsion used in the present invention,
Although it can have a relatively broad grain size distribution, it is preferred to have a narrow grain size distribution, especially where the size of grains accounting for 90% of the weight or number of silver halide grains is ± 40% of the average grain size. (In general, such emulsions are referred to as monodisperse emulsions).

The silver halide grains used in the present invention are preferably fine grains (for example, 0.7 μm or less), particularly preferably 0.4 μm or less.

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 composite 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, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or the like may coexist.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. As a method of chemical sensitization, there is gold sensitization and the like, and sulfur sensitization, reduction sensitization, noble metal sensitization and the like can be used in combination with gold sensitization.

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 thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are U.S. Pat.Nos. 1,574,944 and 2,278,947.
No. 2,410,689, 2,728,668, 3,501,313,
No. 3,656,955.

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer, and specific examples thereof are described in U.S. Pat.No. 2,487,850, 2,518,6
No. 98, 2,983,609, 2,983,610, and 2,694,637.

Further, this silver halide emulsion is optically sensitized for the purpose of increasing the sensitivity and providing sensitivity to a desired wavelength region. As a method of optical sensitization, sensitizing dyes such as cyanine dyes and merocyanine dyes are used alone or in combination, and spectral sensitization and supersensitization are performed.

U.S. Patent No. 2,688,545 describes these techniques,
No. 2,912,329, No. 3,397,060, No. 3,615,635
No. 3,628,964, JP-B-43-4936, 44-14030
And JP-A-55-52050.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes and the like; Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfonate, benzenesulfonamide, and the like, can be added.

Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) 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 (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) 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.), mucohalic acids (mucochloric acid, mucophenoxycyclolic acid, etc.) 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 interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Activator; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene 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 alkyl phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or Amphoteric surfactants such as phosphates, alkyl betaines, and amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic-containing phosphonium or sulfonium salts 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.

In the photographic light-sensitive material used in the present invention, for the purpose of improving the dimensional stability of the photographic emulsion layer and other hydrophilic colloid layers,
It may include a dispersion of a water-insoluble or poorly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth)
Acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate , A polymer having a combination of sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

As a processing solution used in the present invention, a dihydroxybenzene-based developing agent is used as a developing agent, and p is used as an auxiliary developing agent.
It is preferable to use an -aminophenol-based developing agent or a 3-pyrazolidone-based developing agent.

Examples of the dihydroxybenzene-based developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone. Of these, hydroquinone is particularly preferred.

Examples of 1-phenyl-3-pyrazolidone or a derivative thereof as an auxiliary developing agent include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-
4,4-dimethyl-3-pyrazolidone and the like.

Examples of p-aminophenol-based auxiliary developing agents include N-methyl-p-aminophenol, p-aminophenol,
N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl- p-Aminophenol is preferred.

The dihydroxybenzene developing agent is usually 0.05 mol /
It is preferably used in an amount of .about.0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / -0.5 mol / and the latter is 0.0 mol / mol.
It is preferable to use it in an amount of 6 mol / or less.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfite is used in an amount of 0.3 mol / or more, but if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is preferably 1.2 mol /.

The developing solution of the present invention may contain an amino compound as a development accelerator, particularly the compound described in US Pat. No. 4,269,929.

In the developing solution of the present invention, a pH buffering agent such as boric acid, borax, sodium phosphate tribasic, and potassium phosphate tribasic, as well as a pH buffering agent described in JP-A-60-93433 may be used. it can.

Development inhibitors such as potassium bromide and potassium iodide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and methanol; indazole compounds such as 5-nitroindazole; An antifoggant or a black pepper inhibitor such as a benztriazole-based compound such as sodium 2-mercaptobenzimidazole-5-sulfonate and 5-methylbenztriazole;
In particular, when using a compound such as 5-nitroindazole, dissolve it in a portion different from the portion containing the dihydroxybenzene-based developing agent and the sulfite preservative in advance, mix both portions at the time of use, and add water. Is common. Further, if the portion in which 5-nitroindazole is dissolved is made alkaline, it is colored yellow and is convenient for handling.

If necessary, a color tone agent, a surfactant, a water softener,
It may contain a hardener and the like. The pH of the developer is preferably a high pH of 9 or more, more preferably 9.5 to 11.2.
It is.

If the pH of the developer is 11.2 or more, the pH tends to fluctuate due to CO ₂ in the air, and the developer is also easily oxidized and colored. If the pH is 9.5 or less, it is difficult to obtain high contrast, and clear image quality cannot be obtained.

As the fixing agent, those having a generally 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, for example, aluminum sulfate, bright bun and the like. Here, the amount of the water-soluble aluminum salt is usually 0 to 3.0 gAl /. Further, a Fe (III) complex salt of ethylenediaminetetraacetic acid may be used as the oxidizing agent.

The processing temperature is usually selected between 18 ° C and 50 ° C,
Lower temperatures or temperatures above 50 ° C. may be used.

In the processing of the present invention, it is preferable to use an automatic developing machine, in which case, development, fixing, washing, through the steps of drying,
Total time from loading photosensitive material to coming out
Even in a short time of 90 seconds to 120 seconds, it is possible to sufficiently obtain a negative gradation photographic characteristic of ultra-high contrast.

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

Example 1 (Prescription of silver halide emulsion layer) The grain size was controlled to 0.2 using a control double jet method.
A 25 micron cubic monodispersed silver iodobromide emulsion (coefficient of variation 12%, silver iodide 0.5 mol%, iodine distribution uniform) was prepared. To this silver iodobromide emulsion was added K ₃ IrCl ₆ so as to contain 4 × 10 ⁻⁷ mol / Ag.

This emulsion was desalted by the flocculation method, and then kept at 50 ° C. as a sensitizing dye. The following compounds were used as a sensitizing dye in a solution of 5 × 10 ^-4 mol per mol of silver and 10 ^-3 mol per mol of silver in potassium iodide. Was added and the mixture was aged for 15 minutes and then cooled.

Sensitizing dye This emulsion was prepared by adding 4-hydroxy-6methyl- as a stabilizer.
1,3,3a, 7-tetrazaindene, 5-methylbenztriazole, the following compounds (a) and (b) Was added such that 5 mg / m ^{2 was} applied. The following compound was added as a hydrazine compound so as to be 10 mg / m ² .

Hydrazine compounds To this emulsion was added the compound II-9 of the present invention at 8.0 × 10 ^-3 mol / mol.
After the addition of mole Ag, the dye was further added as shown in Table 1. In addition, polyethylene glycol having an average molecular weight of 600
5 mg / m ^2, and a dispersion of polyethyl acrylate was added at a solids ratio of 30 wt% to gelatin, and 1,3-divinyl-sulfonyl-2-propanol as a hardener was added. 3.5g / m silver
² was applied. Gelatin as a protective layer on this
1.2 m / m ² , 40 m irregular SiO ₂ matting agent with particle size of about 3μ
g / m ² , methanol silica 0.1 g / m ² , polyacrylamide 1
00 mg / m ² , hydroquinone 200 mg / m ² , silicone oil and fluorine surfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzenesulfonate.

 The back layer was applied according to the following formulation.

(Back layer formulation)

Gelatin 4 g / m ² matting agent Polymethyl methacrylate (particle size 3.0
~4.0μ) 10mg / m ² latexes polyethyl acrylate 2 g / m ² Surfactant p- sodium dodecylbenzenesulfonate 40 mg / m ² fluorine based surfactant Gelatin hardener Dye Mixture of dyes [a], [b], and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ² (Test method) 1. Evaluation of enlargement image quality (1) Creation of manuscript Monochrome scanner SCAN manufactured by Fuji Photo Film Co., Ltd.
Using ART30 and the special photosensitive material SF-100, a transmission image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed stepwise were created. At this time, the screen frequency was set to 150 lines / inch.

(2) Photographing After engraving the above manuscript on a plate making camera C-440 manufactured by Dainippon Screen Co., Ltd.
The evaluation sample was exposed by irradiating a Xe lamp.

At this time, the exposure was performed so that 95% of the step wedge of the original document was 5%.

(3) Evaluation A sample with good gradation reproducibility (hardness of halftone dots) of the shadow portion of the sample in which the exposure amount is adjusted as in (2) and the small dot side (highlight portion) is adjusted to 5%. , A five-step evaluation (5-1) was performed in order.

2. Evaluation of copy dots (1) Manuscript preparation Monochrome scanner SCAN manufactured by Fuji Photo Film Co., Ltd.
A step wedge was prepared using ART30 and the special paper SP-100wp, in which the screen percentage was changed stepwise. The exposure was performed at a screen ruling of 150 lines / inch.

(2) Photography Dainippon Screen Co., Ltd. Plate making camera C-690
The original and the sample were set at predetermined positions on a (auto-companica, xenon light source), and the Xe lamp was irradiated on the reflective original to photograph. At this time, the exposure time was adjusted so that 80% of the step wedge on the original became 10% on the sample.

(3) Evaluation As described in (2), the exposure time was adjusted so that the gradation reproducibility (the difficulty of halftone dot collapse) of the shadow portion of the sample having a dot percentage of 10% on the small dot side was 5%. Five steps of relative evaluation were performed as 1.

3. Evaluation of sensitivity (1) Stretching sensitivity Exposure time when 95% of the step wedge of the stretched manuscript is 5% on the sample is calculated, and expressed as a relative value when the sensitivity of the comparative sample is 100. .

(2) Copy dot sensitivity The exposure time when the 80% portion of the step wedge of the copy dot original becomes 10% on the sample is obtained, and is expressed as a relative value when the sensitivity of the comparative sample is set to 100.

 The developer used was prepared according to the following formulation.

Treatment liquid formulation (1) Hydroquinone 50.0 g N-methyl-P-aminophenol 1/2 sulfate 0.3 g Sodium hydroxide 18.0 g 5-sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Potassium bromide 10.0 g 5-methylbenzotriazole 0.4 g 2-mercaptobenzimidazole-5-sulfonic acid 0.3 g sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 g N-n-butyldiethanolamine 15.0 g sodium triene sulfonate 8.0 g water was added. 1 pH11.6 Treatment liquid formulation (2) Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-
3-pyrazolidone 0.5 g potassium sulfite 90.0 g disodium ethylenediaminetetraacetate 2.0 g potassium bromide 5.0 g 5-methylbenzotriazole 0.2 g 2-mercaptobenzimidazole-5-sulfonic acid 0.3 g sodium carbonate 50.0 g sodium hydroxide Adjust to pH = 10.7.

Addition of water 1 Developer formulation (1) is a processing solution for a comparative example having a high pH and developer formulation (2) is a developer used for the sample of the present invention.

The fixing solution is a fixing solution manufactured by Fuji Photo Film Co., Ltd.
Automatic processing machine LD manufactured by Dainippon Screen Co., Ltd. using GR-F1
Development was performed at 34 ° C. and 30 ″ using -281Q.

The following compounds d, e, and f were used as dyes for comparative samples.

Comparative compound The results are shown in Table 1.

From Table 1, the sample of the present invention has a small sensitivity decrease and is elongated,
It can be seen that the copy dots are good. The processing solution No. 1 having a high pH had poor image quality, and the comparative dye having a longer wavelength than 420 nm had a large decrease in sensitivity.

Example 2 A sample was prepared by replacing the sample No. 6 of Example 1 with the hydrazine compounds I-18, I-19 and I-41 of the exemplified compounds in the text.

The amount of the hydrazine compound added was as shown in Table 2, and the dye compound D-19 was commonly added to all these samples so as to be 100 mg / m ² . These samples were evaluated in the same manner as in Example-1.

 Table 2 shows the results.

From Table 2, it can be seen that the sample of the present invention was spread and the image quality of the copy dots was good.

The sample to which the hydrazine compound was not added was extremely low-sensitive and the image quality was poor, and the sample treated with the processing solution No. 1 had an image quality inferior to the sample of the present invention even when the addition amount of the hydrazine compound was adjusted so that the optimum sensitivity was obtained. .

Claims (2)

(57) [Claims] A negative photosensitive material having at least one silver halide emulsion layer on a support and having the hydrazine derivative of the general formula (I) in the emulsion layer or another hydrophilic colloid layer at pH 11.3. (2) a method for forming a hard black-and-white image having a gamma of 8 or more by processing with a developing solution of 2 or less, wherein the silver halide photographic light-sensitive material contains at least one dye having an absorption maximum at 300 nm to 420 nm; 42 silver emulsion
An image forming method characterized by being spectrally sensitized to a wavelength longer than 0 nm. General formula (I) 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, a carbamoyl group or an oxycarbonyl group, and G ₁ Carbonyl group, sulfonyl group,
Sulfoxy group, Or A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl Represents a group. 2. A patent comprising a silver halide emulsion layer or another hydrophilic colloid layer containing at least one compound selected from compounds represented by the following general formulas (II) and (III): The image forming method according to claim 1. General formula (II) (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 heterocycle, and the amino group may be substituted, m represents 1, 2 or 3, and n represents 0 or 1. Represents the general formula (III) (Wherein, 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 represents a divalent heterocyclic 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 Represents an amidino group.)