JP2002014435A - Silver halide photographic sensitive material and processing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultrahigh contrast silver halide photographic sensitive material having high sensitivity and low fog and ensuring suppressed occurrence of black spots. SOLUTION: The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer containing hydrophilic colloid on the base and contains at least one compound of formula (1) in the silver halide emulsion layer or another non-photosensitive hydrophilic colloidal layer.

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 light-sensitive material (hereinafter simply referred to as a light-sensitive material or a light-sensitive material) and a processing method thereof. About the method.

[0002]

2. Description of the Related Art In recent years, in the market for printing plate-making image setters, as the speed of output machines has been increased, there has been a demand for higher sensitivity of photosensitive materials for output.

In order to obtain the sensitivity of a silver halide photographic material, chemical ripening or chemical sensitization (formation of a photosensitive nucleus) is performed. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization, and these are used alone or in combination. Specific sensitizers include, for example, Research Disclosure Nos. 17643 (December 1978) 2
No. 3 category III, the same No. 18716 (November 1979
Month) 648 and the same No. 308119 (1989, 1
(February) Item 996, Category III, etc. Among them, sulfur sensitizers are most commonly used. As the sulfur sensitizer, for example, thiosulfates, thioureas, rhodanines, polysulfide compounds and the like can be used. In the chemical ripening step, silver halide grains are placed in a hydrophilic colloid solution such as gelatin in the presence of these sulfur sensitizers.
By aging at a temperature of 40 ° C. to 90 ° C. for several tens of minutes to several hours, photosensitive nuclei are formed on the grains. However, in order to obtain high sensitivity, use of a large amount of a sulfur sensitizer or aging for a long time at a high temperature tends to cause unexposed blackening called fog.

Since the output light-sensitive material is treated as a final positive instead of the conventional return light-sensitive material, an ultra-high contrast type output light-sensitive material in which the density of small points is easily increased is desired. Various photographic techniques are known as photographic techniques capable of reproducing a super-high contrast image in a photosensitive material for printing plate making. Among them, for example, a silver halide photographic light-sensitive material containing a hydrazine derivative as described in U.S. Pat. No. 4,269,929 and a nucleation nucleus as described in JP-A-4-98239. A silver halide photographic material containing an accelerator is known. However, in a photosensitive material using hydrazine, increasing the sensitivity tends to cause generation of minute black spots called black spots.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic material having high sensitivity and low fog. A second object is to provide a high-sensitivity, ultra-high contrast silver halide photographic material with reduced occurrence of black spots.

[0006]

The above objects of the present invention have been attained by the following constitutions.

[0007] 1. The support has at least one photosensitive silver halide emulsion layer containing a hydrophilic colloid, and the silver halide emulsion layer or another non-photosensitive hydrophilic colloid layer is represented by the above formula (1). A silver halide photographic material comprising at least one compound selected from the group consisting of:

[0008] 2. 2. The silver halide photographic material as described in 1 above, wherein the hydrazine derivative is contained in a silver halide emulsion layer or another non-photosensitive hydrophilic colloid layer.

3. 3. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to 1 or 2 is treated with a processing agent containing a compound represented by the general formula (2) as a developing agent.

Hereinafter, the present invention will be described in more detail. First, the compound represented by formula (1) of the present invention will be described in detail. In the general formula (1), EWD represents an electron-withdrawing group, and the electro-withdrawing group represented by EWD is a substituent whose Hammett's substituent constant σp can take a positive value. Include a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a halogen atom, a perfluoroalkyl group, an acyl group, a formyl group, a phosphoryl group, and carboxy. Group (or a salt thereof), a sulfo group (or a salt thereof),
Examples include a saturated or unsaturated heterocyclic group, an alkenyl group, an alkynyl group, an acyloxy group, an acylthio group, a sulfonyloxy group, and an aryl group substituted with these electron-withdrawing groups. These groups may have a substituent.

As the monovalent substituent represented by R ₁ , R ₂ and R ₃ , a group having the same meaning as the electron-withdrawing group represented by EWD, an alkyl group, a hydroxy group (or a salt thereof) , A mercapto group (or a salt thereof), an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Examples include a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a ureido group, an amide group, and a substituted or unsubstituted aryl group. The substituents represented by R ₁ , R ₂ and R ₃ may further have a substituent.

Next, preferred compounds among the compounds represented by the general formula (1) will be described. In Formula (1), the electron-withdrawing group represented by EWD is preferably
Cyano, nitro, alkenyl, acyl, formyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, carbamoyl, sulfamoyl, trifluoromethyl, phosphoryl, saturated or unsaturated Heterocyclic group, or a phenyl group substituted with any electron-withdrawing group, further cyano group, acyl group, formyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, or arylsulfonyl group preferable. Particularly preferred are a cyano group, formyl group, acyl group, alkoxycarbonyl group, or carbamoyl group, and most preferred is a cyano group or a formyl group.

In the general formula (1), R ₁ and R ₂ are
Preferably, one of them is a hydrogen atom and the other is a monovalent substituent. The monovalent substituent is preferably an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an acyloxy group, Acylthio group, amino group, alkylamino group, arylamino group, heterocyclic amino group,
A substituted or unsubstituted phenyl group or a heterocyclic group is preferable. Further, the heterocyclic group is an unsaturated heterocyclic group, among which a nitrogen-containing heterocyclic group (for example, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group) Base)
Is preferred.

In the general formula (1), R ₁ and R ₂ are
Most preferably, one is a hydrogen atom and the other is a hydroxy group (or a salt thereof), an alkoxy group, or an unsaturated nitrogen-containing heterocyclic group.

In the general formula (1), R ₃ is preferably an electron-withdrawing group or an aryl group. When R ₃ represents an electron-withdrawing group, preferably, a cyano group, a nitro group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group,
It is a trifluoromethyl group, a phosphoryl group, or a saturated or unsaturated heterocyclic group, and is more preferably a cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, or a sulfamoyl group. Particularly preferred are a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group.

When R ₃ represents an aryl group, it is preferably a substituted or unsubstituted phenyl group, and examples of the substituent include the same groups as those described for R ₁ and R ₂ .

In formula (1), R ₃ is particularly preferably a cyano group, an alkoxycarbonyl group, or a substituted or unsubstituted phenyl group, and most preferably a cyano group or an alkoxycarbonyl group.

Among the compounds represented by the general formula (1), particularly preferred are those wherein EWD represents a cyano group or a formyl group, R ₃ represents an electron-withdrawing group or an aryl group,
One of R _{1 and} R ₂ is a hydrogen atom, and the other is a hydroxy group (or a salt thereof), an alkoxy group, or an unsaturated heterocyclic group.

The compound represented by the general formula (1) of the present invention may be a commercially available compound, or may be synthesized by a known method. For example, US Pat. No. 5,545,5
No. 15, etc. can be referred to.

The compound represented by formula (1) of the present invention can be added to a photosensitive layer or a non-photosensitive layer.
The photosensitive layer, which is preferably an image forming layer, is preferably used as the additive layer.

The compound represented by the general formula (1) of the present invention varies depending on the desired purpose, but is expressed in terms of an addition amount per mol of Ag of from 10 ^-4 to 1 mol / Ag, preferably from 10 ^-3 to 1 mol / Ag.
It is preferable to add 0.3 mol / Ag, more preferably 10 ^{-3 to} 0.1 mol / Ag. Further, each of the compounds of the general formula (1) may be used alone or in combination of two or more. The compound of the general formula (1) of the present invention can be prepared from water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in cellosolve or the like.

Further, by a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve mechanically. An emulsified dispersion can be prepared and used. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or an ultrasonic wave by a method known as a solid dispersion method. When dispersing the solid fine particles, a dispersing aid may be used.

The hydrazine derivative of the present invention is a compound represented by the following general formula [H].

[0024]

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In the general formula [H], A ₀ is an aliphatic group,
The aromatic group or the heterocyclic group, the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, particularly 1 to 2 carbon atoms.
A linear, branched or cyclic alkyl group of 0 is preferable, and specific examples include, for example, a methyl group, an ethyl group, a t-butyl group,
Octyl, cyclohexyl, benzyl and the like, which are further substituted with a suitable substituent (for example, aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido, etc.). You may.

[0026] In formula (H), the aromatic group represented by A ₀ is an aryl group preferably a monocyclic or condensed, such as a benzene ring or a naphthalene ring can be mentioned, A ₀
As the heterocyclic group represented by, nitrogen in a single ring or a condensed ring,
Sulfur, a heterocyclic ring containing at least one hetero atom selected from oxygen atoms is preferable, for example, pyrrolidine, imidazole, tetrahydrofuran, morpholine, pyridine,
Pyrimidine, quinoline, thiazole, benzothiazole, thiophene, furan ring and the like. Particularly preferred as A ₀ are an aryl group and a heterocyclic group,
The aromatic group and the heterocyclic group of ₀ may have a substituent. As a particularly preferable group, a substituent having an acidic group having a pKa of 7 or more, specifically, a sulfonamide group,
Examples include a hydroxyl group and a mercapto group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and the ballast group is a photographically inert group having 8 or more carbon atoms, for example, an alkyl group, an alkenyl group, an alkynyl group, Examples include an alkoxy group, a phenyl group, a phenoxy group, and an alkylphenoxy group.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439, for example.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P
(O) represents a (G ₁ D ₁ ) — group. Preferred G ₀ is-
A CO- group and a -COCO- group are particularly preferably -COCO.
G ₁ is a mere bond, an —O— group, —S
Or a —N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they are the same. May or may not be.

In the general formula [H], D ₀ is a hydrogen atom,
Aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, preferably a hydrogen atom as a D _0, an alkoxy group, an amino group, and the like, A ₁ , A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl,
Trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (ethoxalyl, etc.).

Among the compounds represented by the above general formula [H], more preferred compounds are those represented by the following general formula [H-2]
The compound represented by these is mentioned.

Formula [H-2] R ₀ -SO ₂ NH-Ar-NHNH-G ₀ -D _{0 In the} formula, R ₀ represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group; Represents a substituted or unsubstituted divalent arylene group or heterocyclic group, and G ₀ and D ₀ are represented by the general formula [H]
Is synonymous with Specific examples of the compound represented by the general formula [H] of the present invention include, for example, H-1 to H described in JP-A-2000-98537, paragraphs 0049 to 0057.
−49 and the like.

Specific examples of other preferred hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative of the present invention can be synthesized by a known method. For example, US Pat.
No. 9,248, column 59 to column 80, can be synthesized by the method as described.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization, the type of the inhibitor, etc., it is generally 10 ^-6 to 10 ^-1 per mol of silver halide.
Molar range, preferably from 10 ^-5 to 10 ^-2 mol.

In order to effectively promote the contrast enhancement by the hydrazine derivative, a quaternary onium compound (also referred to as an onium salt compound) having a quaternary nitrogen compound and / or a quaternary phosphorus compound in the structure is selected from amine compounds. It is preferable to use at least one nucleation accelerator used.

In the present invention, in particular, the following general formula [Na]
It is preferable to use an amine compound represented by

[0038]

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In the general formula [Na], R ¹ , R ² , R ³
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group. R ¹ , R ² and R ³ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable.

Preferred examples of the silver halide-adsorbing group include a heterocyclic group-containing compound, a mercapto group, a thioether group, a thione group and a thiourea group. General formula [Na]
Particularly preferred are compounds having at least one thioether group as a silver halide adsorptive group in the molecule.

Specific examples of the compound represented by the general formula [Na] of the present invention include, for example, those described in Paragraph Nos. 0064 to 0067 of JP-A-11-288060.
Na21 can be mentioned.

Specific examples of other preferred amine compounds are described in JP-A-6-258751, page (13), “006”.
2) to (15), “0065” (2-
Compounds 1) to (2-20) and “006” on page 15
7-1 described in “0068” on page 7
３−3-6.

The above-mentioned amine compound preferably used in the present invention may be a photographic constituent layer on the side of a silver halide emulsion layer,
Any layer may be used, or two or more types may be used in combination.

The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 per mol of silver halide.
The range is preferably 10 to 10 ^-1 mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

Next, the quaternary onium salt compound used in the silver halide photographic light-sensitive material of the present invention will be described. The quaternary onium salt compound used in the present invention is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in a molecule, and is preferably a compound represented by the following formula (P).

[0046]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
_21, R _22, R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent, X ₂₁ ^- represents an anion. Further, R _{21 to} R ₂₄ may be linked to each other to form a ring.

As the substituent represented by R _{21 to} R ₂₄ , an alkyl group (for example, methyl, ethyl, propyl, butyl,
Hexyl, cyclohexyl group, etc.), alkenyl group (eg, allyl, butenyl group, etc.), alkynyl group (eg, propargyl, butynyl group, etc.), aryl group (phenyl, naphthyl group, etc.), heterocyclic group (eg, piperidinyl, piperazinyl, morpholinyl, Pyridyl, furyl, thienyl,
Tetrahydrofuryl, tetrahydrothienyl, sulfolanyl group and the like), amino group and the like. Examples of the ring that can be formed by connecting R _{21 to} R ₂₄ to each other include a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like. Groups represented by R ₂₁ to R ₂₄ is a hydroxyl group, an alkoxy group, an aryloxy group,
It may have a substituent such as a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ , a hydrogen atom and an alkyl group are preferred. X ₂₁ ^- as the anion represented by a halogen ion, sulfate ion, nitrate ion,
Inorganic and organic anions such as acetate ion and p-toluenesulfonic acid ion are exemplified.

The quaternary onium salt compounds used in the present invention include the following general formulas (Pa), (Pb) and (Pc)
Or a compound represented by the following general formula [T].

[0051]

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Wherein A ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A
¹⁵ represents a group of non-metallic atoms for completing the nitrogen-containing heterocyclic ring, which may include an oxygen atom, a nitrogen atom, and a sulfur atom,
The benzene ring may be condensed. A ¹¹ , A ¹² , A ¹³ ,
The heterocyclic ring composed of A ¹⁴ and A ¹⁵ may have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. , Amide group, sulfamoyl group,
Examples include carbamoyl, ureido, amino, sulfonamide, sulfonyl, cyano, nitro, mercapto, alkylthio, and arylthio groups. A
Preferred examples of ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A ¹⁵ include:
A 5- to 6-membered ring (each ring of pyridine, imidazole, thiazole, oxazole, pyrazine, pyrimidine and the like) can be mentioned, and a more preferred example is a pyridine ring.

B _p represents a divalent linking group, and mp represents 0 or 1. Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene _{group, -SO 2 -, - SO -} , -
O -, - S -, - CO -, - N (R 16) - (R 16 is an alkyl group, an aryl group, a hydrogen atom) represents what is configured alone or in combination. B _p is preferably an alkylene group or an alkenylene group.

R ¹¹ , R ¹² and R ¹⁵ each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ¹¹ and R ¹² may be the same or different. As the substituent,
The substituents are the same as those described as the substituents for A ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A ¹⁵ . Preferred examples of R ¹¹ , R ¹² and R ¹⁵ are each an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0055] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. n _p represents the number of counter ions required to balance the charge of the entire molecule, and n _p is 0 in the case of an internal salt.

[0056]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σp) indicating an electron-withdrawing degree.

The Hammett's sigma value for the phenyl group has been reported in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, page 304, 1977. The group having a particularly preferable negative sigma value is, for example, a methyl group (σp = −0.17 or less, σp value), and an ethyl group (−). 0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion, iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzenesulfonic acid anions such as toluenesulfonic acid anion; higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; borate anions such as tetraphenylboron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Specific examples of the quaternary onium salt compounds of the present invention include, for example, paragraph No. 0 of JP-A-11-288060.
P1 to P55 and T described in Nos. 088 to 0097
1 to T18.

The above quaternary onium salt compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews. 55. p.
335-483 can be referred to.

The addition amount of these quaternary onium salt compounds is as follows:
1 × 10 per mole of silver halide ^-8~ 1 mol, good
Preferably 1 × 10^-7~ 1 × 10^-1Is a mole. More preferred
Or 1 × 10^-Five~ 1 × 10^-2Is a mole. These are c
Photosensitive at any time from silver logenide grain formation to coating
Can be added to the material. The amount added to the hydrophilic colloid layer is higher
The amount may be based on the above-mentioned silver halide emulsion layer.

The quaternary onium salt compounds may be used alone or in combination of two or more. It may be added to any of the constituent layers of the light-sensitive material, but preferably at least one of the constituent layers on the side having the silver halide emulsion layer.
Layer and further added to the silver halide emulsion layer and / or the layer adjacent thereto.

The emulsion of the present invention contains iridium salt and rhodium
It is preferable to contain a salt. Preferably halogenated
Silver particles are less likely to form or grow.
At least in one step, and
It is preferably added as a salt. Distribution of these complex salts
As a ligand, a halogen atom, a nitrosyl group, a cyano
Group, aquo group, alkyl group, pseudohalogen group, alkoxy
Groups, ammonium groups, and any combination thereof.
Which can be used. The amount added is
1 × 10 per mole of silver logenide^-9~ 1 × 10^-FiveMole,
Preferably 1 × 10 ^-8~ 1 × 10^-FourIs a mole. Again
Ruthenium salt, osnium salt, iron salt, copper salt, platinum salt, para
Complexes containing elements from groups 3 to 13 of the periodic table, such as the indium salt
Salt may be added together.

The average grain size of the silver halide is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. What is particle size?
In the case where the particles are spherical or particles that can be approximated to spheres, this means particle diameter. If the particle is a cube, convert it to a sphere,
The diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG. K. Mees & T. H. Jam
by es: The theory of the photo
ographic process, 3rd edition, 36-4
See page 3 (1966, published by Mcmillan).

The shape of the silver halide grains is not particularly limited, and may be any of a tabular shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedral shape, and any other shapes. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
So-called monodisperse emulsions containing 0%, preferably 95% are preferred.

The method of reacting the soluble silver salt with the soluble halide salt at the time of preparing the silver halide emulsion may be any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The surface of the silver halide grains can be controlled in halogen composition by using water-soluble halides or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects, and the like. In the present invention, as the silver halide grains, particle size, sensitivity, crystal habit, photosensitive wavelength, halogen composition, monodispersity, amount and type of doping agent, potential, pH, desalting method and other production conditions, surface A plurality of types of particles having different states, chemically sensitized states, and the like can be used in combination. In that case,
These silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (RD).
17643, pages 22 to 23 (December, 1978).

As the sensitizing dye used in the photographic light-sensitive material of the present invention, those described in the following applicable places can be used.

JP-A-5-224330, pages (3) to (13) JP-A-6-194771, page (11) to page (22) JP-A-6-242533, page (2) to (8) Page 6 JP-A-6-337492, pages (3) to (34) JP-A-6-337494, pages (4) to (14) The sensitizing dye may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used especially for supersensitization. A useful combination of a dye exhibiting supersensitization and a substance exhibiting supersensitization are RD1764.
3 (issued December 1978), page 23, IV, section J.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7). -Tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like. Can be. Particularly preferred are a substituted or unsubstituted heterocyclic or fused heterocyclic ring containing any of N, O, S and Se, and a water-soluble halide.

In the silver halide photographic light-sensitive material of the present invention,
It is advantageous to use gelatin as a binder or protective colloid in the hydrophilic colloid layer.

As the gelatin, besides lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used. The amount of addition is 0.5 or more and 3.5 g / m ² or less, more preferably 0.8 g / m ² or less.
It is 3.0 g / m ² or less. When the amount is less than 0.5 g / m ² , the processing suitability is improved, but the deterioration of the stain during the processing is large, and when it is more than 3.0 g / m ² , the rapid processing suitability is lost.

It is advantageous to use gelatin as the binder or protective colloid, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, an amide group and the like, and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, ₃₁ NR ₃₂ -R ₃₃ (R ₃₁ , R ₃₂ , R
₃₃ may be different from each other, a hydrogen atom, an aliphatic group, an aromatic group, a sulfinic acid residue, a carbonyl group, an oxalyl group, a carbamoyl group, an amino group, a sulfonyl group, a sulfoxy group, an iminomethylene group, an alkenyl group, and an alkynyl Group, aryl group, alkoxy group, alkenyloxy group,
Any group bonded via an alkynyloxy group, an aryloxy group, or the like), a cationic group, or the like. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

The emulsion layer and the non-photosensitive hydrophilic colloid of the light-sensitive material of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β-
(Vinylsulfonyl) propionamide]), an active halogen compound (2,4-dichloro-6-hydroxy-s)
-Triazines, etc.), mucohalic acids (mucochloric acid,
Phenoxime cochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, isocyanates, carboxyl group-active hardeners and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer may be coated with various known additives for various purposes such as coating aid, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties. Surfactants may be used.

Various other additives are used in the light-sensitive material of the present invention. For example, a desensitizer, a plasticizer, a development accelerator, oil, colloidal silica and the like can be mentioned.

As these additives and the above-mentioned additives, those described in (RD) No. 17643, pp. 22 to 31, etc. can be used.

The silver halide photographic light-sensitive material of the present invention has a layer structure composed of at least two layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween. Further, it may have a non-photosensitive emulsion. As the non-emulsion layer, any number of layers may be provided as necessary between the support and the emulsion layer closest to the support, between a plurality of emulsion layers, and outside the emulsion layer farthest from the support. Can be. In these layers, a state in which a water-soluble or water-insoluble dye, an imagewise or non-imagewise development adjusting (suppression or acceleration) agent, a contrasting agent, a physical property adjusting agent, etc. are dissolved in an aqueous solution or an organic solvent, Alternatively, it can be contained in a form dispersed in solid fine particles (which may or may not be protected by oil).

The emulsion layer may be on one side or both sides of the support. Even on one side, an arbitrary number of hydrophilic or non-hydrophilic layers can be provided in combination on the opposite side. In particular, when a layer of a hydrophobic polymer is provided outside the hydrophilic colloid layer with respect to the support, the drying property can be improved.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a flexible support usually used for the light-sensitive material. Useful as flexible supports are films of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate synthetic polymers (which may contain colored content), or polyethylene or polyethylene. A paper support coated with a polymer such as terephthalate; These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

The sulfite and metabisulfite used as a preservative in the development processing of the present invention include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. 0.25 mol / sulfite
Liter or more is preferred. Particularly preferably 0.4 mol /
More than a liter.

In the developing solution, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) , Dissolution aids (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 8.5 or more to less than 10.5, and particularly preferably adjusted to 9.0 to 10.4.

Next, the compound represented by formula (2) of the present invention will be described. Examples of the compound represented by the general formula (2) include ascorbic acid and derivatives thereof. Among them, the compound represented by the following general formula (2-a) in which R ₁₁ and R ₁₂ are bonded to each other to form a ring in the general formula (2) ) Is preferred.

[0088]

Embedded image

[0089] In the formula, R ₁₃ is a hydrogen atom, each substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₁₁ is O or S is represented, and Y ₁₂ represents O, S or NR ₁₄ . R ₁₄ represents a substituted or unsubstituted alkyl group or aryl group.

Examples of the substituent of the alkyl group include a halogen atom (for example, Cl, Br, etc.), a hydroxy group, an aryl group having 6 to 20 carbon atoms (for example, phenyl and naphthyl group), and a heterocyclic group (for example, 2 , 2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc., C1-C20 alkoxy group (for example, methoxy group, ethoxy group, etc.), An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group), Heterocyclic oxy group (for example, pyridyloxy group), acylamino group having 1 to 26 carbon atoms (for example, acetylamino, heptylamino, propionylamino group) ), Amino group (e.g. amino, methylamino, dimethylamino, dibenzylamino group, etc.)
And the like.

Examples of the substituent of the amino group include a halogen atom (for example, Cl, Br, etc.), a hydroxy group, an aryl group having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group and the like), and a C 1 to C 20 group. An alkyl group such as methyl,
Ethyl, butyl, cyclohexyl, isopropyl, dodecyl group, etc., heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.) , Carbon number 1-2
0 alkoxy groups (for example, methoxy, ethoxy group, etc.),
An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group), Examples include a heterocyclic oxy group (for example, a pyridyloxy group) and an acyl group having 1 to 20 carbon atoms (for example, an acetyl group, a heptyl group, a propionyl group, and the like).

Examples of the substituent of the alkylthio group include a halogen atom (eg, Cl, Br, etc.), a hydroxy group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group,
A naphthyl group, etc., a heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N'-
Diethylpyrazolidinyl group, pyridyl group, etc.), carbon number 1
An alkoxy group (e.g., methoxy group, ethoxy group, etc.), an aryloxy group having 6-20 carbon atoms (e.g., phenoxy group), an alkenyloxy group having 1-20 carbon atoms (e.g., allyloxy group, etc.), 1 carbon atom Alkynyloxy group (for example, propargyloxy group), heterocyclic oxy group (for example, pyridyloxy group), carbon number of 1-26
(E.g., acetylamino, heptylamino, propionylamino, etc.) and amino (e.g., amino, methylamino, dimethylamino, dibenzylamino, etc.).

Examples of the substituent of the aryl group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group,
An alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl,
Butyl, cyclohexyl, isopropyl, dodecyl group, etc.), heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolidinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), carbon An alkoxy group having 1 to 20 carbon atoms (such as a methoxy group or an ethoxy group), an aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), An alkynyloxy group having 1 to 20 atoms (eg, propargyloxy group), a heterocyclic oxy group (eg, pyridyloxy group), an acylamino group having 1 to 26 carbon atoms (eg, acetylamino, heptylamino, propionylamino group, etc.); An amino group (eg, an amino group,
Methylamino group, dimethylamino group, dibenzylamino group, etc.).

Examples of the substituent of the above alkoxy group include:
A halogen atom (eg, Cl, Br, etc.), a hydroxy group,
An aryl group having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, butyl group, cyclohexyl group, isopropyl group, dodecyl group, etc.), heterocyclic ring Groups (eg, 2, 2,
6,6-tetramethylpiperidyl group, quinolizinyl group,
N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group), alkenyloxy group having 1 to 20 carbon atoms (eg, allyloxy group), carbon atom An alkynyloxy group having the number of 1 to 20 (eg, propargyloxy group), a heterocyclic oxy group (eg, a pyridyloxy group), and a carbon number of 1 to 26;
(E.g., acetylamino group, heptylamino group, propionylamino group, etc.) and amino group (e.g., amino, methylamino, dimethylamino, dibenzylamino group, etc.).

Examples of the substituents of the above sulfo group, carboxyl group, amide group and sulfonamide group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an alkali metal group (eg, sodium, potassium, etc.), 6
To 20 aryl groups (eg, phenyl group, naphthyl group, etc.), alkyl groups having 1 to 20 carbon atoms (eg, methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl group, etc.), and heterocyclic groups (eg, 2, 2, 6) , 6-tetramethylpiperidyl group, quinolizinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), having 1 to 20 carbon atoms
Alkoxy group (for example, methoxy group, ethoxy group, etc.),
An aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group), Heterocyclic oxy group (for example, pyridyloxy group), acylamino group having 1 to 26 carbon atoms (for example, acetylamino, heptylamino, propionylamino group, etc.), amino group (for example, amino, methylamino, dimethylamino, dibenzylamino group, etc.) )
And the like.

The general formula (2) or the general formula (2-
Specific examples of the preferred compound represented by a) include, for example, paragraphs 0112 to 01 of JP-A-11-160835.
B-1 to B-56 described in P.16.

These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In the image forming method of the silver halide photographic light-sensitive material of the present invention, substantially no hydroquinone (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate, etc.) is contained. Is particularly preferred. The term "substantially not contained" means an amount of less than 0.01 mol per liter of the developer.

In the present invention, the developing agent of the present invention and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl) -3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol,
N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) can be used in combination. When used in combination, the developing agents for 3-pyrazolidones and aminophenols are usually
It is preferably used in an amount of 0.01 to 1.4 mol per liter.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, such as aluminum chloride, aluminum sulfate and potassium alum. The fixing solution optionally contains compounds such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. be able to. In the development processing, washing is performed after fixing, and the washing layer may be a method in which fresh water is supplied at a rate of several liters per minute depending on the processing, or the washing water is circulated.
A method of reusing after treating with a chemical, a filter, ozone, light, or the like, or a method of replenishing a small amount of a stabilizing solution in accordance with a treatment amount by using a washing bath as a stabilizing bath containing a stabilizer is used. This step is usually at room temperature, but it may be heated to 30 ° C to 50 ° C. In addition, when a stabilizing bath is used, it is possible to perform a pipeless treatment that does not need to be directly connected to the water supply. A rinsing bath can be provided before and after each treatment layer.

The mother liquor or replenisher of the developing solution, the fixing solution, or the stabilizing solution is usually supplied in the form of the working solution or the concentrated solution diluted immediately before. It may be in the form of a concentrated liquid, a viscous liquid in a semi-kneaded state having a high viscosity, or may be a method in which a simple substance or a mixture of solid components is dissolved at the time of use. When a mixture is used, a method in which components that are difficult to react with each other are adjacently packed in layers and then vacuum-packaged, and then opened and dissolved at the time of use, or a method of tableting can be used. In particular, the method of adding a tablet formed product to the dissolution layer or the directly treated layer is a method which is extremely excellent in workability, space saving and preservation, and is particularly preferably used.

In the drying zone of the automatic developing machine, a method of drying with hot air is usually used. However, a heat transfer material of 90 ° C. or more (for example, a heat roller of 90 ° C. to 130 ° C.) or 150 ° C. or more is used. (For example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, and silicon carbide, etc.) by direct current generation and radiation, and heat energy from a resistance heating element to copper, stainless steel, nickel, various ceramics, etc. That emits infrared rays by transmitting heat to the radiator of the present invention), or those having known drying means such as a dehumidifier, a microwave generator, and a water-absorbing resin. . Further, a control mechanism for a dry state may be provided.

In the present invention, processing is preferably carried out using an automatic developing machine in view of a demand for shortening the developing time. The processing time is preferably 20 seconds or less, and the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone is 10 seconds to 70 seconds. Preferably, it is seconds.

The term "total processing time" as used herein includes the total processing time required for processing a black-and-white photographic light-sensitive material, and specifically, for example, the steps such as development, fixing, washing or rinsing, and drying required for processing. Time including all of the above, that is, Dry to
It is the time of Dry. If the total processing time is less than 10 seconds, desensitization, softening, etc. occur, and satisfactory photographic performance cannot be obtained.
Preferably, the total processing time is 15 seconds to 70 seconds. In order to stably process a large amount of photosensitive material of 10 m ² or more, the developing time is preferably 5 seconds to 20 seconds.

The light-sensitive material of the present invention is most effective when used as an output light-sensitive material.
An r laser, a He-Ne laser, a red laser diode, an infrared semiconductor laser, and a red LED laser are typical, but other arbitrary lasers such as a blue laser such as a He-Cd laser can be used. The output method may be performed by using a single laser or a plurality of lasers simultaneously.

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

[0107]

EXAMPLES Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and Na
A water-soluble halide solution C composed of Cl and KBr is adjusted to pH 3.
The mixture was added at a temperature of 0, 40 ° C. and a constant flow rate in Solution A for 30 minutes by the simultaneous mixing method, and 0.20 μm of AgCl 70 mol%, AgBr 3
0 mol% of cubic crystals were obtained. At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. Unnecessary salts were removed by ultrafiltration, and then 15 g of gelatin per mol of silver was added to adjust the pH to 5.7, followed by dispersion at 55 ° C. for 30 minutes. After dispersion, 4 × 10 ⁻⁴ mol of chloramine T was added per mol of silver. The silver potential of the resulting emulsion is 190 mV (40 ° C.)
Met. A: Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Ion exchange water 700 ml Na [RhCl ₅ (H ₂ O)] 0.02 mg B: Silver nitrate 170 g Nitric acid (5%) 4.5 ml Ion exchange water 200 ml C: NaCl 47.5 g KBr 51.3 g ossein gelatin 6 g Na ₃ [IrCl _6] 0.15mg of silver per mole of the ion-exchanged water 200ml resulting emulsion, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
× 10 ⁻³ mol and 8.5 × 10 ⁻⁴ mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV. Next, the sulfur dispersed in the form of fine particles was converted into sulfur atoms by 2 × 10
^-5 mol and 1.5 × 10 ^-5 mol of chloroauric acid were added, and the mixture was chemically ripened at a temperature of 55 ° C. for 60 minutes.

Then, after the temperature was lowered to 40 ° C., the sensitizing dye d-
1 and d-2 were added in an amount of 2 × 10 ^-4 mol per mol of silver, and the mixture was kept for 20 minutes to obtain a silver halide emulsion A. The silver halide emulsion A was cooled and set, and dissolved and used when preparing a coating solution.

[0109]

Embedded image

Using the obtained emulsion, the following first layer and second layer were simultaneously coated on one side of the undercoated support from the support side and cooled and set. Thereafter, the following backing layer was coated on the undercoating layer having the antistatic layer on the opposite side at a coating speed of 200 m / min, cooled and set at -1 ° C, and dried on both sides simultaneously to obtain a sample. The preparation of the coating solution was performed at 35 ° C., and the time from the start of the addition to the application was within 40 minutes for each coating solution.

(Support, Undercoat Layer) After a corona discharge of 30 W / (m ² · min) was applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition was applied to both sides. And dried at 100 ° C. for 1 minute.

Copolymer of 2-hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) (numbers are mass ratio) 0.5 g / m ² surfactant A 3.6 mg / m ² Hexamethylene-1,6-bis (ethylene urea) 10 mg / m ² (Antistatic layer) Corona discharge of 10 W / (m ² · min) was performed on a polyethylene terephthalate support provided with an undercoat layer. Thereafter, an antistatic layer having the following composition was applied on one surface at a speed of 70 m / min using a roll-fit coating pan and an air knife, dried at 90 ° C. for 2 minutes, and then dried at 140 ° C.
For 90 seconds.

Water-soluble conductive polymer B 0.6 g / m ² hydrophobic polymer particles C 0.4 g / m ² polyethylene oxide compound (MW 600) 0.1 g / m ² Curing agent E 0.1 g / m ² First layer (Emulsion layer) Gelatin 1.2 / m ² silver halide emulsion A 3.3 g / m ² 5-nitroindazole 0.01 g / m ² 2-mercaptohypoxanthine 0.02 g / m ² colloidal silica 75 mass as silver amount % Of vinyl acetate, 12.5% by mass of vinyl acetate, and 12.5% by mass of vinyl pivalinate, a suspension polymer 1.4 g / m ² dextran (average molecular weight 60,000) 0.2 g / m ² 4-mercapto-3, 5,6-fluoro phthalate 0.05 g / m ² sodium polystyrenesulfonate (average molecular weight 500,000) 0.015 g / m ² coating solution pH was 5.2. Second layer (protective layer) Gelatin 0.75 g / m ² dextran (average molecular weight 60,000) 0.2 g / m ² amine compound Na-1 0.15 g / m ² colloidal silica 0.10 g / m ² fungicide Z 0 .005g / m ² polyoxyethylene sodium polyoxyethylene lauryl ether sulfonic acid 0.001 g / m ² dihexyl sulfosuccinate sodium 0.015 g / m ² silica (average particle diameter 5μm) 0.015g / m ² silica (average particle size 8 [mu] m) 0 .15 g / m ² hardener (1) 0.15 g / m ² backing layer Gelatin 1.8 g / m ² F-1 0.01 g / m ² F-2 0.03 g / m ² F-3 0.10 g / m ² colloidal silica 75 wt% and a vinyl acetate 12.5 wt%, and the vinyl peak burrs sulphonate 12.5% by weight of the suspension polymerization product 0.7 g / m ² sodium polystyrenesulfonate 0 010g / m ² Matting agent: monodispersed polymethylmethacrylate 0.045 g / m ² hardener having an average particle size of 3μm ⁽²⁾ 0.05g / m 2 Backing protective layer Gelatin 1.8 g / m ² Matting agent: Mean particle diameter 3μm of monodisperse polymethyl methacrylate 0.045 g / m ² polyoxyethylene lauryl ether sodium sulfonate 0.005 g / m ² sodium dihexyl sulfosuccinate 0.005 g / m ² hardener (1) 0.15g / m ²

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

The addition position and amount of the compound represented by the general formula (1) shown in Table 1 were added. As a comparative example, a sample in which the amount of the sulfur sensitizer or the aging temperature was increased was prepared.

The obtained film sample A was prepared using a 633 nm HeNe light source and a spot system of 14 μm at 2400 d.
Solid exposure was performed at a resolution of pi. The following processing was performed on this sample. (Dpi is the number of dots per 2.54 cm.) (Per liter of developer) Diethylenetriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium hydrogen carbonate 17 g 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone 1.5 g Sodium erythorbate monohydrate 40 g 1-phenyl-5-mercaptotetrazole 0.025 g Potassium bromide 4 g 5-methylbenzotriazole 0.21 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.07 g Was added to give a pH of 9.8, and the mixture was made up to 1 liter.

(Per liter of fixing solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Na gluconate 5 g Citric acid 3Na · 2H ₂ O 12 g Citric acid 12 g Adjusted to pH 5.4 with sulfuric acid, Finished to 1 liter.

(Washing Water) To 1 liter of tap water, 8.8 ml of the following purifying agent was added and placed in a washing tank to obtain washing water.

(Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35 mass% hydrogen peroxide water 171 g Pluronic F-68 3.1 g Hoksite F-150 15 g DTPA / 5Na 10 g Make up to 1 liter with pure water.

[0122] <Evaluation of Sensitivity and Fog> The sensitivities in the following table indicate the values of Sample No. 1
Was expressed as a relative sensitivity when the sensitivity at a density of 2.5 was taken as 100. The PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).
The fog was measured by setting the density of the unexposed portion to zero for air. The smaller the value, the lower the fog. The automatic developing machine is an automatic developing machine LD-M1090 manufactured by Dainippon Screen Mfg. Co., Ltd.
Was processed.

[0123]

[Table 1]

[0124]

Embedded image

As is clear from Table 1, in the embodiment of the present invention, sensitization can be achieved without deteriorating fog as compared with sulfur sensitization or strengthening of the ripening temperature.

Example 2 Sample No. 1 was prepared by adding the hydrazine compound D shown in Table 2 to the emulsion layer coating solution in accordance with the formulation of the samples Nos. 1, 2, 3, and 7 in Table 1. 9, 10, 11 and 12 were prepared, and sample N
o. Compound B as compound of general formula (1)
Using the sample No. 13 was produced. The same evaluation as in Example 1 was performed. Table 2 shows the results.

<Evaluation of Gamma Value> The gamma value is a ratio of a change in density corresponding to a change in exposure amount, and is a value commonly used as a measure of high contrast in the art, and a higher value indicates a higher contrast. Values were determined for concentrations from 0.1 to 3.0.

(Evaluation of Black Pots) The obtained developed samples were visually evaluated using a 100 × loupe manufactured by PEEAK, and the number of black pots generated per visual field was counted. The smaller the better. The number is preferably 5 or less, and 30 or more is not practical.

[0129]

[Table 2]

[0130]

Embedded image

It can be seen that the sample of the present invention was excellent in sensitizing effect without deteriorating black potatoes in combination with the hydrazine compound.

Example 3 In Example 1, the formula (2) of the present invention in the developer formulation was used.
A developer composition was prepared by replacing sodium erysorbate, a compound represented by the formula, with 20 g / liter of hydridoquinone, and processing was carried out at a pH of the developer of 10.2.
Table 3 shows the results.

[0133]

[Table 3]

As compared with the results of Examples 1 and 2, the effect of the present invention is more significant in the case of the developer containing the compound of the general formula (2) of the present invention instead of hydroquinone.

[0135]

According to the present invention, an ultra-hard silver halide photographic light-sensitive material having high sensitivity, low fog, and reduced occurrence of black spots can be provided.

Claims (3)

[Claims] A photosensitive silver halide emulsion layer containing at least one layer of a hydrophilic colloid is provided on a support, and said silver halide emulsion layer or another non-photosensitive hydrophilic colloid layer is represented by the following general formula: A silver halide photographic material comprising at least one compound represented by the formula (1). Embedded image [Wherein, EWD represents an electron-withdrawing group, and R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a monovalent substituent. However, R ₁ and R ₂ do not simultaneously represent a hydrogen atom. ] 2. The silver halide photographic material according to claim 1, wherein the hydrazine derivative is contained in the silver halide emulsion layer or another non-photosensitive hydrophilic colloid layer. 3. A silver halide photographic material characterized by processing the silver halide photographic material according to claim 1 or 2 with a processing agent containing a compound represented by the following general formula (2) as a developing agent. Processing method of photosensitive material. Embedded image [In the formula, R ₁₁ and R ₁₂ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group, which may have a substituent or may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ]