JPH10221804A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material for making a printing plate capable of enhancing red sensitivity and practicable density and improving dot reproduction performance and restraining residual dye stains by incorporating each specified plural kinds of compounds in a silver halide emulsion layer. SOLUTION: The silver halide emulsion layer contains the compounds represented by formula I and formula II in both of which each of R1 -R4 is an aliphatic group and at least one of R2 and R4 is substituted by a water- solubilizing group; each of V1 -V8 is an H atom or a substituent, and each of V1 -V4 and each of V5 -V8 are each a group having the sum of all the Hammett's substituent constants σp being >0.12; each of Y1 -Y3 is a -N(R)- group or an oxygen atom or the like; R5 is a <=10 C aliphatic group substituted by a water- solubilizing group; each of R, R6 , and R7 is an aliphatic or aryl group or the like and at least 2 of them is substituted by the water-solubilizing group; each of V9 and V10 is an H atom or an alkyl group; each of L1 -L7 is a methine group; and each of M1 and M2 is an ion necessary to neutralize a charge in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly, to a silver halide photographic material for plate-making printing and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, with the rapid processing of silver halide photographic light-sensitive materials, dyes, dyes, and the like remain on the processed film due to a reduction in processing time, an anhydrous washing, and recycling of a processing solution. That is, so-called residual color contamination tends to occur.

[0003] The dye contamination not only significantly lowers the commercial value of the light-sensitive material, but also it is preferable from a practical point of view that the image is clear. Therefore, reduction of residual color contamination has become an important technical problem.

Heretofore, as a typical countermeasure against dye stain, reduction of residual color stain has been attempted by introducing a water-soluble group into a dye molecule.

[0005] Increasing the water solubility of the sensitizing dye, however, can improve the residual color contamination, but does not provide sufficient spectral sensitization, and may cause stagnation of the emulsion coating solution or storage over time after production. There has been a problem that the sensitivity is likely to fluctuate.
In particular, dyes that spectrally sensitize in the red wavelength region had many such negative effects.

Hitherto, it has been well known that two or more sensitizing dyes are combined and spectrally sensitized for the purpose of increasing the spectral sensitivity in the red wavelength region as in the present invention. Representative examples include the combined use of cyanine dyes, but these spectral sensitization methods do not improve residual color contamination. In particular, when the silver halide photographic light-sensitive material is used for plate-making printing, it has the disadvantage that not only residual color contamination but also poor dot reproducibility are obtained.

Further, a technique has been disclosed in which the spectral sensitivity is increased by using a spectral sensitizing dye and a specific supersensitizer in combination to reduce the load of residual color contamination, but a necessary and sufficient amount of the dye is used. In some cases, the level was insufficient, and further improvement was required.

On the other hand, in recent photographic processing, a developing solution having a low pH and a low replenishment is also desirable from the viewpoint of environmental protection, and it has been desired to design a photosensitive material that can withstand this demand.

[0009]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having improved red light sensitivity and practical density as well as improved halftone dot reproducibility and residual color contamination as a photographic material for plate making printing. It is to provide materials.

[0010]

The object of the present invention has been attained by the following. That is, in a silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, the silver halide emulsion layer is represented by the following general formula (I). A silver halide photographic material comprising at least one compound represented by the formula (I) and at least one compound represented by the following formula (II):

[0011]

Embedded image

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a substituted or unsubstituted aliphatic group, and at least one of R ₂ and R ₄ substitutes for a water-solubilizing group. V ₁ , V ₂ , V ₃ , V ₄ ,
V ₅ , V ₆ , V ₇ and V ₈ each represent a hydrogen atom or a substituent, and V ₁ and V ₂ , V ₂ and V ₃ , V ₃ and V ₄ , V ₅ and V ₆ , V ₆
And V ₇ and V ₇ and V ₈ may each form a condensed ring. Here, V _{1 to} V _{4 and} V _{5 to} V ₈ are substituents whose sum of the added Hammett σp values is greater than 0.12. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group. M ¹ represents an ion necessary for neutralizing the charge in the molecule, and ¹ represents the number of ions required for neutralizing the valence in the molecule.

[0013]

Embedded image

Wherein Y ₁ , Y ₂ and Y ₃ are each independently —N
R represents a (R) -group, an oxygen atom, a sulfur atom or a selenium atom, R ₅ represents an aliphatic group having 10 or less carbon atoms substituted with a water solubilizing group, and R, R ₆ and R ₇ each represent an aliphatic group; Represents a group, aryl or heterocyclic group, and at least two of R, R ₆ and R ₇ substitute a water solubilizing group. V
₉ and V ₁₀ are each a hydrogen atom, an alkyl group, an alkoxy group,
An aryl group or V ₉ and V ₁₀ may be combined to form a ring, and L ₆ and L ₇ represent a methine group. M ² represents an ion necessary to neutralize the charge in the molecule, and m represents the number of ions required to neutralize the valence in the molecule.

In a silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, the silver halide emulsion layer is represented by the above formula (I). And at least one compound represented by the above general formula (II),
A silver halide photographic light-sensitive material characterized in that the silver halide emulsion layer or the hydrophilic colloid layer contains at least one hydrazine derivative and / or quaternary onium salt.

A method for processing a silver halide photographic light-sensitive material, comprising, after exposing the silver halide photographic light-sensitive material described above, processing with a developer replenishment rate of 40 to 200 ml / m ² .

The method for processing a silver halide photographic material as described in the above item, wherein the processing is performed at a developer pH of 9.0 to 11.0.

Hereinafter, the present invention will be described in detail.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer and a hydrophilic colloid layer on one side of a support. At least one of the silver halide emulsion layers is a photosensitive layer. The hydrophilic colloid layer referred to in the present invention includes, for example, a silver halide photograph such as an intermediate layer, a protective layer, a dye layer, a filter layer, an undercoat layer, an antistatic layer or a substantially light-insensitive silver halide emulsion layer. Refers to a layer constituting a photosensitive material.

In the silver halide photographic light-sensitive material of the present invention, the aliphatic sensitizing dye represented by R _{1 to} R ₄ of the spectral sensitizing dye represented by formula (I) contained in the silver halide emulsion layer. Examples of the group include a branched or linear alkyl group having 1 to 10 carbon atoms (for example, each group such as methyl, ethyl, n-propyl, n-pentyl, and isobutyl), a vinyl group, and a 2 to 10 carbon atom. (For example, 3-butenyl, 2-propenyl, etc.) or a group having 3 carbon atoms
To 10 aralkyl groups (for example, benzyl, phenethyl, etc.). Examples of the water-solubilizing group that substitutes for at least one of R ₂ and R ₄ include acid groups such as a sulfo group, a carboxy group, a phosphono group, a sulfate group, and a sulfino group.

Each aliphatic group represented by R _{1 to} R ₄ is a hydroxy group, a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group, etc.), aryloxy group (for example, phenoxy group, p-sulfophenoxy group, etc.), cyano group, carbamoyl group (for example, carbamoyl group, N-methylcarbamoyl) Group, N, N-tetramethylenecarbamoyl group, etc.),
Sulfamoyl group (for example, sulfamoyl group, N, N
-3-oxapentamethyleneaminosulfonyl group, etc.),
Methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamino group ( Specific examples of the aliphatic group which may be substituted with a substituent such as acetylamino group) and the like, and substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, and the like.
Sulfopentyl, 3-sulfobutyl, 6-sulfo-3-
Oxahexyl, ω-sulfopropoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-
Sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl,
Each group includes o-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl and the like.

Examples of the substituent represented by V _{1 to} V ₈ include an electron-donating group selected such that the sum of the added Hammett σp values is greater than 0.12, and an arbitrary electron-withdrawing group. . Specifically, a cyano group, a carboxy group, a linear or branched alkyl group (eg, methyl, ethyl, is
o-propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.), alkoxy groups (eg, methoxy, ethoxy, propoxy, etc.), alkylthio groups (eg, methylthio group), for example, Halogen atoms such as fluorine, chlorine and bromine, carbamoyl groups (for example,
Carbamoyl, N-methylcarbamoyl, N, N-pentamethylenecarbamoyl, etc.), sulfamoyl group (eg, N-methylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, etc.), acylamino group (eg, , Acetylamino, propionylamino, benzoylamino, etc.), sulfonylamino group (for example, methanesulfonylamino, benzenesulfonylamino, m-chlorobenzenesulfonylamino, perfluoromethanesulfonylamino, etc.), alkoxycarbonyl group (for example, , Methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), alkylsulfonyl group (for example, methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, etc.),
An arylsulfonyl group (for example, a group such as benzenesulfonyl), an acyl group (for example, each group such as acetyl and benzoyl), a perfluoroalkyl group (for example, each group such as trifluoromethyl and pentafluoroethyl), and a perfluoroalkoxy group ( For example, trifluoromethoxy, each group such as pentafluoroethoxy), perfluoroalkylthio group (for example, each group such as trifluoromethylthio, pentafluoroethylthio), aryl group (for example, each group such as phenyl, m-chlorophenyl), Heterocyclic groups (for example, pyrrolyl, pyridyl, imidazolyl, furyl, phenyl, etc.).

The Hammett's σp value is a substituent constant determined by Hammett et al. From the electronic effect of the ring group on the hydrolysis rate of benzoic acid ethyl ester, and the value of each group is, for example, Chemical Review (Chemical Review).
Reviews, 17, 125-136 (1935), Journal of Organic Chemistry (Jou)
rnal of Organic Chemistr
y) Volume 23, 420-427 (1958), Experimental Chemistry Course 14 (Maruzen Publishing Co., Ltd.), Physical Organic
Chemistry (Physical Organic C
hemistry; McGraw Hill Boo
k: 1940), Drug Design Volume VII (Drug)
design VII Academic Press;
New York: 1970), Structure-activity relationship of drugs (Nankodo: 1979), Substitute Constants for Correlation Analysis in Chemistry and Biology (Subst)
title Constants for Corr
elation Analysis in Chemi
try and Biology; John Wil
eye and Sons: 1979).

The aryl group, heterocyclic group and alkyl group represented by V _{1 to} V ₈ may have any of the above-mentioned substituents at any positions.

The fused rings formed between V ₁ and V ₂ , V ₂ and V ₃ , V ₃ and V ₄ , V ₅ and V ₆ , V ₆ and V _7, and V ₇ and V ₈ , respectively, A cyclic group such as a 5- to 7-membered saturated carbocyclic ring, aromatic carbocyclic ring, heterocyclic ring and the like can be mentioned, and it may have the above-mentioned optional substituent at an arbitrary position.

Examples of the group substituted with the methine carbon represented by L _{1 to} L ₅ include a lower alkyl group (for example, each group such as methyl and ethyl) and a cyclic alkyl group (for example, cyclopropyl and cyclopentyl). Each group), a substituted alkyl group (for example, each group such as 2-methoxyethyl and 2-thienylmethyl), an aralkyl group (for example, each group such as benzyl and phenethyl), and a phenyl group (for example, each group such as phenyl and carboxyphenyl). Groups, a heterocyclic group (for example, thienyl, furyl, imidazolyl, etc.), an alkoxy group (for example, methoxy, ethoxy, etc.), and a fluorine atom.

L ₁ can form a condensed ring with R ₁ or R ₂ , and L ₂ can form a condensed ring with R ₃ or R ₄ . M ₁ represents a cation or an acid anion. Specific examples of the cation include:
Examples thereof include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, each cation such as lithium, sodium, and calcium). Specific examples of the acid anion include a halogen ion. (Eg, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like.

1 is 0 when an internal salt is formed to neutralize the charge.

Specific examples of the dye represented by formula (I) are shown below, but the present invention is not limited thereto.

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

Next, the dye represented by formula (II) of the present invention used in combination with the dye represented by formula (I) will be described in detail.

In the general formula (II), R ₅ , R ₆ , R
Examples of the water-solubilizing group to be substituted for ₇ and R include the same acid groups as those described in the formula (I), such as sulfo group, carboxy group, phosphono group, sulfate group, and sulfino group. Examples of the aliphatic group include a branched or straight-chain alkyl group having 1 to 10 carbon atoms (for example, each group such as methyl, ethyl, n-propyl, n-pentyl and isobutyl), and a C3 to C10 alkyl group. Examples thereof include an alkenyl group (for example, 3-butenyl, 2-propenyl and the like) and an aralkyl group having 3 to 10 carbon atoms (for example, benzyl and phenethyl). Examples of the aryl group include a phenyl group. Examples of the heterocyclic group include a pyridyl group (2-, 4-), a furyl group (2-), a thienyl group (2-), a sulfolanyl group, a tetrahydrofuryl group, Examples include a piperidinyl group.

Each of R ₅ , R ₆ , R ₇ and R is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), an aryloxy group (for example, Phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3) -Oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group,
It may be substituted with a substituent such as a carboxyphenyl group or an acyl group (for example, an acetyl group or a benzoyl group).

Specific examples of the aliphatic group substituted with a water-solubilizing group include, for example, carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, ω-sulfo Propoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3
-Phosphonopropyl, 4-sulfo-3-butenyl, 2
-Carboxy-2-propenyl, o-sulfobenzyl,
There are various groups such as p-sulfophenethyl and p-carboxybenzyl, and specific examples of the aryl group substituted with a water-solubilizing group include p-sulfophenyl and p-carboxyphenyl. Specific examples of the heterocyclic group substituted with a solubilizing group include groups such as a 4-sulfothienyl group and a 5-carboxypyridyl group.

As the alkyl group represented by V ₉ and V ₁₀ , a linear or branched group (eg, methyl, ethyl, iso
-Propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.). Examples of the alkoxy group include each group such as methoxy, ethoxy, and propoxy.Examples of the aryl group may have a substituent at any position, such as phenyl, p-tolyl, p-hydroxyphenyl, Each group such as p-methoxyphenyl is exemplified. Examples of the condensed ring formed together with the azole ring by bonding to each other at V ₉ and V ₁₀ include benzoxazole, 4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d] oxazole, naphtho [2 , 3-d] oxazole, benzothiazole,
4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, benzoselenazole, naphtho [1,2-d]
And condensed rings such as selenazole.

The above-mentioned substituents represented by V ₉ and V ₁₀ and the formed condensed ring may have a substituent at an arbitrary position, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom). Atom, iodine atom), trifluoromethyl group, alkoxy group (for example, unsubstituted alkyl groups such as methoxy, ethoxy, butoxy, substituted alkoxy groups such as 2-methoxyethoxy, benzyloxy), hydroxy group, cyano group, aryl An oxy group (for example, a substituted or unsubstituted group such as phenoxy or tolyloxy), an aryl group (for example, a substituted or unsubstituted group such as phenyl or p-chlorophenyl), a styryl group, or a heterocyclic group (for example, furyl or thienyl) Carbamoyl group (eg, carbamoyl,
Groups such as N-ethylcarbamoyl), sulfamoyl groups (eg, groups such as sulfamoyl, N, N-dimethylsulfamoyl), acylamino groups (eg, groups such as acetylamino, propionylamino, benzoylamino), and acyl groups (Eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group), sulfonamide group (eg, methanesulfonylamide, benzenesulfonamide, etc.), sulfonyl group (eg, methanesulfonyl, p- Each group such as toluenesulfonyl) and any group such as a carboxy group.

Examples of the group substituted on the methine carbon represented by L ₆ and L ₇ include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, each group such as phenyl and carboxyphenyl). And alkoxy groups (for example, methoxy, ethoxy and the like).

M ² represents a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (eg, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (eg, each ion such as lithium, sodium and calcium). Cation), and specific examples of the acid anion include, for example, a halogen ion (eg, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like. Can be m is
It is 0 when the charge is neutralized by forming an inner salt.

In the above general formula (II), it is preferable that R ₅ is an alkyl group substituted with a sulfo group, and at least two of R, R ₆ and R ₇ are each a carboxymethyl group. .

Hereinafter, specific examples of the sensitizing dye represented by formula (II) will be shown.

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

The dyes represented by the general formulas (I) and (II) are described, for example, in F.I. M. Hama, "Cyanine Soybeans and Related Compounds" (1964,
The compound can be easily synthesized by referring to a conventionally known method described in, for example, Interscience Publishers).

In the present invention, the above general formulas (I) and (I)
The addition amount of the dye represented by I) to the silver halide emulsion varies greatly depending on the conditions to be used and the type of emulsion, but is preferably 1 × 10 ^{−6 to} 5 × 5 per mol of silver halide.
× 10 ⁻³ mol, more preferably 2 × 10 ⁻⁶ to 2 × 10 ⁻³
Range of moles. 0.3 in the light-sensitive material 1 m ² per
The range may be 300 mg.

The addition amount of the combination according to the present invention is such that the dyes represented by the general formulas (I) and (II) are 1: (10-0.1)
Is selected from the range of the addition molar ratio.

The above dyes used in the present invention can be added to the emulsion by a conventionally known method. For example, a protonation dissolution addition method, a dispersion addition method with a surfactant, a dispersion addition method in a hydrophilic substrate, a addition method as a solid solution, or a method disclosed in Research Disclosure 21
802 or the like (for example, water, low-boiling solvents such as methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohols, and high-boiling solvents such as dimethylformamide, methyl cellosolve, and phenyl cellosolve) alone or A method of dissolving in a mixed solvent thereof and adding the solution may be arbitrarily selected and added to the emulsion.

The dye may be added at any stage during the emulsion production process from physical ripening to completion of chemical ripening, but is preferably added between physical ripening and completion of chemical ripening. High spectral sensitivity can be obtained during physical ripening or during the chemical ripening step before or immediately after the addition of the chemical sensitizer.

Incidentally, it can be used in combination with a photosensitive dye other than that according to the present invention. These photosensitive dyes may be added to the emulsion at the same time or separately at different times, and the order and time interval at that time may be arbitrarily determined depending on the purpose.

The spectral sensitivity of the photosensitive dye used in the present invention can be further increased by using a compound having another supersensitizing effect. Examples of the compound having such a supersensitizing effect include a compound having a pyrimidinylamino group or a triazinylamino group, an aromatic organic formaldehyde condensate, a calixarene derivative,
Halogenated benzotriazole derivative, bispyridinium compound, aromatic heterocyclic quaternary salt compound, electron-donating compound, polymer containing aminoallylidenemalononitrile unit, hydroxytetrazaindene derivative, 1,3-oxadiazole derivative, amino -1,2,3,4-thiatriazole derivatives and the like.

The timing for adding these supersensitizers is not limited.
The photosensitive dye can be arbitrarily added according to the timing of addition. The addition amount is 1 × 10 ⁻⁶ to 1 × 10 per mol of silver halide.
^-1 mol is selected in the range of 1/10 to 10
/ 1 molar ratio.

The silver halide photographic material spectrally sensitized by the method of the present invention preferably contains a hydrazine derivative in a silver halide emulsion layer or a hydrophilic colloid layer.

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

[0075]

Embedded image

In the general formula [H], A represents an aliphatic group, an aromatic group or a heterocyclic group.

The aliphatic group represented by A preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 2 carbon atoms.
0 linear, branched or cyclic alkyl group. Examples include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, a benzyl group, and the like. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, A sulfoxy group, a sulfonamide group, an acylamino group, a ureido group, etc.).

The aromatic group represented by A is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring.

The heterocyclic group represented by A is preferably a monocyclic or condensed heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, such as a pyrrolidine ring, an imidazole ring and a tetrahydrofuran ring. , Morpholine ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring,
Examples include a thiophene ring and a furan ring.

Particularly preferred as A are an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents include an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or condensed ring having 1 to 3 carbon atoms in the alkyl portion), and an alkoxy group (preferably Is an alkyl moiety having 1 to 20 carbon atoms, a substituted amino group (preferably an amino group substituted with an alkyl group or an alkylidene group having 1 to 20 carbon atoms), an acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), hydroxyl And a phosphoamide group (preferably having 1 to 40 carbon atoms).

A preferably has at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [H], B is an acyl group (for example, formyl, acetyl, propionyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chloro Benzoyl, etc.), alkylsulfonyl group (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, methanesulfinyl, etc.), arylsulfinyl group (benzenesulfinyl, etc.), carbamoyl group (Eg, methylcarbamoyl, phenylcarbamoyl, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, methoxyethoxycarbonyl, etc.), aryloxycarbonyl group Phenoxycarbonyl, etc.), sulfamoyl group (eg, dimethylsulfamoyl), sulfinamoyl group (eg, methylsulfinamoyl), alkoxysulfonyl group (eg, methoxysulfonyl), thioacyl group (eg, methylthiocarbonyl), thiocarbamoyl group (For example, methylthiocarbamoyl and the like), an oxalyl group (for example, a methyloxalyl group, an ethoxalyl group) and a heterocyclic group (for example, a pyridine ring and a pyridinium ring).

As B, an acyl group or an oxalyl group is particularly preferred.

In the general formula [H], A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.);
Represents a sulfonyl group (such as methanesulfonyl and toluenesulfonyl) or an oxalyl group (such as ethoxalyl).

Particularly preferred among the hydrazine derivatives used in the present invention are compounds represented by the following general formula [Ha].

[0088]

Embedded image

In the general formula [Ha], R ⁵ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group) , Chenyl group,
These groups are preferably further substituted with a substituent represented by X described below. G
Represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and R ⁶ represents a hydrogen atom or a blocking group. X represents a substitutable group;
Represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different.

R ⁵ preferably contains at least one diffusion-resistant group or silver halide adsorption-promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. Alternatively, those containing a repeating structure of an alkyleneoxy unit and a structure containing a quaternary ammonium salt described in JP-A-5-61143 are preferably used.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], the substitutable group represented by X includes a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group (preferably an alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 alkenyl groups, an alkynyl group, an aryl group (for example, phenyl, etc.), an alkoxy group (preferably having an alkyl portion having 1 to 20 carbon atoms or an alkyleneoxy repeating structure), an alkenyloxy group (for example, Allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, phenoxy, etc.), acyloxy group (eg, acetyloxy, propionyloxy, benzoyloxy, etc.), acylamino group (eg, acetylamino,
Propionylamino, butanoylamino, octanoylamino, benzoylamino, etc., sulfonamide group (for example, methanesulfonamide, ethanesulfonamide, propanesulfonamide, butanesulfonamide, hexanesulfonamide, octanesulfonamide, dodecanesulfonamide, benzene) Sulfonamides, etc.), ureido groups (eg, methyl ureide, ethyl ureide, propyl ureide, butyl ureide, hexyl ureide, cyclohexyl ureide, octyl ureide, dodecyl ureide, octadecyl ureide, phenyl ureide, naphthyl ureide, etc.), oxamoyl amino groups (for example, Methyl oxamoyl amino, ethyl oxamoyl amino, butyl oxamoyl amino, octyl oxamoyl amino, phenyl oxa Ylamino etc.), hydrazinocarbonyl amino group (e.g., methyl hydrazino carbonyl amino, ethyl hydrazino carbonylamino, dimethylhydrazino carbonylamino, diphenyl hydrazinocarbonyl amino, phenyl hydrazino carbonyl amino,
Phenylmethylhydrazinocarbonylamino, etc.), an alkylamino group (eg, methylamino, ethylamino, butylamino, octylamino, dodecylamino, etc.), a dialkylamino group (eg, dimethylamino, diethylamino, dibutylamino, methyloctylamino, etc.), An amino group, a hydroxy group, a halogen atom, an alkylthio group (preferably having an alkyl portion having 1 to 20 carbon atoms),
Alkenylthio groups (eg, allylthio, butenylthio, etc.), mercapto groups, sulfo groups, carboxyl groups, thioureido groups (eg, methylthioureido, ethylthioureido, butylthioureido, cyclohexylthioureido, octylthioureido, dodecylthioureido,
Phenylthioureido, etc.), cyano group, sulfonyl group (eg, methanesulfonyl), sulfamoyl group (eg, methylsulfamoyl, ethylsulfamoyl, butylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl group (eg, methylcarbamoyl) , Ethyl carbamoyl, butyl carbamoyl, octyl carbamoyl, phenyl carbamoyl, etc.). These groups may be further substituted with a substituent having the same meaning as the substitutable group represented by X in the general formula [Ha].

[0093] In Formula [Ha], A ₁ and A ₂ have the same meanings as A ₁ and A ₂ in formula (H). A ₁ and A ₂ are preferably both hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ⁶ is
Hydrogen atom, aliphatic group as a blocking group (eg, methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, 4-methoxybenzenesulfonylmethyl, 1-pyridiniomethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl, etc.) An aromatic group (eg, phenyl, hydroxymethylphenyl, chlorophenyl, etc.), a heterocyclic group (eg, pyridyl, thienyl, furyl, N-methylpyridinio, etc.), an amino group (eg, methylamino, dimethylamino, phenylamino, etc.), alkoxy Preferred are groups (eg, methoxy, ethoxy, butoxy, etc.), aryloxy groups (eg, phenoxy, etc.), —COOR ₈ groups, and —CON (R ₉ ) (R ₁₀ ) groups. Here, R ₈ is a hydrogen atom, an alkyl group (eg, methyl, ethyl, benzyl, hydroxyethyl, etc.),
Alkenyl groups (eg, allyl, butenyl, etc.), alkynyl groups (eg, propargyl, butynyl, etc.), aryl groups (eg, phenyl, naphthyl, etc.) or heterocyclic groups (eg, 2,2,6,6-tetramethylpiperidinyl, N -Ethylpiperidinyl, tetrahydrofuryl, a saturated heterocyclic ring such as sulfolane and an unsaturated heterocyclic ring such as pyridyl, pyrimidinyl, thienyl, furyl, etc., wherein R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group (for example, Methyl, ethyl, benzyl, hydroxyethyl, etc.), alkenyl group (eg, allyl, butenyl, etc.), alkynyl group (eg, propargyl, butynyl, etc.), aryl group (eg, phenyl, naphthyl, etc.), heterocyclic group (eg, 2,2,2) 6,
Saturation such as 6-tetramethylpiperidinyl, N, N'-diethylpyrazolidinyl, quinuclidinyl, N-ethylpiperidinyl, N-benzylpiperidinyl, N-benzylpyrrolidinyl, tetrahydrofuryl, sulfolane Heterocyclic ring and unsaturated heterocyclic group such as pyridyl, pyrimidinyl, thienyl, furyl, etc.), hydroxyl group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.) An alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), an aryloxy group (eg, phenoxy, naphthyloxy, etc.),
Represents a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.) or an amino group (eg, amino, methylamino, dimethylamino, dibenzylamino, phenylamino, etc.).

As R ⁶ , a hydrogen atom, an aliphatic group, an aromatic group, a —COOR ₈ group and a —CON (R ₉ ) (R ₁₀ ) group are preferable, and a —COOR ₈ group and a —CON (R ₉ ) ( R ₁₀ )
Groups are more preferred.

In the formula [Ha], the most preferred R
⁶ includes —COOR ₈ ′ group and —CON (R ₉ ′)
(R ₁₀ ') groups (R _8' represents an alkynyl group or a saturated heterocyclic radical, R ₉ 'represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic radical, R ₁₀ 'is an alkenyl group, an alkynyl group,
Represents a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] or [Ha] are shown below, but the present invention is not limited thereto.

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

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

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in JP-A-29,248.

In the present invention, the hydrazine derivative is contained in the hydrophilic colloid layer (including the silver halide emulsion layer) on the side of the silver halide emulsion layer on the support. Preferably, it is contained in a silver halide emulsion layer and / or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The amount of addition may be any amount that makes the contrast higher (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 the present invention, it is preferable to use a nucleation accelerator in order to effectively promote the nucleation reaction by the hydrazine derivative. As the nucleation accelerator, the following general formula [N
a], [Na2] or [Nb].

[0112]

Embedded image

In the general formula [Na], R ₁ , R ₂ and 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, a substituted aryl group, or a saturated or unsaturated heterocyclic ring. R ₁ , R ₂ and R ₃ may 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.
And those having the same meanings as those of the non-diffusion group. Preferred examples of the adsorptive group include a heterocycle, a mercapto group, a thioether group, a thione group, and a thiourea group.

A nucleation accelerator more preferable than the nucleation accelerator represented by the general formula [Na] includes a compound represented by the following general formula [Na2].

[0115]

Embedded image

In the general formula [Na2], R ¹ , R ² , R
³ and R ⁴ are each a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
Represents a substituted alkynyl group, an aryl group, a substituted aryl group, or a saturated or unsaturated heterocyclic ring. These can be linked to each other to form a ring. Also, R ¹ and R ² are not simultaneously hydrogen atoms, and R ³ and R ⁴ are not simultaneously hydrogen atoms. X represents an S, Se or Te atom. L ¹ and L ² each represent a divalent linking group. Specifically, the following groups or combinations thereof: —CH ₂ —, —CH ＝ CH—, —C ₂ H ₄ —, pyridinediyl, —N (Z ₁ ) — (Z ₁ is a hydrogen atom, an alkyl group or an aryl Represents a group), -O-, -S-,-(CO)-,
— (SO ₂ ) —, —CH ₂ N—, and groups having an appropriate substituent (such as an alkylene group, an alkenylene group, an arylene group, an acylamino group, and a sulfonamide group) are exemplified.

Further, the linking group represented by L ¹ or L ² preferably contains at least one or more of the following structures in the linking group.

-CH ₂ CH ₂ O-, -C (CH ₃ ) HCH _{2
O -, - OC (CH 3} ) HCH 2 O -, - OCH 2 C (O
H) HCH _2- Specific examples of the nucleation accelerator represented by the general formula [Na] or [Na2] are shown below.

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

In the present invention, a compound represented by the following general formula [Nb] can be used as a nucleation accelerator.

[0124]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaromatic ring. R ₁₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group or an optionally substituted aryl group. Ar and R ₁₂ may be linked by a linking group to form a ring. The nucleation accelerator represented by the general formula [Nb] preferably has a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight is preferably 120 or more, particularly preferably 300 or more, in order to impart a preferable diffusion resistance. As the silver halide adsorbing group, those having the same meaning as the silver halide adsorption accelerating group in the general formula [H] are preferably used.

Specific compounds of the nucleation accelerator represented by the general formula [Nb] include the following.

[0127]

Embedded image

[0128]

Embedded image

In the silver halide photographic light-sensitive material of the present invention, a quaternary nitrogen compound and / or a quaternary compound are required in the structure in order to effectively promote hardening with a hydrazine derivative as in the case of the above-mentioned nucleation accelerator. A nucleation accelerator selected from quaternary onium compounds having a phosphorus compound can be used.

The quaternary onium compound used in the present invention is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in the molecule, and is preferably a compound represented by the following formula (P).

[0131]

Embedded image

In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

Examples of the substituent represented by R _{1 to} R ₄ include groups such as alkyl, alkenyl, alkynyl, aryl, heterocycle, amino and the like. Specifically, alkyl groups (methyl, ethyl, propyl, Butyl, hexyl, cyclohexyl, etc.), alkenyl group (allyl, butenyl, etc.), alkynyl group (propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (piperidinyl,
Piperazinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.).

The ring which R _{1 to} R ₄ can form by connecting to each other includes rings such as piperidine, morpholine, piperazine and pyridine.

The groups represented by R _{1 to} R ₄ include substituents (hydroxyl, alkoxy, aryloxy, carboxyl,
Sulfo, alkyl, aryl groups, etc.).

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

[0137] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as p- toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
It is a pyridinium compound represented by b) or (Pc).

[0139]

Embedded image

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
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, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiazole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

B _p represents a divalent linking group, and m represents 0 or 1
Represents Examples of the divalent linking group include an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, -
S -, - CO -, - N (R 6) - (R 6 is an alkyl group, an aryl group, a hydrogen atom) represents what is configured alone or in combination. Preferably, B _p is an alkylene or alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include A ¹ , A ² , A ³ , A ⁴
And the substituents mentioned as the substituents for A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl group and a substituted alkyl group.

[0144] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt. Next, specific examples of the pyridinium compound according to the present invention are shown below, but the present invention is not limited thereto.

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

[0151]

Embedded image

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

The addition amounts of the nucleation accelerator and the quaternary onium compound shown above are not uniform depending on the conditions, but are generally 1 × 10 ^-6 to 2 × 10 ^-2 mol per mol of silver halide. And preferably in the range of 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is a silver halide emulsion having a composition having a silver chloride content of 60 mol% or more, and has an average grain size of silver halide. It is preferably 0.6 μm or less, particularly preferably 0.5 to 0.05 μm.

The shape of the silver halide grains is not particularly limited, and may be any of tabular, spherical, cubic, tetradecahedral, octahedral, and other shapes. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

As the tabular grains, tabular grains having a (100) plane having 60 mol% or more of silver chloride as a main plane can be used.

The emulsion may be prepared by any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. 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. To obtain a silver halide emulsion having a nearly uniform grain size.

The silver halide emulsion may or may not be chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used.

As the binder or protective colloid of the photographic emulsion according to the present invention, it is advantageous to use gelatin.
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 such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

As the gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

As one method for remarkably exhibiting the effects of the present invention, it is preferable that at least one constituent layer contains a hydrophilic polymer. Preferred hydrophilic polymers include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan and the like.

The molecular weight of the hydrophilic polymer is from 600 to 100
Up to ten thousand can be appropriately selected. The lower the molecular weight is, the better to elute into the processing solution quickly during the processing, but if it is too low, the film strength of the film is deteriorated. When a hydrophilic polymer is used, the abrasion resistance of the film deteriorates. Therefore, it is preferable to add inorganic colloidal silica, colloidal tin, colloidal zinc, colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite, and the like. As zeolites, analsite, erionite, mordenite, shabasite, gmelinite, levinite, and as synthetic zeolites, zeolite A,
X, Y, L and the like. Examples of apatite include hydroxyapatite, fluorospatite, and chlorapatite.

The preferred amount of addition is from 1% to 200% by weight per hydrophilic binder. By treating the inorganic compound with a silane coupling agent, the inorganic compound hardly aggregates even when added to the emulsion, and can stabilize the coating solution.

Examples of silane coupling agents capable of preventing cracking due to inorganic compounds include triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropyl methacrylate, trimethoxysilanopropylglycidyl, 1-mercapto-3- Examples include triethoxysilanopropane, 1-amino-3-triethoxysilanopropane, triethoxysilanophenyl, and triethoxymethylsilane. By treating the silane coupling agent at a high temperature together with the above-mentioned inorganic compound, the characteristics can be improved as compared with the simple mixing. The mixing ratio is preferably selected in the range of 1: 100 to 100: 1.

As one method for remarkably exhibiting the effects of the present invention, it is preferable to have at least two silver halide emulsion layers. The sensitivity of these emulsion layers may be the same or different. These emulsion layers may be adjacent to each other, or may have one or more intermediate layers between each emulsion layer.

In order for the effects of the present invention to be more remarkably exhibited, at least one silver halide photographic emulsion layer is provided on the side opposite to the silver halide photographic emulsion layer.
It is preferred to have a hydrophilic colloid layer as a layer and to have at least one hydrophobic polymer layer outside the layer. Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called back layer.

It is preferable that at least one hydrophobic polymer layer is provided outside the back layer. The hydrophobic polymer layer is a layer using a hydrophobic polymer as a binder.

Specific examples of the binder for the polymer layer include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, and tetrafluorocarbon. Fluorinated resins such as ethylene and polyvinylidene fluoride,
Butadiene rubber, chloroprene rubber, rubbers such as natural rubber, polymethyl methacrylate, acrylic acid or methacrylic acid esters such as polyethyl acrylate, polyester resins such as polyethylene phthalate, nylon 6,
Examples include polyamide resins such as nylon 66, cellulose resins such as cellulose triacetate, water-insoluble polymers such as silicone resins, and derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferred binders include alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid copolymers (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is 5 mol% or less), styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid
Mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile-methyl methacrylate-ethyl acrylate-acrylic acid copolymer (acrylic acid 5 mol% or less), ethyl acrylate -Glycidyl methacrylate-acrylic acid copolymer. These may be used alone or in combination of two or more.

If necessary, a matting agent, a surfactant, a dye, a sliding agent, a crosslinking agent, a thickener,
V absorbers and photographic additives such as inorganic fine particles such as colloidal silica may be added. Regarding these additives, the description in Research Disclosure Magazine, Vol. 176, No. 17646 (December, 1978) can be referred to.

The hydrophobic polymer layer may be a single layer or two or more layers. There is no particular limitation on the thickness of the polymer layer. However, if the thickness of the hydrophobic polymer layer is too small,
The water resistance of the hydrophobic polymer layer becomes insufficient, and the back layer swells in the treatment liquid, which is inappropriate. Conversely, if the thickness of the hydrophobic polymer layer is too large, the water vapor permeability of the polymer layer will be insufficient, and the moisture absorption and desorption of the hydrophilic colloid layer of the back layer will be inhibited, resulting in poor curl. Of course, the thickness of the hydrophobic polymer layer also depends on the physical properties of the binder used. Therefore, the thickness of the polymer layer needs to be determined in consideration of both. The preferred thickness of the hydrophobic polymer layer depends on the binder type of the hydrophobic polymer layer, but is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm.
m. When the hydrophobic polymer layer comprises two or more layers, the sum of the thicknesses of all the hydrophobic polymer layers is defined as the thickness of the hydrophobic polymer layer of the photosensitive material.

The method for applying the hydrophobic polymer layer is not particularly limited. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be simultaneously coated and then dried. The hydrophobic polymer layer may be applied in a solvent system by dissolving in a solvent of a binder of the polymer layer, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

On the side opposite to the emulsion layer of the silver halide photographic light-sensitive material of the present invention, an adhesive layer / antistatic layer /
It is preferable to provide a back layer / hydrophobic polymer layer containing a hydrophilic colloid. Further, a protective layer may be provided thereon. As an adhesive layer, after coating a vinylidene chloride copolymer or a styrene-glycidyl acrylate copolymer in a thickness of 0.1 to 1 μm on a corona-discharged support, an average particle diameter of 0.01 μm doped with indium or phosphorus is used. ~ 1μ
And a gelatin layer containing fine particles of tin oxide and vanadium pentoxide. Further, a styrene sulfonic acid / maleic acid copolymer can be formed by forming a film with an epoxy compound, an aziridine compound, or a carbonyl active crosslinking agent. A dye back layer can be provided on these antistatic layers. These layers should contain inorganic fillers such as colloidal silica for dimensional stability, silica or methyl methacrylate for preventing adhesion, and silicone-based slipping agents or release agents for controlling transportability. Can be. The backing layer may contain a backing dye, and a benzylidene dye or an oxonol dye is used as the backing dye. These alkali-soluble or decomposable dyes can be fixed as fine particles. The concentration for preventing halation is preferably 0.1 to 2.0 at each photosensitive wavelength.

The support used in the present invention may be either permeable or non-permeable, but is preferably a permeable plastic support. As the plastic support, a support composed of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound, or the like is used.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after forming the film. The most preferable is before the emulsion coating after the film formation, but may be after the emulsion coating. The condition of the heat treatment is preferably 45 ° C. or higher and the glass transition temperature or lower, and preferably between 1 second and 10 days. 1 in terms of productivity
It is preferable to be within hours.

In the silver halide photographic light-sensitive material according to the present invention, the following compounds can be contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound (3) described in JP-A-62-237445, page 11, lower left column, line 11 to page (25) right lower column, line 3 ) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Supersensitizer: JP-A-6-347938, page (3) [0011]-
(16) Compound described on page [0066] (5) Tetrazolium compound JP-A-6-208188, (8) page [0059] to
(10) Compound described on page [0067] (6) Redox compound Compound described on pages (7) to (22) of JP-A-4-245243.

(7) SPS support The support described in JP-A-3-54551 is used.

The above-mentioned additives and other known additives can be used in the silver halide photographic light-sensitive material according to the present invention. These are described in Research Disclosure (RD) Nos. 17643 (December 1978
18716 (November 1979) and 308
119 (Dec. 1989).

The above-mentioned various additives used in the present invention may be used by dissolving them in water or an organic solvent, or may be used by dispersing them in a crystal state of fine particles. As the dispersion method, for example, a ball mill, a sand mill, a colloid mill, an ultrasonic disperser or a high-speed impeller disperser can be used.

In the present invention, for example, JP-A-58-10514
No. 1, the method of mechanically high-speed stirring, or
A method of dissolving by heating after dissolving with an organic solvent described in JP-A-4-2948, removing the solvent and dispersing; dissolving in an acid or alkali described in JP-A-50-80119 or JP-A-2-15252, and then crystallizing out in a polymer; A dispersing method or the like can be applied. In the present invention, the hydrazine derivative which is hardly soluble in water can be dissolved with reference to, for example, the method described in JP-A-2-3033. This method can be applied to other compounds. In addition, a method in which the dye having a carboxy group, the spectral sensitizing dye, an additive, and the like are used to increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxy group.

In the method for processing a silver halide photographic light-sensitive material of the present invention, any known photographic processing agents can be used.

For example, as a developing agent, hydroquinone,
Dihydroxybenzenes such as chlorohydroquinone, methylhydroquinone, potassium hydroquinone monosulfonate, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
3-pyrazolidones such as pyrazolidone, N-methyl-
Aminophenols such as p-aminophenol or a mixture thereof, ascorbic acids such as ascorbic acid, sodium ascorbate, erythorbic acid, etc., or EDTA iron salt as a metal complex salt, DTP
A iron salt, DTPA nickel salt and the like can be used alone or in combination.

Of these, it is preferable to use ascorbic acid and its derivatives in combination with the above-mentioned 3-pyrazolidones or dihydroxybenzenes.

An alkali agent (eg, sodium hydroxide, potassium hydroxide) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Is preferred. As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.5 mol or more and 2.5 mol or less, more preferably 0.75 mol or more and 1.5 mol or less per liter.

If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers, surfactants, defoamers, antifoggants (eg, potassium bromide, sodium bromide, etc.) Halides, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc., chelating agents (eg, ethylenediaminetetraacetic acid or alkali metal salts thereof, nitrilotriacetic acid salts, polyphosphates, etc.), Development accelerators (for example, U.S. Pat. No. 2,304,025, JP-B-47-45541)
And the like, a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent.

In the processing method of the present invention, after the silver halide photographic light-sensitive material of the present invention is exposed, it is processed with a developer containing the above-mentioned known materials. The developer used in the present invention is treated with a developer whose pH at the time of use is adjusted to 9.0 to 11. Particularly preferably, it is processed with a developer having a pH of 9.5 or more and 10.6 or less. This pH is lower than a normal developer pH, and is preferable from the viewpoint of safety during handling or pollution.

As the fixing solution, those having a commonly used composition can be used. As fixing agents, thiosulfates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate can be used. In addition to the thiocyanate, an organic sulfur compound capable of forming a soluble stable silver complex and known as a fixing agent can be used.

To the fixing solution, a water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, an aldehyde compound (for example, glutaraldehyde or an adduct of glutaraldehyde with sulfurous acid) can be added. .

If desired, compounds such as preservatives (for example, sulfites and bisulfites), pH buffering agents (for example, acetic acid and citric acid), pH adjusters (for example, sulfuric acid), chelating agents having a water softening ability, and the like. Can be included.

The pH of the fixing solution is preferably 3 or more and less than 8. After the fixing treatment, the sheet is washed with water and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, an inorganic or organic acid and a salt thereof, or an alkali agent and a salt thereof (for example, an inorganic or organic acid and a salt thereof) for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8). Borate, metaborate, borax,
Phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. are used in combination, and aldehydes (for example, formalin) ,
Glioxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and anti-bacterial agents (eg, phenol, 4-chlorophenol, cresol,
O-phenylphenol, chlorophen, dichlorophen, formaldehyde, P-hydroxybenzoate, 2- (4-thiazoline) -benzimidazole, benzoisothiazolin-3-one, dodecyl-benzyl-
Methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.),
Color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptobenzthiazole
Mercaptohypoxanthine). Among them, it is preferable that the stabilizing bath contains an anti-binder.
These may be replenished in liquid or solid form.

[0195] From demands of the processing method of the amount of waste reduction, the developer replenishing amount in 1 m ² per 50 to 150, more preferably 30~130ml per 1 m ^2. Here, the developer replenishment amount indicates the replenishment amount. Specifically, it is the volume of a solution obtained by dissolving a replenisher for granule development in water.

The developing replenisher and the fixing replenisher may be the same or different from the developing starter and the fixing starter in the tank of the automatic developing machine, respectively. The development start solution and the fix start solution may be prepared from a granule processing agent, may be prepared from a liquid concentrate, or may be a liquid in use.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

In the present invention, 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 when processing using the automatic developing machine is 10 because of the demand for shortening the developing time. It is processed in seconds to 60 seconds.

The term "total processing time" as used herein includes the total processing time required for processing the black-and-white light-sensitive material, and specifically includes the development, fixing, water washing, stabilizing processing, drying, and other steps required for processing. It is a time that includes all the time. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening.
Preferably, the total processing time (Dry to Dry) is 15
~ 60 seconds. To stably process a large amount of photosensitive material of 100 m ² or more, the development time is 2 hours.
The time is preferably not less than seconds and not more than 22 seconds.

In order to exhibit the effects of the present invention remarkably, a heat transfer material (for example, 60.degree.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Heat energy of copper, stainless steel,
Those which transmit infrared rays by transmitting heat to a radiator such as nickel or various ceramics) and have a zone for drying are preferably used.

Examples of the heat transfer material having a temperature of 60 ° C. or higher include:
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a driving means and a driving transmission means. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

The temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller. The temperature controller detects the temperature of the thermistor from 60 ° C. to 150 ° C., preferably 70 ° C. to 130 ° C. Thus, it is preferable that the halogen heater be turned on and off.

The following examples are given as radiating objects emitting a radiation temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer body of 60 ° C. or more and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. (2) upper left column to (3) upper left column (2) Washing water regenerating purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638, lower left column of page (2) to lower left column of page (5) (4) developing bath and fixing Rinse bath during bath: JP-A-4-31
No. 3749 (18) “0054” to (21) “006”
5 "(5) Water replenishment method: JP-A-1-281446, page 2 (2) lower left column to lower right column (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745 No. (2) Bottom right column
(7) Lower right column of the page and JP-A-2-108051 (2)
(3) Silver recovery method of fixing waste liquid: JP-A-6-27623, page (4), "0012" to page (7), "0071".

[0208]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1 (Preparation of silver halide emulsion A) NaCl, gelatin and an antifoaming agent were prepared so that the silver halide content was 70 mol% and the silver bromide content was 30 mol%. , An aqueous solution of silver nitrate, an antifoaming agent and 2 moles per mole of silver.
× 10 ^-7 moles of K ₂ RhCl ₆ and 1 × 1 per mole of silver
NaCl containing 0 ^-6 mol of Na ₂ IrCl ₆ and KBr
Were mixed by a control double jet method to grow silver halide grains. At this time, mixing was performed under the conditions of a silver potential EAg of 130 mV and a pH of 3.0.

Thereafter, the pH was lowered using denatured gelatin treated with phenyl isocyanate, desalted by the ordinary flocculation method, raised in pH, dispersed by adding water, and adjusted again for pH by desalting three times. And then dispersed in gelatin, and used as antioxidants (A), (B) and (C)
Was added to obtain a silver halide emulsion having cubic, monodisperse (particle size distribution variation coefficient: 13%) silver halide grains having an average particle size of 0.18 μm. In addition, the mixing ratio of the following protective agent is [A]: [B]: [C] = 46: 50: 4 (molar ratio).
And

[0211]

Embedded image

The emulsion obtained in this manner was adjusted to pH 5.
4. Adjust the silver potential EAg to 50 mV, add 3 mg of chloroauric acid and 0.5 g of sulfur per mole of silver, and add 50 g at 54 ° C.
Min. And ripened at the end of ripening.
900 mg of 6-methyl-1,3,3a, 7-tetrazaindene per mole of silver, 50 mg of 1-phenyl-5-mercaptotetrazole and 200 mg of KI were added,
A silver halide emulsion A was obtained.

(Preparation of a silver halide photographic light-sensitive material) A polyethylene terephthalate support having a thickness of 100 µm provided with an undercoat layer having a thickness of 0.1 µm on both sides (see Example 1 of JP-A-59-19941). On one side, the following formula (4)
, A photosensitive silver halide emulsion layer of the following formula (1), and upper and lower emulsion protective layers of the following formulas (2) and (3). On one surface, a backing layer of the following formula (5) and a backing protective layer of the following formula (6) were simultaneously coated to form a silver halide photographic material 13 shown in Table 1.
Seeds were prepared.

Formula (1) (Composition of photosensitive silver halide emulsion layer) Gelatin 1.5 g / m ² Silver halide emulsion A Silver coating amount 3.5 mg / m ² Sensitizing dye [General formula (I), (II) ) and comparative dye] table 1, wherein 10 mg / m ² antifoggant: 5-nitroindazole 10 mg / m ² antifoggant: 2-mercapto hypoxanthine 10 mg / m ² surfactant: saponin 0.10 mg / m ² surface Activator: (sodium isoamyl-N-decylsulfosuccinate) 8.0 mg / m ² hydrazine derivative Described in Table 1 15 mg / m ² Quaternary onium compound Described in Table 1 10 mg / m ² Hydroquinone 100 mg / m ² 8-mercaptoadenine 3 mg / m ² Polymer latex P 0.5 mg / m ² Hardener H-1 60 mg / m ²

[0215]

Embedded image

Formulation (2) (Emulsion protective layer lower layer composition) Gelatin 0.6 g / m ² Surfactant: S-2 (sodium di-2-ethylhexylsulfosuccinate) 5 mg / m ² Surfactant: S-3 2 mg / M ² polymer latex P 0.3 mg / m ²

[0219]

Embedded image

Formulation (3) (Emulsion protective layer upper layer composition) Gelatin 0.8 g / m ² Surfactant: S-2 (sodium di-2-ethylhexylsulfosuccinate) 10 mg / m ² Surfactant: S-3 2 mg / M ² matting agent: monodisperse silica having an average particle size of 3.5 μm 20 mg / m ² Hardening agent: formalin 30 mg / m ² Formulation (4) (composition of antihalation layer) Gelatin 0.7 g / m ² Surfactant: Saponin 0.1 mg / m ² 1-phenyl-5-mercaptotetrazole 2 mg / m ² Dye A 20 mg / m ²

[0219]

Embedded image

Formula (5) (backing layer composition)

[0221]

Embedded image

Gelatin 2.4 g / m ² Surfactant: sodium dodecylbenzenesulfonate 50 mg / m ² Formulation (6) (backing protective layer composition) Gelatin 1 g / m ² Matting agent: monodisperse with average particle size of 5.0 μm Polymethyl methacrylate 50 mg / m ² Surfactant: S-2 (sodium di-2-ethylhexylsulfosuccinate) 10 mg / m ² Hardener: glyoxal 25 mg / m ² Hardener: 2-hydroxy-4,6-dichloro Triazine 35 mg / m ^{2 The} obtained film sample was subjected to imagesetter DT-R30.
75 [manufactured by Dainippon Screen Co., Ltd.], and exposed by changing the laser intensity in a step pattern in which the screen percentage was changed stepwise, and using the following developing solution and fixing solution, an automatic developing machine GR-
27 (manufactured by Konica Corporation) under the following processing conditions.

(Developer formulation) (Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-methylbenzotriazole 200 ml 1-phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount for adjusting the pH of the working solution to 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg The above composition A and composition B in 500 ml of water when using a developer.
, And finished to 1 liter to obtain a working solution. p
H was 10.4. The replenishment amount of the developer is 150 ml
/ M ² .

[Formulation of Fixing Solution] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g acetic acid (90% W / W aqueous solution) 8.1 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% W / W aqueous solution) 5.8 g aluminum sulfate (content in terms of Al ₂ O ₃ is 8.1) 26.5 g of the above composition A and composition B in 500 ml of water when using a fixing solution.
, And finished to 1 liter to obtain a working solution. The pH of the fixing solution was about 4.3. 400m refill
1 / m ² .

(Development processing conditions) Process temperature Time Tank capacity Development 34 ° C. 15 seconds 3 liters Fixing 34 ° C. 15 seconds 2 liters Water washing Room temperature 10 seconds 2 liters Drying 40 ° C. 10 seconds Each process time is a so-called wading transfer time to the next process. Including.

The obtained sample was used as an optical densitometer Konica PDA-
The sensitivity was measured using 65 [manufactured by Konica Corporation].

At this time, the relative value of the laser intensity reproduced at the halftone dot 50% where the halftone dot 50% was set was expressed as the sensitivity (S50). The halftone dot reproducibility in the table is evaluated at halftone dots at 5% and 95%, and the value is 5% each.
% And closer to 95%, the more preferable the dot reproducibility is. The practical density in the table is the density of a 100% halftone dot portion in the exposure amount when 50% halftone dots are reproduced, and the higher the value, the better. The term "dye stain" in the table means that each film sample was treated with the above-mentioned fixing solution, and the dye stain degree of the obtained sample was visually evaluated on a five-point scale. The larger the value is, the less the stain is and the clearer the sample is.

The above results are shown in Table 1 below.

[0229]

[Table 1]

As is clear from the table, when processed with a developer having a pH of 10.4, the sample according to the present invention had high sensitivity, high density, and excellent dot reproducibility. Further, a clear image was obtained in which the amount of dye contamination was very small as compared with the comparison.

[0231]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and high density, which has little residual color contamination by a dye and excellent dot reproducibility, can be obtained. Further, a processing method capable of obtaining the above-described performance even when low replenishment processing was performed with a relatively low pH developer was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/29 501 G03C 5/29 501 5/31 5/31 // C07D 235/20 C07D 235/20

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer has the following general formula (I): A silver halide photographic material comprising at least one compound represented by formula (II) and at least one compound represented by formula (II) below. Embedded image In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a substituted or unsubstituted aliphatic group, and at least one of R ₂ and R ₄ substitutes for a water solubilizing group. _{V 1, V 2, V 3} , V 4, V 5, V 6, V
₇ and V ₈ each represent a hydrogen atom or a substituent, and V ₁ and V ₂ , V ₂ and V ₃ , V ₃ and V ₄ , V ₅ and V ₆ , V ₆ and V _7, and V ₇
And V ₈ may each form a fused ring. However, V ₁
~V ₄ and V ₅ ~V ₈ are each the sum of the Hammett σp value obtained by adding is larger substituent than 0.12. L ₁ ,
L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group. M ¹ represents an ion necessary for neutralizing the charge in the molecule, and ¹ represents the number of ions required for neutralizing the valence in the molecule. Embedded image In the formula, Y ₁ , Y ₂ and Y ₃ are each independently a —N (R) — group,
Represents an oxygen atom, a sulfur atom or a selenium atom, and R ₅ represents an aliphatic group having 10 or less carbon atoms substituted with a water solubilizing group;
R, R ₆ and R ₇ each represent an aliphatic group, an aryl group or a heterocyclic group, and at least two of R, R ₆ and R ₇ substitute a water-solubilizing group. . V ₉ and V ₁₀ may be each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or V ₉ and V ₁₀ to form a ring, and L ₆ and L ₇
Represents a methine group. M ² represents an ion necessary to neutralize the charge in the molecule, and m represents the number of ions required to neutralize the valence in the molecule. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, wherein the silver halide emulsion layer has the above-mentioned formula (I). Containing at least one compound represented by formula (II) and at least one compound represented by formula (II),
A silver halide photographic light-sensitive material characterized in that the silver halide emulsion layer or the hydrophilic colloid layer contains at least one hydrazine derivative and / or quaternary onium salt. 3. A replenishing amount of a developing solution after exposing the silver halide photographic light-sensitive material according to claim 2 is 40 to 200 ml / m.
^{2. A method} for processing a silver halide photographic light-sensitive material, wherein the processing is performed in 2. 4. The method for processing a silver halide photographic material according to claim 3, wherein the processing is carried out at a developer pH of 9.0 to 11.0.