JPH10301223A - Silver halide photographic sensitive material and developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material for manufacturing a printing plate high in sensitivity and γ value, free from occurrence of black spots and variation of dots due to fluctuation of sensitivity is storage by incorporating a combination of 2 kinds of specified sensitizing dyes in a silver halide emulsion layer. SOLUTION: This silver halide photographic sensitive material is provided on a support with a gelatine undercoat layer, the silver halide emulsion layer and a hydrophilic colloidal layer and this emulsion layer contains the 2 kinds of sensitizing dyes different from each other in the proportion of Y<1> , Y<2> , and Y<3> represented by the formula in which each of Y<1> -Y<3> is, independently, a -N(R)- group or an O atom or the like; each of one of R and R1 -R3 is, independently, an H atom or an aliphatic or aryl group or the like and one of R and R1 -R3 is a water-soluble group; each of V<1> and V<2> is an H atom or an alkyl group or the like; each of L<1> -L<4> is, independently, and optionally substituted methine group; (n) is 1 or 2; (m) is 0 or 1; M<1> is an ion necessary to cancel the total charge in the molecule; and (n) is a number necessary to cancel the charge.

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, and more particularly to a silver halide photographic light-sensitive material for printing plate making and a development processing method thereof.

[0002]

2. Description of the Related Art In recent years, in the market for printing plate making scanners and imagesetters, a screening method for forming an image with smaller halftone dots than before, such as high definition and FM screening, has begun to spread. For such a screening method, a super-high contrast type photographic material in which the density of small points is easy to be applied is preferable, and further improvement is desired.

[0003] In photosensitive materials for printing plate making, many photographic techniques have been proposed for obtaining an image with a super-high contrast.
For example, U.S. Pat. No. 4,269,929 discloses a silver halide photographic light-sensitive material containing a hydrazine derivative, and JP-A-4-98239 discloses a silver halide photographic light-sensitive material containing a nucleation accelerator. It has been disclosed.

[0004] However, while these prior arts provide high contrast, they have a serious drawback in that spot-like failures, which are called "black spots" and occur in unexposed areas after development processing, are likely to occur.

Further, in the prior art, there is a problem that the sensitivity of the photosensitive material greatly fluctuates due to storage, and the% of halftone dots is not constant. Particularly, in a method such as recent high-definition or FM screening, a large change in sensitivity is a fatal defect because a minute halftone dot is used. Therefore, the change in sensitivity during storage is small, and black spots are not generated. A light-sensitive material free of generation has been strongly desired.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for printing plate making which has high sensitivity, high gamma, no black spots, and no halftone dot fluctuation due to sensitivity fluctuation during storage. Another object of the present invention is to provide a silver halide photographic light-sensitive material for printing plate making having such performance and suitable for high definition and FM screening, and an image forming method thereof.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be solved by the following.

(1) A silver halide photographic material comprising a gelatin subbing layer on a support, at least one silver halide emulsion layer and a hydrophilic colloid layer,
A sensitizing dye represented by the following general formula [S], wherein at least two sensitizing dyes having different combinations of Y ¹ , Y ² and Y ³ are used in combination in the silver halide emulsion layer. Silver halide photographic material.

[0009]

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Wherein Y ¹ , Y ² and Y ³ are each independently-
Represents an N (R)-group, an oxygen atom, a sulfur atom or a selenium atom. However, the case where Y ¹ , Y ² and Y ³ are composed of only a sulfur atom and a selenium atom is excluded. R, R ¹ , R ² and R ³ each represent an aliphatic group, an aryl group or a heterocyclic group, and at least one of R, R ¹ , R ² and R ³ replaces a water-soluble group.

V¹And V^TwoRepresents a hydrogen atom, an alkyl group,
Alkoxy group, aryl group or V¹And V^TwoCombine with
A group forming a condensed ring together with an azole ring;¹,
L^Two, L ^ThreeAnd L^FourAre independently substituted or unsubstituted
Represents tin carbon.

N represents 1 or 2, and m represents 0 or 1.

M ¹ represents an ion necessary to offset the total charge of the molecule, and n ¹ represents a number required to neutralize the charge of the molecule.

(2) Core / shell type silver halide grains wherein the silver halide grains contained in the silver halide emulsion layer coated on the silver halide photographic light-sensitive material have a laminated structure of two or more layers. And core / shell type silver halide grains in which at least one metal compound containing Rh, Re, Ru or Os is present in a higher content in the innermost core than in the outer shell. The silver halide photographic light-sensitive material according to the above (1), which is characterized in that:

(3) The silver halide photographic material as described in (1) or (2) above, wherein the metal compound contained in the silver halide grains is a compound containing Rh.

(4) The silver halide photographic light-sensitive material as described in any one of (1) to (3) above, wherein a hydrazine derivative is contained in the silver halide photographic light-sensitive material constituting layer.

(5) After exposing the silver halide photographic light-sensitive material, at least when developing, fixing and washing with an automatic developing apparatus, at least one replenishing amount selected from a developing solution and a fixing solution is halogen. The method for developing a silver halide photographic material according to any one of the above (1) to (4), wherein the amount is 75 to 250 ml per square meter of the silver halide photographic material.

(6) After the silver halide photographic light-sensitive material is exposed, it is developed using a developing solution, a fixing solution, a washing water, or a stabilizing solution and processed by an automatic developing machine to form an image. The above (1) to (1), wherein the total processing time from the insertion of the tip of the silver halide photographic light-sensitive material into the automatic developing machine until it comes out of the drying zone is 10 to 60 seconds.
The method for developing a silver halide photographic material according to any one of (4) and (4).

(7) The total processing time from when the leading end of the silver halide photographic light-sensitive material to be processed is inserted into the automatic developing machine until it comes out of the drying zone is 10 to 60 seconds. The method for developing a silver halide photographic light-sensitive material according to the above (5).

It has been found that these can solve the problem.

Hereinafter, the present invention will be described specifically.

First, the sensitizing dye represented by the general formula [S] used in the present invention will be described.

In the compound represented by the general formula [S] used in the present invention, Y ¹ , Y ² and Y ³ each independently represent-
Represents an N (R)-group, an oxygen atom, a sulfur atom or a selenium atom.

R, R ¹ , R ² and R ³ have at least one water-soluble group. Specifically, for example, a sulfo group,
Examples include acid groups such as a carboxy group, a phosphono group, a sulfate group, a sulfino group, a sulfonamide group, and a sulfamoyl group. The number of water-soluble groups is preferably two or more, and more preferably three or more.

The aliphatic group represented by R, R ¹ , R ² and R ³ is, for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, n-propyl, n-alkyl).
Each group such as -pentyl and isobutyl), an alkenyl group having 3 to 10 atoms (for example, each group such as 3-butenyl and 2-propenyl) or an aralkyl group having 3 to 10 carbon atoms (for example, benzyl and phenethyl) Etc.).

The aryl group represented by R, R ¹ , R ² and R ³ includes, for example, a phenyl group, and the heterocyclic group includes, for example, a pyridyl group (2-, 4-) and a furyl group (2
-), Thienyl group (2-), sulfolanyl group, tetrahydrofuryl group, piperidinyl group and the like.

Each of R, R ¹ , R ² and R ³ 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 carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, p Specific examples of the aryl group substituted with a water-solubilizing group include each group such as -carboxybenzyl and the like, and examples thereof include a p-sulfophenyl group and a p-carboxyphenyl group, each of which is substituted with a water-solubilizing group. Specific examples of the heterocyclic group include 4-sulfothienyl groups, 5-carboxypyridyl groups and the like.

As the alkyl group represented by V ¹ and V ² , a linear or branched group (eg, methyl, ethyl, iso
-Propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.). Examples of the alkoxy group represented by V ¹ and V ² include, for example, methoxy, ethoxy, propoxy and the like.

The aryl group represented by V ¹ and V ² may have a substituent at any position, and examples thereof include phenyl, p-tolyl, p-hydroxyphenyl and p-methoxyphenyl. Groups. Examples of the condensed ring formed by V ¹ and V ² together with an azole ring 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] condensed ring such as selenazole.

Specific examples of the alkoxy groups represented by V ¹ and V ² include, for example, unsubstituted alkyl groups such as methoxy, ethoxy, butoxy, 2-methoxyethoxy,
Examples include alkoxy groups such as a benzyloxy group.

The above-mentioned substituents represented by V ¹ and V ² , and the formed condensed ring may have a substituent at any 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 for 2-methoxyethoxy, benzyloxy, etc.), alkylthio group (for example, methylthio, ethoxy) A substituted / unsubstituted alkyl group such as an ethylthio group, a hydroxy group, a cyano group, and an aryloxy group (eg, a substituted group such as phenoxy and tolyloxy;
An unsubstituted group) or an aryl group (e.g., phenyl,
substituted or unsubstituted groups such as p-chlorophenyl), styryl groups, heterocyclic groups (for example, groups such as furyl and thienyl),
A carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl), a sulfamoyl group (for example, each group such as sulfamoyl, N, N-dimethylsulfamoyl), and an acylamino group (for example, acetylamino, propionylamino, and benzoylamino) Each group), an acyl group (for example, each group such as acetyl and benzoyl), an alkoxycarbonyl group (for example, a group such as ethoxycarbonyl), a sulfonamide group (for example, each group such as methanesulfonylamide and benzenesulfonamide), and a sulfonyl group ( For example, any groups such as methanesulfonyl, p-toluenesulfonyl, etc.) and carboxy groups.

Examples of the group substituted by the methine carbon represented by L ¹ , L ² , L ³ and L ⁴ include a lower alkyl group (eg, each group such as methyl and ethyl) and a phenyl group (eg, phenyl, carboxy). Groups such as phenyl) and alkoxy groups (for example, groups such as methoxy and ethoxy).

N represents 1 or 2, and m represents 0 or 1. M ¹ represents a cation or an acid anion,
Specific examples of the cation 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 For example, halogen ions (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like can be mentioned. n ¹ is
It is 0 when the charge is neutralized by forming an inner salt.

In the above formula [S], it is preferred that R ¹ is an alkyl group substituted with a sulfo group, and at least two of R, R ² and R ³ are each a carboxymethyl group. .

Specific examples of the sensitizing dye represented by the general formula [S] are shown below.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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The compounds of the present invention are described, for example, in F. M. Reference is made to a conventionally known method described in Hama, "Cyanine Soybeans and Rated Compounds" (1964, published by Interscience Publishers), U.S. Pat. Nos. 2,454,629 and 2,493,748. And can be easily synthesized.

In the present invention, the silver halide emulsion contains
A sensitizing dye represented by the general formula [S], wherein Y ¹ ,
By using at least two kinds of sensitizing dyes having different combinations of Y ² and Y ³ , compared with the case of using only one kind of sensitizing dye, the sensitizing property is not impaired, and the photographic characteristics change during storage and It has been found that the residual color can be improved at the same time.

In the combination of the sensitizing dyes represented by the general formula [S], one of the sensitizing dyes Y ¹ is -N (R)-
Or a combination of a sensitizing dye of an oxygen atom and ^{one in} which Y ¹ of the other sensitizing dye is a sulfur atom or a selenium atom,
More preferably, it is used in combination with a sensitizing dye in which ^one Y ¹ is an oxygen atom and the other Y ¹ is a sulfur atom.

The weight ratio of the combination of at least two sensitizing dyes is in the range of 0.1 to 0.9, preferably 0.3 to 0.7, and more preferably 0.4 to 0.9.
0.6.

The total amount of at least two sensitizing dyes according to the present invention varies greatly depending on the conditions used and the type of emulsion, but is preferably 1 to 1 mol per mol of silver halide.
× 10 ^{-6 to} 5 × 10 ^-3 mol, more preferably 2 × 10 ^-6
２2 × 10 ⁻³ mol.

The silver halide photographic light-sensitive material of the present invention contains R
Metal compounds containing h, Re, Ru or Os can be used, and are disclosed in JP-A-63-2042 and JP-A-1-285.
It is preferably added in the form of a water-soluble complex salt described in Nos. 941, 2-20852, 2-20855 and the like. Particularly preferred are the six-coordinate complexes shown below.

[ML ⁶ ] ^-n (wherein M represents Rh, Re, Ru or Os, L represents a bridging ligand, and -n represents 0, 1, 2 or 3). The counter ion is not important, and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl, thionitrosyl ligands and the like.

Next, specific examples of the complex used in the present invention will be shown. These metal complexes can be powdered or NaCl or KC
It is desirable to add it to the halogen solution during the formation of the particles by dissolving together with 1).

[RhCl ₆ ] ^-3 , [RhCl ₅ (H
₂ O)] ^-2 , [RhBr ₅ (NO)] ^-2 , [RhCl
₅ (NS)] ^-2 , [RhCl ₄ (NO) (CN)] ⁻¹ ,
[RhCl ₄ (NO) (CN) ₄ ] ^-2 , [ReC
l ₆ ] ^-3 , [ReBr ₆ ] ^-3 , [ReCl ₅ (N
O)] ^-2 , [Re (NS) Br ₃ ] ^-2 , [Re (NO)
(CN) ₃ ] ^-2 , [RuCl ₆ ] ^-3 , [RuCl ₄ (H
₂ O) ₂ ] ^-1 , [RuCl ₅ (NO)] ^-2 , [RuBr
₅ (NS)] ^-2 , [OsCl ₆ ] ^-3 , [Os (NO) (C
N) ₃ ] ^-2 , [Os (NS) Br 5] ^-2 The silver halide grains used in the present invention may be doped with another heavy metal salt to increase the sensitivity. Especially K ₃ IrC
Doping with Ir salt or Fe salt such as l ₆ , K ₄ [Fe (CN) ₆ ] is advantageously performed.

Next, the core / shell type emulsion having a laminated structure used in the present invention will be described.

The laminated structure may have two to ten layers.
Further, two or more layers and five or less layers are preferable. The laminated structure is distinguished from the laminated structure by a difference in the content of a metal compound selected from Rh, Re, Ru, and Os. The content of the metal compound forming this layer was 1 × with respect to 1 mol of silver.
The range of 10 ^-9 to 1 × 10 ^-5 mol is preferable for achieving the effects of the present invention, and the range of 1 × 10 ^-8 to 1 × 10 ^-6 mol is more preferable. Of these metals, Rh compounds are most preferred in the present invention. These metal compounds may be used in combination of two or more. The content ratio of the metal compound is such that the ratio of the content of the innermost core: the content of the outer shell is 1: 1 to 10
0: 1, more preferably 1: 1 to 20: 1.

Next, the core / shell type silver halide grains having a laminated structure used in the present invention will be described. The silver halide composition may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride. The halogenated grains may be of any crystal type, for example, may be a single crystal such as a cubic, octahedral, or tetrahedral, or may be polytwin grains having various shapes. Good.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. Monodisperse here means, when the average particle diameter is measured by an ordinary method,
Silver halide grains in which at least 95% of the grains by number or weight are within ± 40%, preferably within ± 30% of the average grain size.

The crystal structure of silver halide may have a different silver halide composition between the inside and the outside. For example, a high silver iodide core portion is coated with a low silver iodide shell layer to form a clear multilayer. It may be a core / shell type monodispersed emulsion having a structure.

The method for producing the above-mentioned core / shell type emulsion is known. Photo. Sci, 24.198. (1
976), U.S. Pat. Nos. 2,592,250 and 3,50
5,068, 4,210,450, 4,44
4,877 or JP-A-60-143331 can be referred to.

The method for producing the above-mentioned monodispersed emulsion is well known. Photo. Sci, 12.242-251, (19
63), JP-A-48-36890, and JP-A-52-1636.
No. 4, No. 55-142329, No. 58-49938
No. 1,413,748, U.S. Pat.
No. 4,628, 3,655,394 and the like.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is prepared by, for example, using a seed crystal as a method for obtaining the above-mentioned monodisperse emulsion and supplying silver ions and halide ions using the seed crystal as a growth nucleus. An emulsion that has been grown may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain diameter / grain thickness) of 3 or more.

Next, in the present invention, as the hydrazine derivative, a compound represented by the following general formula [H] is preferably used.

[0065]

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In the formula, A is an aryl group, or a sulfur atom or
Represents a heterocyclic ring containing at least one oxygen atom, and G is-
(CO)_nGroup, sulfonyl group, sulfoxy group, -P
(= O) R_TwoA group or an iminomethylene group, wherein n is
Represents an integer of 1 or 2;₁, A _TwoAre both hydrogen atoms
Is an alkyl in which one is a hydrogen atom and the other is a substituted or unsubstituted
Rusulfonyl group or a substituted or unsubstituted acyl group
R represents a hydrogen atom, each of which is a substituted or unsubstituted alkyl.
Group, alkenyl group, aryl group, alkoxy group,
Kenyloxy group, aryloxy group, heterocyclic oxy
Group, amino group, carbamoyl group, or oxycarbonyl
Represents a group. R_TwoIs a substituted or unsubstituted alkyl
Group, alkenyl group, alkynyl group, aryl group, alk
Xy, alkenyloxy, alkynyloxy, a
Represents a reeloxy group, an amino group or the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0068]

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In the formula, R ¹ represents 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, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the ballast group, ballast groups (diffusion preventing groups) commonly used in immobile photographic additives such as couplers
The ballast group includes, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group and an alkylphenoxy group which are relatively inert to photographic properties having 8 or more carbon atoms.

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], X represents a group that can be substituted for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, Xs may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and preferably both are 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, preferably a carbonyl group.

In the formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵⁾ groups (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group,
R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

A more preferred R ² is an alkyl group. R ² is preferably a substituted alkyl group, more preferably a substituted methyl group, and most preferably a tri-substituted methyl group. Specific examples of the substituent include alkoxy, aryloxy, heterocyclic oxy, mercapto, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, heterocyclic sulfonyl, acyl, cyano, chlorine, bromine, fluorine, nitro, alkoxy Carbonyl, aryloxycarbonyl, carboxyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl, amino, alkylamino, arylamino, acylamino, alkoxycarbonylamino,
Examples include groups such as aryloxycarbonylamino, acyloxy, alkylaminocarbonyloxy, arylaminocarbonyloxy, sulfo, sulfamoyl, arylsulfamoyl, and alkylsulfamoyl.
Preferred are chlorine, bromine and fluorine, and more preferred is fluorine.

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

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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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 used in the present invention is
It can be synthesized by a known method, for example, by the method described in US Pat. No. 5,229,248, column 59 to column 80.

The hydrazine derivative used in the present invention can be used in any layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. The amount of addition may be an amount which makes the contrast high (the amount of the contrast enhancement), and the optimum amount 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. In general, the range of 10 ^-6 to 10 ^-1 mol per mol of silver halide is preferable, and the range of 10 ^-4 to 10 ^-1 mol is particularly preferable.

In the present invention, in order to effectively promote the contrast enhancement by the hydrazine compound, the following general formula [N
It is preferable to use a nucleation accelerator represented by a), [Nb] or [Nc].

[0088]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ 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 adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorbing group in the molecule.

Specific examples of the nucleation accelerator [Na] will be described below.

[0092]

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[0093]

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[0094]

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[0095]

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Next, in the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group,
Ar and R ₁₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific examples of the nucleation accelerator [Nb] will be described below.

[0098]

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[0099]

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Next, in the general formula [Nc], Q represents an N or P atom, and R _{21 to} R ₂₃ represent a hydrogen atom or a substitutable group. L represents an m-valent organic group. R _{21 to} R ₂₃ and L
May have a plurality of groups bonded to each other to form a ring. m represents an integer of 1 to 5. X represents an n-valent anion. n represents an integer of 1 to 5. X may be linked to L.

Specific examples of the displaceable group represented by R _{21 to} R ₂₃ include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group). Group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group) Etc.), alkoxy groups (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy groups (eg, phenoxy group, etc.), cyano groups, acylamino groups (eg, acetylamino group, propionylamino group, etc.) An alkylthio group (eg, a methylthio group, an ethylthio group, an n-butylthio group, etc.), Reelthio group (eg, phenylthio group), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido) Group), a sulfamoylamino group (such as a dimethylsulfamoylamino group), a carbamoyl group (for example, a methylcarbamoyl group,
Ethylcarbamoyl group, dimethylcarbamoyl group, etc.),
Sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methane Sulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (for example, acetyl group, propanoyl group,
Butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group, imide group (eg, phthalimide group), heterocyclic group (eg, pyridyl group, benzimidazolyl group, benzothiazolyl group) Benzoxazolyl group). These groups may be further substituted with the groups described above. In addition to alkylene groups described above as examples of the group represented by L, an _{arylene, -SO 2 -, - SO -} , - O-,
—S—, —N (R ₅ ) — (R ₅ is a hydrogen atom, an alkyl group,
M represents an aryl group) alone or in combination. m is preferably 1 or 2, and particularly preferably 2. When Q is a P atom, R _{21 to} R ₂₃ are preferably an aryl group,
Particularly preferred is a phenyl group. L is preferably a phenyl group or an alkylene group. When Q is an N atom, R _{21 to} R ₂₃ and L preferably form a ring by bonding a plurality of groups to each other, and the formed ring is preferably a pyridine ring. Examples of the anion represented by X include chloride ion, bromine ion, iodine ion, acetate ion, oxalate ion, fumarate ion, benzoate ion, toluene sulfonate ion, methane sulfonate ion, benzene sulfonate ion, sulfate ion, and perchloric acid. Ions, carbonate ions, nitrate ions and the like.

Specific examples of the nucleation accelerator [Nc] will be described below.

[0103]

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[0104]

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Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258751.
No. 51 (3-1) to (3-6).

The nucleation accelerator used in the present invention can be used in any layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. . The optimum amount to be added depends 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 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

Next, the redox compound that can be used in the present invention will be described.

The redox compound has, as a redox group, hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones, α-aminoketones and the like.
Preferred redox compounds are -NH as a redox group.
A compound having an NH- group and the following general formula [7],
[8],

A compound represented by [9], [10], [11] or [12].

[0109]

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[0110]

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The general formulas [7], [8],

[9], [1
[0], [11] or [12], R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. R ₅ to R ₉ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r
₁ , r ₂ and r ₃ represent a substituent capable of substituting on a benzene ring. X ₁ and X ₂ represent O or NH. Z ₁ represents an atom group necessary for constituting a 5- to 6-membered heterocyclic ring. W is N
(R ₁₀ ) represents R ₁₁ or OH, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. CO
UP represents a coupler residue capable of causing a coupling reaction with an oxidized form of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group. m ₁ and p ₁ represent an integer of 0 to 3. q ₁ is an integer of 0 to 4. n represents 0 or 1. PUG represents a development inhibitor.

The general formulas [7], [8],

[9], [1
0], [11] or [12], R ₁ and R _{5 to} R
Preferred examples of the alkyl group, aryl group, and heterocyclic group represented by ₁₁ include a methyl group, a p-methoxyphenyl group, and a pyridyl group. Of the acyl groups represented by R ₂ and R ₃ , a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, preferably an acyl group, A carbamoyl group and a cyano group.
The total number of carbon atoms in these groups is preferably 1 to 20. R _{1 to} R ₁₁ may further have a substituent, for example, a halogen atom (a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group) , A methoxymethyl group,
Trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p -Tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), cyano group, acylamino group (eg, acetylamino group) , Propionylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (eg, phenylthio group, etc.),
Sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (Dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group ( For example, methoxycarbonyl group, ethoxycarbonyl group, etc., aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group) , Propanoyl group, butyroyl group, etc.), amino group (eg, methylamino group, ethylamino group, dimethylamino group, etc.), hydroxyl group, nitro group, imide group (eg, phthalimido group, etc.), heterocyclic group (eg, pyridyl group) , Benzimidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.). The following can be mentioned as the coupler residue represented by COUP.

Examples of the cyan coupler residue include a phenol coupler and a naphthol coupler. Examples of the magenta coupler include a 5-pyrazolone coupler, a pyrazolone coupler, a cyanoacetylcoumarone coupler, an open-chain acylacetonitrile coupler, and an indazolone coupler.
Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. Non-colored coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic diester, imidazolinone, oxazolinone, thiazolinone, etc.).
Further, among the coupler residues represented by COUP, those preferably used in the present invention are represented by the following general formula (Coup)
-1) to general formula (Coup-8).

[0114]

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In the formula, R ₁₆ represents an acylamide group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups. .

[0116]

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In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamide group, an alkoxycarbonylamide group, a sulfoureido group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₀ and R ₂₁ each represent an aliphatic group. Represents an aromatic group, an aromatic group or a heterocyclic group. One of R ₂₀ and R ₂₁ may be a hydrogen atom. a is an integer of 1 to 4, b
Represents an integer of 0 to 5. When a and b are plural, R ₁₈ may be the same or different, and R ₁₉ may be the same or different.

[0118]

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In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group,
Represents an alkoxy group, a halogen atom or a sulfonamide group.

[0120]

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In the formula, R ₂₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group,
A diacylamino group and R ₂₆ represent a hydrogen atom, a halogen atom, or a nitro group.

[0122]

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R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The general formulas [7], [8],

[9], [1
0], [11] or [12], the 5- or 6-membered heterocyclic ring represented by Z ₁ may be a single ring or a condensed ring,
5 having at least one of O, S, and N atoms in a ring
And a 6-membered heterocyclic ring. These rings may have a substituent, and specific examples include the aforementioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
No. 23 or 3,674,478, Research
Disclosure 21228 (December 1981)
) Or JP-A-57-56837, JP-A-4-43
No. 8 and the like.

Preferred development inhibitors as PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336
No. 50 or 61-11743.

Next, general formulas [7] to
Specific examples of the compound represented by [12] are listed, but the present invention is not limited thereto.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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The compounds represented by the general formulas [7] to [12] are used in an amount of from 1 × 10 ^-6 mol to 5 ×
It is preferably contained in an amount of 10 ^-2 mol, particularly preferably from 1 x 10 ^-4 mol to 2 x 10 ^-2 mol.

The redox compound can be present in the silver halide emulsion layer, in a layer adjacent to the emulsion layer, or in another layer via the adjacent layer. Particularly preferred is an emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer. Most preferably, a hydrophilic colloid layer is provided between the emulsion layer and the emulsion layer closest to the support, and the hydrophilic colloid layer is added to the hydrophilic colloid layer.
Further, the redox compound may be contained in a plurality of different layers.

The light-sensitive material used in the present invention is most effectively used as an output light-sensitive material, and the light source is typically an Ar laser, a HeNe laser, a red laser diode, an infrared semiconductor laser, or a red LED laser. However, any other laser such as a blue laser such as a HeCd laser can be used. The effects of the present invention are not limited to laser output light-sensitive materials, but are also effective in applications such as shooting light-sensitive materials and return light-sensitive materials.

In the present invention, generally known sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization may be appropriately selected and used in combination. Further, the chemical sensitization may not be performed. As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfate,
Thioureas, rhodanines, polysulfide compounds and the like can be used.

In the present invention, the silver halide composition in the silver halide emulsion may be pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, or chloroiodide containing 60 mol% or more of silver chloride. Preferably, it is silver bromide. 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. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and 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. By James: The the
ory of the photographic p
process, 3rd edition, 36-43 (1966 Mc
Millan).

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.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any 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. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are formed in at least one of the steps of forming or growing the grains, such as cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, rhodium salts, ruthenium salts. It is preferable to add a complex salt containing an element from Groups 3 to 13 of the periodic table, such as an osmium salt, an iron salt, a copper salt, a platinum salt, and a palladium salt. As a ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used. 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.

For details of the silver halide emulsion and its preparation method, see RD17643, pp. 22-23 (197)
(December 2008) or in the literature cited.

In the silver halide photographic light-sensitive material of the present invention,
The silver content of the silver halide emulsion layer is preferably 2.0 g / m ² or more and 3.5 g / m ² or less, more preferably 2.5 g / m ² or more and 3.5 g / m ² or less. When the silver content is high, the running stability is poor, and when the silver content is low, a sufficient density cannot be obtained.

The light-sensitive material according to 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, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazain Denes, tetrazaindenes (especially 4-
Hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes and the like; antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like Many compounds known as can be added. 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.

The photographic emulsion and the non-photosensitive hydrophilic colloid used in 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 (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,3,5-triacryloyl) -Hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis-
[Β- (vinylsulfonyl) propionamide] and the like),
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid and phenoxymucochloric acid) isoxazoles, dialdehyde starch, and 2-chloro-6-hydroxytriazine Nylated gelatin, isocyanates, carboxyl group activated hardeners and the like can be used alone or in combination.

The light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsifying dispersion, an adhesion preventing agent and a photographic material. Various known surfactants may be used for various purposes such as property improvement.

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As gelatin, acid-processed gelatin may be used in addition to lime-processed gelatin, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, an amide group, etc., and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, an —NR group. ₁ NR ₂ -R ₃ (R ₁ , R ₂ and R ₃ 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,
Carbamoyl group, amino group, sulfonyl group, sulfoxy group, iminomethylene group, alkenyl group, alkynyl group,
An arbitrary group bonded through an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, etc.), a cation 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 photosensitive material of the present invention contains various other additives. For example, desensitizers, plasticizers, slip agents,
Development accelerators, oils, colloidal silica and the like can be mentioned.

As these additives and the above-mentioned additives, those described in RD17643 (supra), pages 22 to 31, and the like can be used.

The silver halide photographic light-sensitive material of the present invention has a layer constitution comprising at least two layers of a silver halide emulsion layer and a hydrophilic colloid layer. 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 one side or both sides with respect to 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, a 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.

As the developing agent which can be used in the image forming method of the silver halide photographic light-sensitive material of the present invention, dihydroxybenzenes (for example, hydroquinone,
Chlorhydroquinone, bromohydroquinone, 2,3
-Dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 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., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-amino) Phenol, N-methyl-p-aminophenol, 2,4
-Diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-
Aminopyrazoline, etc.), transition metal complex salts (Ti, V, C
A complex salt of a transition metal such as r, Mn, Fe, Co, Ni, Cu, etc. These may be in any form having a reducing power in order to be used as a developer. For example, Ti ³⁺ , V ²⁺ , Cr ²⁺ , F
e2 ^{+ and the} like, and as ligands, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof;
Phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid, and salts thereof, and the like. And the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid; It is preferable to use a combination of an aminophenol and ascorbic acid, a combination of a 3-pyrazolidone and a transition metal complex, or a combination of an aminophenol and a transition metal complex. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

In the present invention, silver sludge inhibitors are disclosed in JP-B-62-4702, JP-A-3-51844,
4-26838, 4-362942, 1-3
19031 and the like.

The developing waste liquid can be regenerated by energizing. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material of the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

The sulfite and metabisulfite used as a preservative in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / 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 to 12.0, and particularly preferably adjusted to 9.0 to 10.9.

The developer used in the image forming method for a silver halide photographic light-sensitive material of the present invention may not substantially contain a dihydroxybenzene compound. in this case,
It is preferable to contain a compound represented by the following general formula (A).

[0162]

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[0163] Each R _1, R ₂ in the general formula (A) represents independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, R _1, R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X represents -CO-
Or a -CS- group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Among the compounds represented by the general formula (A), a compound represented by the following general formula (Aa) wherein R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0165]

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In the above formula (Aa), R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group. , A sulfo group, a carboxy group, an amide group, or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Examples of the substituent of the alkyl group include a halogen atom (eg, Cl, Br and the like), a hydroxy group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl and naphthyl group), and a heterocyclic group (eg, 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 and the like), a hydroxy group, an aryl group having 6 to 20 carbon atoms (for example, a phenyl group and a naphthyl group), a C1 to C20 group and the like. 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 (for example, Cl and Br), a hydroxy group, an aryl group having 6 to 20 carbon atoms (for example, 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.), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (eg, allyloxy group, etc.), carbon 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, heptylamino, propionylamino, etc.) and amino (e.g., amino, methylamino, dimethylamino, dibenzylamino, etc.).

Examples of the substituents of the above-mentioned 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.

Next, the formula (A) or the formula (A-
Examples of the compound represented by a) are shown below, but the present invention is not limited thereto.

Formula (A)

[0175]

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[0176]

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Formula (Aa)

[0178]

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[0179]

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[0180]

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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, development substantially free of hydroquinones (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate, etc.) is carried out. Liquid can be used. The term "substantially not contained" means an amount of less than 0.01 mol per liter of the developer.

In the present invention, a developing agent comprising the transition metal complex according to the present invention and a 3-pyrazolidone (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 such as 3-pyrazolidones and aminophenols are usually used in an amount of 0.01 to 1.4 per liter of developer.
It is preferably used in molar amounts.

The inhibitor which can be used in the image forming method for a silver halide photographic light-sensitive material of the present invention refers to a compound having a mercapto group or a monocyclic or condensed heterocyclic compound. A monocyclic or fused heterocyclic compound having a mercapto group is also an inhibitor in the present invention.

Specific examples are shown below, but the compounds of the present invention are not limited to the following. Specifically, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, an imidazole compound,
Benzimidazole compounds, pyrazole compounds, indazole compounds, triazole compounds, benzotriazole compounds, tetrazole compounds, pyrimidine compounds, triazine compounds, quinoline compounds, quinarizone compounds,
Purine compounds and the like can be mentioned, and all compounds may have a substituent and a mercapto group. Substituents include a methyl group, a sulfo group, a nitro group, an amino group, a carboxy group,
Examples thereof include a hydroxy group, a phenyl group, and a halogen atom, but are not limited thereto. The amount of the inhibitor is usually 0.3 to 1.5 g, more preferably 0.3 to 0.75 g per liter.

In the method for forming an image of a silver halide photographic light-sensitive material of the present invention, a silver halide anti-sludge agent is used in a developer as disclosed in
The compounds described in JP-A-281365, pages (3) to (11), may be contained.

As a special type of development processing of the light-sensitive material of the present invention, a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and is used in an activator processing solution for performing development by processing the light-sensitive material in an alkaline aqueous solution. You may. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions. In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution. 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.

As a mother liquor or a replenisher of a developing solution, a fixing solution, or a stabilizing solution, it is usual to supply a used solution or a concentrated solution diluted immediately before. The stock of the mother liquor and the replenisher may be in the form of a working solution or a concentrated solution, a viscous liquid in a semi-kneaded state having a high viscosity, or a system 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 the tablet-formed product to the dissolution layer or the direct treatment layer is a workability,
This method is extremely excellent in terms of space saving and preservation, and can be particularly preferably used.

In the development processing, the development temperature is set to 20 to 5
The temperature can be set to a normal temperature range of 0 ° C. The silver halide photographic material of the present invention is preferably processed using an automatic processor. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. The development replenishment amount and the fixing replenishment amount are 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably it is 75 to 250 ml per meter.

According to 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 preferably from 60 seconds to 60 seconds. If the time is less than 10 seconds, sufficient drying property cannot be obtained due to the problem of the performance of the automatic developing machine. The total processing time referred to here includes the total process time required for processing the black and white photosensitive material, and specifically, for example, development, fixing,
This is a time including all the times of steps such as bleaching, washing, stabilizing treatment, and drying, that is, a dry-to-dry time.

In the drying zone of the automatic developing machine, a method of drying using 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.

[0194]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsions A1 to A10) Silver chlorobromide core particles having an average particle size of 0.09 μm and comprising 70 mol% of silver chloride and 30% of silver bromide by a double jet method. Was adjusted. At the time of mixing the core particles, the metal complexes shown in Table 1 were added. In their presence, at 40 ° C., pH 3.0, silver potential (EAg) 1
While maintaining the temperature at 65 mV, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed. The EAg was reduced to 125 mV with an aqueous NaCl solution and a shell was attached to the obtained core particles using a double jet method. At that time, the metal complexes shown in Table 1 were added to the halide solution.

The emulsion thus obtained had an average particle size of 0.1
5 micron core / shell monodispersion (coefficient of variation 10%)
Silver chlorobromide emulsion (cubic crystal composed of 70 mol% of silver chloride and 30% of silver bromide).

Next, a modified gelatin described in JP-A-2-280139, page 287 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-280)
Desalting was carried out using the exemplified compound (G-8) of No. 39, page 287 (3). The EAg after desalting was 190 mV at 50 degrees.

The resulting emulsion was mixed with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 1.5 × 10 ^-3 mol per mol of silver and potassium bromide at 8.5 × 10 ³ mol.
PH 5.6 with addition of ^-4 mol and citric acid, EAg1
Adjusted to 23 mV.

Next, sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added thereto at a concentration of 5 × 10 ⁻⁴ per mole of silver and reacted, and then solid-dispersed inorganic sulfur (S8) compound (Seisin Corporation) PM-
1200) and a surfactant dispersed to an average particle size of 0.5 μm, and 1.5 × 10 ⁻⁵ mol of chloroauric acid were added thereto and chemically ripened at 55 ° C. until the maximum sensitivity was obtained. After that, at 55 ° C., 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver and 1-phenyl-5-mercaptotetrazole in 1.5 mol. × 10 ^-4 mol was added. Thereafter, the temperature was lowered to 40 ° C., and potassium iodide was further added at 5 mol / mol of silver.
After the addition of × 10 ^-3 mol, the pH was adjusted to 5.1 with citric acid, and finally, a solution obtained by dissolving the spectral sensitizing dyes shown in Table 1 by a method suitable for each dye was added.
1 to A10.

(Preparation of a silver halide photographic light-sensitive material for a printing plate-making scanner containing a hydrazine derivative) On a support, a gelatin subbing layer of the following formula 1 was prepared with a gelatin content of 0.5.
The silver halide emulsion layer of Formulation 2 was overlaid with a silver halide emulsion layer having a silver content of 3.15 g / m ² and a gelatin content of 1.15 g / m ^{2 so as} to be 5 g / m ² .
So as to 4g / m ^2, the amount of gelatin protective layer coating solution of the formulation 3 the upper layer was simultaneously coated so as to 6 g / m ² more. On the other side of the undercoat layer, a backing layer of Formulation 4 was prepared so that the amount of gelatin was 2.5 g / m ² .
On top of this, a backing protective layer of Formulation 5 was added with a gelatin content of 1.
Simultaneous multi-layer coating was performed so as to be 1 g / m ² .

Formulation 1 (Gelatin undercoat layer composition) Gelatin 0.55 g / m ² Saponin 56 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² Fungicide Z 0.5 mg / m ² Formulation 2 (Halogenated) Silver Emulsion Layer Composition) Silver halide emulsions A1 to A10 3.15 g / m ² equivalent of silver amount Hydrazine compound H-156 6 × 10 ⁻³ mol / Ag 1 mol Amino compound AM-1 14 mg / m ² Compound a 100 mg / m ² polymer latex L1 (particle size 0.25 micron) 0.9 g / m ² saponin 63 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 2.4 mg / m ² sodium naphthalene sulfonate 8 mg / m ² gallic acid n- propyl ester 50 mg / m ² mercaptopyrimidine 1 mg / m ² 2-mercapto 6-hydroxy purine ^{1mg / m 2 EDTA 50mg / m} 2 5- nitroindazole 5 mg / m ² sodium polystyrenesulfonate 15 mg / m ² Formulation 3 (Emulsion protective layer composition) Gelatin 1.6 g / m ² amino compound AM-1 14 mg / M ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² matting agent: spherical polymethyl methacrylate having an average particle size of 3.5 microns 30 mg / m ² surfactant S-1 52 mg / m ² slip agent (Silicone oil) 4 mg / m ² Compound a 50 mg / m ² Colloidal silica (average particle size 0.05 micron) 400 mg / m ² 3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h2 30 mg / m ² Sterilization agent Z 0.5 mg / m ² formulation 4 (backing layer composition) gelatin 2.5 g / m ² Sodium Iso - amyl -n- decyl sulfosuccinate 5 mg / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 micron) 100 mg / ^{m 2} sodium polystyrenesulfonate 10 mg / m ² Dye f1 65 mg / m ² dye f2 16.8 mg / m ² dye f3 95 mg / m ² hardener h3 100 mg / m ² formulation 5 (backing protective layer) gelatin 1.1 g / m ² matting agent: monodisperse poly average particle size of 5 microns Methyl methacrylate 50 mg / m ² Average particle size 3 μm Amorphous silica 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant S-1 1 mg / m ² Dye f124 .6mg / m ² dye f2 6.36mg / m ² dye f3 36 mg / m ² compound a 50 mg / m ² hardener The breakdown of 2 20 mg / m ² sodium polystyrenesulfonate 10 mg / m ² obtained sample in Table 1 below.

[0202]

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[0203]

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[0204]

[Table 1]

(Developer Composition) Diethylenetriamine pentaacetic acid / pentasodium salt 1 g per liter of working solution 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.3 g KOH was added in an amount to bring the pH of the working solution to pH 10.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per liter of working solution 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) The pH of the working solution was adjusted to 4.9 with 25 ml of sulfuric acid.

(Processing conditions) (Step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / dry 50 ° C. 30 seconds Total 100 seconds (Evaluation of sensitivity and gamma) 1.5 × with a laser sensitometer using a 633 nm He-Ne laser
The step exposure is performed while changing the light amount in 10 ^-7 seconds, and the automatic developing machine GR-27 (Konica Corporation) is used under the above developing conditions.
Manufactured). The obtained developed sample was used for PDA-
65 (Konica Digital Densitometer).

The sensitivities shown in Table 2 are as follows. 2.5 concentration of 1
Is expressed as a relative sensitivity when the sensitivity at 100 is taken as 100.
Gamma is represented by a tangent between densities of 0.1 and 3.0, and indicates that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

(Evaluation of Storage Property) A change in sensitivity due to storage (time) of the photosensitive material is evaluated.

The sample was conditioned under the conditions of 23 ° C. and 45% RH, and was placed in a 55 ° C. thermostat while maintaining the humidity control condition.
It was evaluated how much the sensitivity after 72 hours fluctuated compared to before the introduction.

(Evaluation of Black Pots) The developed samples thus obtained were visually evaluated using a 100-fold loupe, and were ranked in five stages of 5, 4, 3, 2, and 1 in ascending order of occurrence of black pots. Divided. Ranks 1 and 2 are levels that are not practically desirable.

(Evaluation of Remaining Color) Five processed samples processed under the above processing conditions were superimposed on five sheets, and the color depth of the samples was evaluated. This residual color is the sensitizing dye remaining on the film, and the lighter the color, the better. The intensity of this color is 5, 4,
The ranking was made in three stages of 3, 2, and 1. In addition, rank 1
And 2 are levels that are not practically desirable.

Table 2 shows the results of the evaluation.

[0214]

[Table 2]

As is clear from the results in Table 2, all of the samples according to the present invention can obtain high sensitivity and high gamma, and
It can be seen that there is no black spot. Also, regarding the fluctuation of sensitivity due to storage, the fluctuation width was small and excellent. Further, it is understood that the coloring of the film due to the residual color is small, and the commercial value of the sample of the present invention is greatly improved.

[0216]

According to the present invention, a silver halide photographic material for plate making having high contrast, high sensitivity, and suppressed generation of black spots can be obtained. Further, according to the present invention, a silver halide photographic light-sensitive material for printing plate making which has a small fluctuation in sensitivity due to storage and is excellent in terms of residual color and an image forming method thereof can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/26 G03C 1/26 5/26 5/26 5/29 501 5/29 501 5/31 5/31 5/395 5 / 395

Claims (7)

[Claims] In a silver halide photographic light-sensitive material comprising a gelatin subbing layer on a support, at least one silver halide emulsion layer and a hydrophilic colloid layer, the silver halide emulsion layer comprises: A sensitizing dye represented by the following general formula [S], wherein at least two sensitizing dyes having different combinations of Y ¹ , Y ² and Y ³ are used in combination. . Embedded image Wherein Y ¹ , Y ² and Y ³ are each independently —N (R) —
Represents a group, an oxygen atom, a sulfur atom or a selenium atom. However, the case where Y ¹ , Y ² and Y ³ are composed of only a sulfur atom and a selenium atom is excluded. R, R ¹ , R ² and R ³ each represent an aliphatic group, an aryl group or a heterocyclic group, and at least one of R, R ¹ , R ² and R ³ replaces a water-soluble group. V ¹ and V ² each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a group which forms a condensed ring together with an azole ring by bonding with V ¹ and V ² ;
L ¹ , L ² , L ³ and L ⁴ each independently represent a substituted or unsubstituted methine carbon. n represents 1 or 2, and m represents 0 or 1. M ¹ represents an ion necessary to offset the total charge of the molecule, and n ¹ represents a number required to neutralize the charge of the molecule. ] 2. Silver / silver halide grains contained in a silver halide emulsion layer coated on the silver halide photographic material are core / shell type silver halide grains having a laminated structure of two or more layers. Core / shell type silver halide grains in which at least one metal compound containing Rh, Re, Ru, and Os is present at a higher content in the innermost core than in the outer shell. The silver halide photographic material according to claim 1, wherein 3. The silver halide photographic material according to claim 2, wherein the metal compound contained in the silver halide grains is a compound containing Rh. 4. The silver halide photographic light-sensitive material according to claim 1, wherein said hydrazine derivative is contained in said silver halide photographic light-sensitive material constituting layer. 5. After exposing the silver halide photographic material, at least at least one replenishing amount selected from a developing solution and a fixing solution is subjected to halogenation at the time of developing, fixing and washing with an automatic developing device. Silver photographic material 1m2
The method for developing a silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the amount of the silver halide photographic material is 75 to 250 ml. 6. A halogen which is developed when a silver halide photographic light-sensitive material is exposed to light and then processed with an automatic developing machine using a developing solution, a fixing solution, a washing water or a stabilizing solution to form an image. The total processing time from when the tip of the silver halide photographic material is inserted into the automatic processor to when it comes out of the drying zone is 1
5. The method for developing a silver halide photographic light-sensitive material according to claim 1, wherein the time is from 0 to 60 seconds. 7. The total processing time from the insertion of the leading end of the silver halide photographic light-sensitive material to be processed into the automatic developing machine until it comes out of the drying zone is 10 to 60 seconds. Item 6. The method for developing a silver halide photographic light-sensitive material according to Item 5.