JPH10282600A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the deterioration in sensitivity and gamma fluctuation and the generation of black dots even after preservation with laps of time by providing the surface of a base with one layer of specific silver halide emulsion layer. SOLUTION: The surface of the base is provided with the silver halide emulsion layer which is spectrally sensitized by at least two kinds of the sensitizing dyestuffs expressed by formula I, contains hydrazine derivatives and are hardened by at least one kind of the respective compds. expressed by formulas II, III. In the formula I, Y<1> to Y<3> denote oxygen atoms, etc. R, R<1> to R<3> denote aliphat. groups and at least one group among these groups denotes a water-soluble group. V<1> , V<2> denote hydrogen atoms, etc.; L<1> to L<4> denote substd. methyl groups; (n) denotes 1 or 2; (m) denotes 0 or 1; M<1> denotes the ion necessary for offsetting the total charge of the molecule; n<1> denotes the number necessary for charge neutralization of the molecule. In the formula II, R1 , R2 denote alkyl groups, etc., R3 denotes a (substd.) acyl group, etc.; X<-> denotes an anion and (n) and (m) respectively denote 0 or 1. In the formula III, X1 denotes a halogen atom, etc., and Y1 denotes a hydrogen atom, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Black-and-white silver halide photographic materials (hereinafter, referred to as "silver halide photographic materials").
In particular, a photosensitive material for printing plate making requires high-contrast photographic characteristics in order to faithfully reproduce a halftone image or a line image. Conventionally, various techniques have been known as methods for obtaining high-contrast photographic characteristics. For example, a high-contrast technique according to US Pat. No. 4,269,929 using a hydrazine derivative is widely known.

In recent years, in the scanner and imagesetter markets in the printing and plate making industry, a screening method for forming an image with a smaller halftone dot, such as high definition and FM screening, has begun to spread. For such a screening method, a super-high contrast photographic material using a hydrazine derivative having a small concentration of dots is suitable.

[0004] However, silver halide photographic materials tend to fluctuate and deteriorate in photographic performance when left under high temperature and high humidity for a long time. In particular, in the case of the above-described ultra-high contrast light-sensitive material, a fatal obstacle such as sensitivity fluctuation, softening, and increase of black spots (generation of fine spot-like fog in the unexposed area) increases with time. Had the problem of inviting.

On the other hand, in recent years, shortening of working time has been called for as one of improvement of working environment, and therefore, shortening of processing time of photosensitive material has been strongly desired in the printing and plate making industry.

In the rapid processing of a photosensitive material, the film properties are important because the film is conveyed at a high temperature and a high speed in addition to the improvement of the developing property. That is, a photosensitive material that can withstand high-speed conveyance by an automatic developing machine, has no damage to the film surface, and has a film property of a high drying speed after the development processing is required.

Conventionally, many compounds have been known as a hardening agent for silver halide photographic light-sensitive materials. For example, for a light-sensitive material which can be rapidly processed at a high temperature, a special compound using a vinyl sulfone type hardening agent is used. Kaihei 1-121849, 3-
No. 9343, No. 4-122924, No. 5-11942
No. 2 and the like are disclosed. Further, JP-A-2-230 using dichloro-s-triazine or an active halogen type hardener is disclosed.
No. 137, JP-A-63-128338 or a carboxyl group-active hardener.

However, these known techniques also have disadvantages depending on individual hardeners. For example, a vinyl sulfone type hardener or a carboxyl group-active type hardener generally has a low hardening speed, and thus has a heat treatment. However, there is a problem that the film is used after a few months from the application of the film, or after a few months from the application.

An acid-releasing type such as an s-triazine type or an active halogen type hardening agent has a disadvantage that the emulsion sensitivity is lowered due to halogen generated after the hardening reaction. In particular, a hydrazine derivative is used as a hardening agent. The printing photosensitive material used has a problem that desensitization and softening are large.

Further, formaldehyde, which is known as an aldehyde-based hardener, has a drawback that the degree of hardening varies due to variations in drying conditions due to its high volatility. or,
Aldehyde hardeners such as glyoxal and glutaraldehyde have the drawback that, when used in an amount sufficient to obtain the required hardening degree, fog tends to occur during storage of the photosensitive material over time.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material hardened with a hydrazine derivative, which is free from fluctuations in sensitivity and gamma and generation of black spots even when stored over time. Another object of the present invention is to provide a silver halide photographic light-sensitive material which has a fast drying property and can obtain a stable halftone dot quality even in a rapid processing by an automatic developing machine, and a processing method therefor.

[0012]

The object of the present invention has been attained by the following.

In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains at least two sensitizing dyes represented by the following general formula [S]. The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and contains at least one compound represented by the following general formula [I]. A silver halide photographic material, which is hardened with at least one compound represented by the following general formula [II]:

[0014]

Embedded image

In the formula, Y ¹ , Y ² and Y ³ each independently represent a —N (R) — group, an oxygen atom, a sulfur atom or a selenium atom. 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 V ¹ and V ² bonded to a group which forms a condensed ring with the azole ring, L ^1, L ^2,
L ³ and L ⁴ each independently represent a substituted or unsubstituted methine group. n represents 1 or 2, and m represents 0 or 1. M ¹
Represents an ion required to offset the total charge of the molecule, and n ¹
Represents the number required to neutralize the molecular charge.

[0017]

Embedded image

In the formula, R ₁ and R ₂ represent an alkyl group or an aryl group which may be substituted, and may be the same or different. R ₁ and R ₂ may combine with each other to form a heterocyclic ring together with a nitrogen atom. R ₃ represents an alkyl group, an alkoxy group, an acyl group, or an acylamino group which may have a substituent. X ^- represents an anion, n and m are each 0
Or represents 1.

[0019]

Embedded image

In the formula, X ₁ represents a halogen atom (for example, a chlorine atom), an N-methylolamino group, a glycidoxy group, or an ethyleneimine group. Y ₁ represents a hydrogen atom, a halogen atom (for example, a chlorine atom), —ON ₂ , an alkoxy group, a substituted or unsubstituted amino group (an alkyl group, a phenyl group, a sulfonated phenyl group, a carboxylated phenyl group, a hydroxyalkyl Group, sulfonated alkyl group),
Represents an N-methylolamino group, a glycidoxy group, an ethyleneimine group, or a substituted mercapto group.

In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains at least two of the sensitizing dyes represented by formula (S). The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and contains at least one compound represented by the general formula [I]. A silver halide photographic material, which is hardened with at least one compound represented by the following general formula [III]:

[0022]

Embedded image

In the formula, Y represents a vinyl group, and A represents a divalent group. p is 0 or 1. R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be the same or different.

In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains at least two of the sensitizing dyes represented by formula (S). The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and contains at least one compound represented by the general formula [II]. A silver halide photographic material, which is hardened with at least one compound represented by the following general formula [IV]:

[0025]

Embedded image

Wherein R ₅ and R ₆ are a hydrogen atom, an alkyl group,
Represents an aralkyl group, an aryl group or a heterocyclic group, and these groups may be substituted. q represents 0 or 1.

In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains at least two of the sensitizing dyes represented by formula (S). The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and contains at least one compound represented by the general formula [III]. A silver halide photographic material, which is hardened with at least one of the compounds represented by the general formula [IV].

By processing the silver halide photographic material described in any one of the above items with a developing solution having a pH of 9.0 to 11.0, a high contrast image having a gamma of 10 to 40 can be obtained. A method for processing a silver halide photographic material.

The method for subjecting a silver halide photographic material as described in any one of the above to at least development, fixing, washing or stabilization using an automatic development processor after exposure, the method comprising the steps of: Alternatively, the replenishing amount of the fixing solution is 75 to 25 per m ^{2 of the} silver halide photographic material.
0 ml of a silver halide photographic light-sensitive material.

The method for processing a silver halide photographic light-sensitive material according to or described above, wherein the total processing time (Dry to Dry) of the silver halide photographic light-sensitive material is 10 to 60 seconds.

Hereinafter, the present invention will be described in detail.

The silver halide emulsion layer of the light-sensitive material of the present invention is spectrally sensitized with at least two kinds of sensitizing dyes represented by the above formula [S].

In the formula, Y ¹ , Y ² and Y ³ each independently represent a —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.

As the aliphatic group represented by R, R ¹ , R ² and R ³ , for example, a branched or linear alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, n-propyl, n −
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) Each group).

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-sulfopropoxycarbonyl. Methyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, p- There are various groups such as carboxybenzyl,
Specific examples of the aryl group substituted with a water solubilizing group include p
-Sulfophenyl group, p-carboxyphenyl group and the like. Specific examples of the heterocyclic group substituted with a water-solubilizing group include 4-sulfothienyl group and 5-carboxypyridyl group.

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 group, ethoxy group and butoxy group, and alkoxy groups such as 2-methoxyethoxy group and benzyloxy group. Is mentioned.

The above-mentioned substituents represented by V ¹ and V ² and the condensed ring formed 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 groups (for example, unsubstituted alkyl groups such as methoxy, ethoxy and butoxy, substituted alkoxy groups such as 2-methoxyethoxy and benzyloxy), and alkylthio groups (for example, substitution of methylthio and ethoxyethylthio groups)
An unsubstituted alkyl group), a hydroxy group, a cyano group, an aryloxy group (for example, a substituted or unsubstituted group such as phenoxy or tolyloxy), or an aryl group (for example, a substituted or unsubstituted group such as phenyl or p-chlorophenyl) Group), styryl group, heterocyclic group (for example, each group such as furyl and thienyl), carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl), and sulfamoyl group (for example, sulfamoyl and N, N-dimethylsulfamoyl) An acylamino group (for example, acetylamino, propionylamino, benzoylamino, etc.), an acyl group (for example, acetyl, benzoyl, etc.), an alkoxycarbonyl group (for example, ethoxycarbonyl, etc.),
Examples include an arbitrary group such as a sulfonamide group (for example, each group such as methanesulfonylamide and benzenesulfonamide), a sulfonyl group (for example, each group such as methanesulfonyl and p-toluenesulfonyl), and a carboxy group.

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 (for example, each group such as methyl and ethyl) and a phenyl group (for example, phenyl and 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 general 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.

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

The spectral sensitizing dyes of the present invention include, for example,
F. M. Hammer, "Cyanine Soybeans and Related Compounds" (1964, published by Interscience Publishers), US Patent 2,454,629.
No. 2,493,748, and the like, and can be easily synthesized with reference to conventionally known methods.

The addition amount of the above-mentioned spectral sensitizing dye of the present invention is
It is not uniform depending on the type of emulsion used, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ per mol of silver halide.
Mol, more preferably in the range of 2 × 10 ⁻⁶ to 2 × 10 ⁻³ mol.

The dyes of the present invention are used in combination of two or more, and can be used arbitrarily in the above-mentioned amount range. The addition timing of the spectral sensitizing dye to the emulsion may be any step.
In addition, you may mix and use the pigment | dye outside this invention.

When the above-mentioned spectral sensitizing dye is used, it may be dissolved in water or a hydrophilic solvent (eg, methanol, ethanol, methyl cellosolve, etc.) and added to the silver halide emulsion. May be added. When two or more kinds are used as a mixture, they may be dissolved or dispersed individually and then mixed, or they may be simultaneously dispersed. When a solid fine particle dispersion of a dye is produced in the presence of an aqueous dispersion medium, a surfactant is preferably co-present during or after dispersion.

The silver halide photographic light-sensitive material of the present invention includes:
A hydrazine derivative is contained in the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto. As the hydrazine derivative to be used, a compound represented by the following general formula [H] is preferable.

[0061]

Embedded image

In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) _n -group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ₂ — group or an iminomethylene group, n represents an integer of 1 or 2, both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group. A carbamoyl group or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

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

[0064]

Embedded image

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 diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, 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 [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X 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, and G is preferably a carbonyl group.

In the general 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,
Represents 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).

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

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

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 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 columns 59 to 80 of No. 29,248.

The hydrazine derivative preferably used in the present invention is added to a silver halide emulsion layer and / or an adjacent layer. The hydrazine compound used in the present invention can be used in any layer as long as it is 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. Molar ranges are preferred,
Particularly, the range of 10 ^-5 to 10 ^-2 mol is preferable.

In order to effectively promote the hardening by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following formula [Na] or [Nb].

[0082]

Embedded image

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 adsorptive group in the molecule.

The following are specific examples of these nucleation accelerators [Na].

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₁₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
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 compound represented by the general formula [Nb] include the following.

[0091]

Embedded image

[0092]

Embedded image

Specific examples of other preferred nucleation promoting compounds include 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 hardener represented by the above formula [I] used in the silver halide emulsion layer or the adjacent hydrophilic colloid layer of the silver halide photographic material of the present invention will be described.

[0096] R _1, R ₂ is an alkyl group having 1 to 3 carbon atoms which may be the same or different in the formula of the general formula (I), an aryl group, an aralkyl group, R _1, R ₂ are bonded to each other To form a heterocyclic ring (eg, a piperidine ring or a morpholine ring), and R ₃ represents an alkyl group, an alkoxy group, an acyl group, or an acylamino group which may have a substituent;
X ⁻ is an anion and represents, for example, a halogen atom (Cl, Br, etc.).

Specific examples of the compound represented by the above general formula [I] are shown below, but the present invention is not limited thereto.

[0098]

Embedded image

[0099]

Embedded image

Next, the hardener represented by the formula (II) used in the silver halide emulsion layer or the adjacent hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention will be described.

In the general formula [II], X ₁ in the formula represents a halogen atom (for example, a chlorine atom), an N-methylolamino group, a glycidoxy group, or an ethyleneimine group. Y ₁ represents a hydrogen atom, a halogen atom (for example, a chlorine atom), —O
N ₂ , alkoxy group, substituted or unsubstituted amino group (alkyl group, phenyl group, sulfonated phenyl group, carboxylated phenyl group, hydroxyalkyl group, sulfonated alkyl group as a substituent), N-methylolamino group, glycidoxy Group, ethyleneimine group, and substituted mercapto group.

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

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

In the present invention, one or more hardening agents represented by the above general formulas [I] and [II] are used in combination. The amount used may be usually in the range of 0.01 to 100% by weight based on the dry weight of the silver halide emulsion layer and / or the adjacent hydrophilic colloid layer of the present invention,
Preferably, it is used in the range of 0.1 to 10% by weight.

In the present invention, the above general formulas [I] and [I
The ratio of the amount of the hardener represented by I] may be arbitrary, but preferably the ratio of [I] to [II] is 1:10 to 10: 1.

When used, both may be dissolved separately or mixed and added to the coating solution. The timing of addition is arbitrary, but it is preferable to add it after the preparation of the coating solution or at the time of coating.

Next, the hardener represented by formula (III) used in the silver halide emulsion layer or the adjacent hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention will be described.

In the formula [III], Y represents a vinyl group, A represents a divalent group, and p represents 0 or 1. R
₄ is a hydrogen atom or a carbon number of 1-4 which may be the same or different
Represents a hydrocarbon group.

The divalent group is not particularly limited, and is a cyclic or acyclic hydrocarbon group having 1 to 10 carbon atoms, in which 1 to 3 of which are substituted with a hetero atom such as N, S, or O. May be. More preferably, it is a chain hydrocarbon group having 1 to 5 carbon atoms, which may be branched or linear. This chain may have a substituent such as halogen, alkoxy, hydroxy, acetoxy and the like. R ₄ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

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

[0113]

Embedded image

[0114]

Embedded image

In the present invention, one or more hardening agents represented by the above general formulas [I] and [III] are used in combination. The amount and method of use may be the same as the combination of the hardeners represented by the general formulas (I) and (II),
The dry weight of the silver halide emulsion layer of the present invention and / or the adjacent hydrophilic colloid layer is usually 0.01 to 100%.
% By weight, preferably from 0.1 to 10%.
It is used in the range of weight%.

In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and at least one of the compounds represented by the above general formula [II]. The film is hardened with one kind and at least one kind of the compound represented by the general formula [IV].

Next, the hardener represented by the general formula [IV] will be described. In the general formula [IV], R in the formula
₅ , R ₆ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (such as methyl and ethyl groups), an aralkyl group having 6 to 20 carbon atoms (such as benzyl and phenethyl groups), and an aryl group having 5 to 20 carbon atoms. (For example, a phenyl or naphthyl group), a heterocyclic group (for example, a pyridyl group),
These groups may be substituted, and examples of the substituent include a hydroxy group, a sulfonic group, and a carboxyl group. q represents 0 or 1. q is preferably 0.

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

[0119]

Embedded image

[0120]

Embedded image

In the present invention, one or more hardening agents represented by the above general formulas [II] and [IV] are used in combination. The amount and method of use are the same as those described in the above general formula [I]
And the hardening agent represented by [II].

In the present invention, the compound represented by the general formula [II]
The hardeners represented by I] and [IV] are used in combination of one or more kinds. The amount and method of use may be the same as those for the combination of the hardeners represented by the general formulas [I] and [II].

As described above, according to the hardening method of the present invention in which two specific hardeners are used in combination, the silver halide photographic light-sensitive material, which has been super-hardened with a hydrazine derivative, is stored over time. And the effect of improving photographic performance for printing plate making can be obtained.

In the silver halide photographic light-sensitive material of the present invention,
Dyes dispersed in solid fine particles can be used. As the dye that can be preferably used, it is preferable to use compounds represented by the following general formulas [1] to [6].

[0125]

Embedded image

In the formula, A and A 'may be the same or different and each represents an acidic nucleus, B represents a basic nucleus,
Q represents an aryl group or a heterocyclic group; Q ′ represents a heterocyclic group; X ₄ and Y ₁ may be the same or different and each represents an electron-withdrawing group; L ₁ , L ₂ and L ₃ Each represents a methine group. m ₂ represents 0 or 1, t is 0,
Represents 1 or 2, and p ₂ represents 0, 1 or 2. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The acidic nucleus represented by A and A 'in the general formulas [1], [2] and [3] is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thione Hydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole, indole.

Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q and Q 'in formulas [1], [4] and [6] include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group and an indolyl group. Group, furyl group,
And a thienyl group. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, and a cyano group. Group, hydroxy group,
Examples include a mercapto group, an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfamoyl group, and a sulfonamide group. These substituents may be used in combination of two or more. Preferred substituents include an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a t-butyl group, an octyl group,
2-hydroxyethyl group, 2-methoxyethyl group, etc.),
Hydroxy group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, etc.), alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, butoxy group, etc.) A substituted amino group (for example, a dimethylamino group, a diethylamino group,
Di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (Eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group,
Methylsulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The electron-withdrawing groups represented by X ₄ and Y ₁ in the general formulas [4] and [5] may be the same or different,
Σp value of substituent constant Hammett (edited by Toshio Fujita, “Structure-Activity Relationship of Drugs in Chemical Domain No. 122,” 96-1
Page 03 (1979), Nankodo, and the like. Is preferably 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, -Hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group) , 4-
An ethylsulfonylcarbonyl group, an alkylsulfonyl group (eg, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group), and an arylsulfonyl group (eg, a phenylsulfonyl group, a 4-chlorosulfonyl group). .

L ₁ , L ₂ and L _{3 of the} general formulas [1] to [5]
The methine group represented by includes those having a substituent, for example, an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (eg, a phenyl group, Tolyl group, 4-hydroxyphenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), heterocyclic group (eg, pyridyl group, furyl group, thienyl group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group) , Anilino group, etc.) and alkylthio groups (eg, methylthio group, etc.).

In the present invention, among the dyes represented by the general formulas [1] to [6], a dye having at least one carboxyl group in the molecule is preferably used, and more preferably a dye having the general formula [1] And particularly preferably a dye in which Q in the general formula [1] is a furyl group.
Specific examples of preferably used dyes are shown below, but are not limited thereto.

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

Other preferred specific examples of the compounds represented by the formulas [1] to [6] include, for example, Japanese Patent Application No. 5-27.
No. 7011, pp. 19-30. I-1 to No. 1;
I-30, II-1 to II-12, III-1 to III-8, IV-
Examples include, but are not limited to, 1 to IV-9, V-1 to V-8, and VI-1 to VI-5.

A method for producing a solid fine particle dispersion of a dye is described in JP-A-52-92716 and JP-A-55-15553.
No. 50, No. 55-155351, No. 63-19794
No. 3 and No. 3-182743, world patent WO88 / 0
The method described in No. 4794 or the like can be used.
Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound to be dispersed in solid fine particles is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, dissolve the compound in a weakly alkaline aqueous solution and then lower the pH to make it weakly acidic. A method of precipitating fine solid particles or a weakly alkaline solution of the compound and an aqueous acidic solution, pH
A dispersion of the compound can be obtained by a method in which the particles are mixed at the same time while adjusting the particle size to produce a particulate solid.

The solid fine particle dispersion may be used alone, or two or more kinds may be used as a mixture, or may be used as a mixture with a solid fine particle dispersion other than the present invention. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

When the solid fine particle dispersion is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant is present during or after the dispersion. Examples of such a surfactant include an anionic surfactant, a nonionic surfactant,
Although any of a cationic surfactant and an amphoteric surfactant can be used, preferably, for example, an alkyl sulfonate,
Anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and saponins, for example. And nonionic surfactants such as alkylene oxide derivatives and alkyl esters of sugars. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include, for example, Japanese Patent Application No. 5-277011 32-
Compounds 1 to 32 described on page 46 may be mentioned, but not limited thereto.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion of the dye, but is usually preferably from 0.1 to 2000 mg per g of the dye. , More preferably 0.5 to 1000 mg, particularly preferably 1 to 50 mg.
0 mg may be sufficient.

The concentration of the dye in the dispersion is 0.01
使用 50% by weight is preferably used,
More preferably, it is 0.1 to 30% by weight. The addition position of the surfactant is preferably added before the start of dispersion of the dye,
If necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone, respectively, or two or more kinds may be combined, and both activators may be combined.

The solid fine particle dispersion has an average particle size of 0.0
It is preferable that the particles are dispersed so as to have a thickness of 1 to 5 μm, more preferably 0.01 to 1 μm, and particularly preferably 0.01 to 0.5 μm. Further, the coefficient of variation of the particle size distribution is preferably 50% or less,
It is more preferably at most 40%, particularly preferably at most 30%.
% Or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) × 100 The dispersion of solid fine particles may be added with a hydrophilic colloid used as a binder for a photographic component layer before or after the start of dispersion. it can. As the hydrophilic colloid, it is advantageous to use gelatin.In addition, for example, phenylcarbamylated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin, and gelatin having a polymerizable ethylene group-containing monomer. Graft polymer,
Synthetic hydrophilicity such as carboxymethylcellulose, hydroxymethylcellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, polymethacrylic acid, etc. , Agar, gum arabic, alginic acid, albumin, casein and the like can be used. These may be used in combination of two or more. The amount of the hydrophilic colloid to be added to the solid fine particle dispersion of the present invention is 0.1 to 1 in weight percentage.
It is preferably added so as to be 2%, more preferably 0.5 to 8%.

The solid fine particle dispersion to be used may be a layer constituting a photographic material, for example, a silver halide emulsion layer, an upper layer of the emulsion layer,
It can also be used as a layer such as a lower layer of an emulsion layer, a protective layer, an undercoat layer of a support, and a backing layer. In particular, in order to enhance the antihalation effect, it is preferably added to a layer between the support and the emulsion layer or a constituent layer opposite to the emulsion layer. In order to particularly enhance the effect of improving the safelight property, it is preferable to add the compound to the layer above the emulsion layer.

The preferred amount of the solid fine particle dispersion of the dye is not uniform depending on the type of the dye and the characteristics of the photographic material, but is preferably 1 mg to 1 g per 1 m ^{2 of} the photographic material, and more preferably. The amount is 5 to 800 mg, particularly preferably 10 to 500 mg.

A layer containing the above dye dispersed in a solid state may be provided between the light-sensitive emulsion layer and the support. Other layers, that is, other light-sensitive and light-insensitive emulsion layers, non-emulsion The layers (hydrophilic colloid layer, hydrophobic polymer layer) may also contain a dye dispersed in a solid state. It may be contained in any layer on the side opposite to the emulsion layer with respect to the support. Further, any layer may have a water-soluble dye. The amount of the dye dispersed in a solid state in the present invention is 0.001 as an absorbance in at least a part of a wavelength region of a light source used for exposure.
It is preferable to add the amount in which the above absorbance becomes 0.005 to 1.5. In the present invention, a dye having another absorption wavelength can be used in any layer.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention can be prepared by using generally known sulfur sensitization, Se
Alternatively, sensitization can be carried out by using Te sensitization, reduction sensitization, a noble metal sensitization method, or the like alone or by appropriately selecting them. or,
These chemical sensitizations may not be performed.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanines, polysulfide compounds and the like can be used in addition to the sulfur compounds contained in gelatin. As the selenium sensitizer, triphenylselenophosphine and the like are preferably used.

A wide variety of selenium compounds can be used as the selenium sensitizer. For example, US Pat.
74,944, 1,602,592, 1,62
3,499, JP-A-60-150046, JP-A-4
-25832, 4-109240, 4-147
Compounds described in No. 250 and the like can be used. Useful selenium sensitizers include colloidal selenium metal,
Isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenourea,
N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4- Nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone,
Selenoacetophenone, etc.), selenoamides (for example,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), and selenophosphates (eg,
Tri-p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferred. Solid dispersion As a method for adding these sensitizers, if they are water-soluble, they can be added as they are, but if they are hardly soluble in water, various methods can be adopted. For example, there is a method in which a sulfur sensitizer and / or a selenium sensitizer and / or a tellurium sensitizer are sufficiently mixed in advance with a gelatin solution and then added. Alternatively, a method of dissolving in a low-boiling organic solvent in which a sensitizer is dissolved and then emulsifying and dispersing in the presence of a surfactant to add the sensitizer can also be adopted. In this method, it is preferable to remove the low-boiling organic solvent after emulsification and dispersion. Further, JP-A-4-
According to the method disclosed in No. 140739, it is also possible to add the compound in the form of an emulsified dispersion of a mixed solution with a water-insoluble and organic solvent-soluble polymer. Also, among the noble metal sensitization methods which can employ a method of arbitrarily dispersing the average particle diameter from 0.01 to 6 μm by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, etc., gold sensitization is a typical one. And a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

As the reduction sensitizer, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used. Oxidizing agent In the present invention, an oxidizing agent for silver can be used in the production process of the light-sensitive material. The oxidizing agent usable in the present invention, for example, as inorganic oxidizing agent, hydrogen peroxide (water), adducts of hydrogen peroxide (e.g., _{NaBO 2 · H 2 0 2 ·} 3H 2 O,
_{2NaCO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2N
a ₂ SO ₄ .H ₂ O ₂ .2H ₂ O, etc., peroxy acid salts (eg, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₄ P ₂ O ₈ ), peroxy complex compounds (eg, K ₂ [Ti (O ₂ ) C ₂ O ₄ ]
· 3H ₂ O, 4K ₂ SO ₄ · Ti (O ₂ ) · OH · SO ₄ ·
2H ₂ O, Na ₂ [VO (O ₂ ) (C ₂ O ₄ ) ₂ ] · 6H ₂ O
Oxyacids such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ CrO), halogen elements such as iodine and bromine, and perhalates (eg, potassium periodate) , High valent metal salts (such as potassium ferricyanide) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (eg, N-bromosuccinimide, chloramine T, chloramine B, etc.). Is given as an example.

The halogen composition of the silver halide photographic light-sensitive material of the present invention may be pure silver chloride, silver chlorobromide containing 50 mol% or more of silver chloride, or silver chloroiodobromide containing 50 mol% or more of silver chloride. Preferably, there is.

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

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. 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 silver halide grains in the presence of excess silver ions (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 subjected to cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt during at least one of the steps of forming or growing the grains. 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.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

In the silver halide photographic light-sensitive material of the present invention,
Various compounds can be contained for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, azoles,
For example, benzothiazolium salts, nitroindazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole ( Mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1). , 3,3a, 7-tetrazaindenes), pentazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, bromide Many compounds known as antifoggants or stabilizers, such as helium can be added. Particularly preferred are substituted or unsubstituted heterocyclic or fused heterocyclic rings containing any of N, O, S, and Se, and water-soluble halides.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention may contain an inorganic or organic hardener other than the present invention. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Hardening agents such as mucohalogenic acids (such as mucochloric acid and phenoxymucochloric acid), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, and isocyanates may be used alone or in combination. it can.

The silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may contain a coating aid, an antistatic,
Various known surfactants may be used for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties.

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.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability, reducing silver sludge, and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth)
Acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, alone or in combination thereof, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, A polymer having a combination of hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used. Further, a monomer having a plurality of ethylenically unsaturated groups may be used as a monomer component. These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group, and an amide group, and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, -NR 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 the synthesis method, in addition to the ordinary synthesis method,
The polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohol. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

In the light-sensitive material used in the present invention, various other additives are used. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, colloidal silica, and the like can be used.

For these additives and the above-mentioned additives, specifically, Research Disclosure 176
No. (supra), pp. 22-31, etc. can be used.

In the light-sensitive material used in the present invention, the emulsion layer may be a single layer or a multi-layer composed of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween. Further, it may have a non-photosensitive emulsion. As the non-emulsion layer, any number of layers may be provided as necessary between the support and the emulsion layer closest to the support, between a plurality of emulsion layers, and outside the emulsion layer farthest from the support. Can be. These layers include:
Water-soluble or water-insoluble dyes, image-wise or non-image-wise development adjustment (suppression or acceleration) agents, contrasting agents, physical property modifiers, etc. dissolved in aqueous solution or organic solvent, or in the form of solid fine particles It can be contained in dispersed form (which may or may not be protected by oil). The emulsion layer may be on one side or both sides of the support. Even on one side, an arbitrary number of hydrophilic or non-hydrophilic layers can be provided in combination on the opposite side. In particular, when a layer of a hydrophobic polymer is provided outside the hydrophilic colloid layer with respect to the support pair, the drying property can be improved.

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

In the method for processing a silver halide photographic light-sensitive material of the present invention, the processing can be performed with a processing solution containing substantially no dihydroxybenzene compound. In this case, a compound represented by the following general formula [A] is preferably contained.

[0171]

Embedded image

In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, R ₁ and 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 represents -CS-.

Of the compounds represented by the above general formula [A], those represented by the following general formula [Aa] in which R ₁ and R ₂ are bonded to each other to form a ring are preferred.

[0174]

Embedded image

In the formula, 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 carboxyl group, It represents 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.

In the general formula [A], the alkyl group in the general formula [Aa] is preferably a lower alkyl group,
For example, an alkyl group having 1 to 5 carbon atoms, an amino group is preferably an unsubstituted amino group or an amino group substituted with a lower alkyl group, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably A phenyl group or a naphthyl group, and these groups may have a substituent. Examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group,
Preferred examples of the substituent include a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or (Aa) according to the present invention are shown below.
The present invention is not limited to these.

[0178]

Embedded image

[0179]

Embedded image

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.

The term "substantially free of hydroquinones (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate, etc.)" means an amount of less than 0.01 mol per liter of developer.

In the present invention, 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone,
-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 preferably used usually in an amount of 0.01 to 1.4 mol per liter of developer.

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 according to 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 and the like which can be added to the developer can be added. 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 and used, a transition metal complex is preferably used as a developing agent of the developer used.

Examples of the sulfite and metabisulfite used as a preservative in the developer 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 alkaline 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 in the processing method of the present invention is preferably adjusted to 9.0 to 11.0, and particularly preferably adjusted to 9.5 to 10.7.

In the method for processing a light-sensitive material of the present invention, a compound represented by the following general formula (S) can be contained in a developer.

Formula (S) Z ¹ -SM ^{1 In the} formula, Z ¹ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M group, a —COOO.
At least one selected from the group consisting of an M group (M is a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium group), a substituted or unsubstituted amino group, a substituted or unsubstituted ammonium group, or It represents one substituted by a substituent having at least one selected. M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

As a special form of the 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 processing the light-sensitive material in an alkaline aqueous solution to perform development. 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 in the processing method of the present invention, 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.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like. 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 carried out at normal temperature, but may be carried out at 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 use solution or a concentrated solution diluted immediately before. The stock of the mother liquor and 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. Particularly, a method of adding a tablet formed product to a dissolution layer or a directly treated layer is a method which is extremely excellent in workability, space saving and preservation, and is particularly preferably used.

In the development processing of the present invention, the development temperature can be set to a normal temperature range of 20 to 50 ° C. The black and white photosensitive material according to 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. In the processing method of the present invention, the replenishing amount of the developing solution and the replenishing amount of the fixing solution are 75 to 25 per m ² in order to reduce the amount of waste liquid.
Preferably, it is treated with 0 ml. More preferably 1
m is ² per 100~200ml. 1m ² per 75
If the developer replenishment amount is less than 10 ml, satisfactory photographic performance cannot be obtained due to desensitization and softening.

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 to the emergence from 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. More preferably, it is 30 to 50 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, for example, development, fixing, bleaching, washing, stabilizing processing, Time including all the time of the process such as drying, that is, Dr
It is the time of y to Dry.

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 to 130 ° C.) is used.
Alternatively, a radiating object of 150 ° C. or more (for example, tungsten,
Direct current flow through carbon, nichrome, zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc. to generate heat and radiate heat, or transfer heat energy from resistance heating elements to radiators such as copper, stainless steel, nickel and various ceramics Examples include a device having a zone for drying by generating heat or emitting infrared rays), or a device provided with a known drying unit such as a dehumidifier, a microwave generator, or a water-absorbing resin. Further, a dry state control mechanism as described in JP-A-1-315745 may be provided.

[0198]

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

Example 1 (Preparation of Silver Halide Emulsion A1) A silver chlorobromide core particle having an average diameter of 0.09 μm and comprising silver bromide and the remainder being silver bromide was prepared by a double jet method. K at the core particle mixture _{3 Rh (N0) 4 (H} 2 O) 2 a 7 × 1 mol of silver when silver mole per grain formation ended
10 ⁻⁸ mol, K ₃ OsCl ₆ at 8 ° C. in the presence of 8 × 10 ⁻⁶ mol, 40 ° C., pH 3.0, silver potential (EAg) 165 mV
While keeping the pH of the mixture, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed.

The EAg was added to the core particles with a salt solution of 125 m.
V and shelled using a double jet method. At this time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 3 per mole of silver.
^-7 mol and 9 × 10 ^-8 mol of K ₃ RhCl ₆ were added. Further, KI conversion was performed using silver iodide fine particles, and the resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (70 mol% silver chloride, iodine iodine) having an average diameter of 0.15 μm. (A silver bromide of 0.2 mol%, the balance being silver bromide). Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-280139)
No. 139, p. 287 (3), Exemplified compound G-8). The EAg after desalting was 190 mV at 50 ° C.

The obtained 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, EAg12 with addition of ^-4 mol and citric acid
After adjusting to 3 mV and reacting by adding 1 × 10 −3 mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T), inorganic sulfur (S8) dispersed in a solid and PM-1200 ( Saponin was added and dispersed to an average particle size of 0.5 μm using Seishin Enterprise Co., Ltd.) and 1.5 × 10 ^-5 mol of chloroauric acid was added to obtain the highest sensitivity at a temperature of 55 ° C. After chemical ripening until 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 was added in an amount of 3 × 10 ⁻⁴ mol. And then add potassium iodide 5 ×
10 ^-3 mol was added, the pH was adjusted to 5.1 with citric acid,
The sensitizing dye according to the present invention shown in Table 1 was added.

(Preparation of a photosensitive material for a printing plate making scanner containing a hydrazine derivative)
Of a gelatin undercoat layer so that the amount of gelatin is 0.45 g / m ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, the amount of gelatin 0.65 g / m ^The silver halide emulsion layer 2 of Formulation 3
Was coated simultaneously so that the amount of silver was 1.5 g / m ² , the amount of gelatin was 0.65 g / m ^2, and the coating solution for the protective layer of the following formula 4 was 0.7 g / m ² . . On the other side of the undercoating layer, a backing layer of the following formulation 5 was provided with a gelatin amount of 1.5 g / m ^2, and a backing protective layer of the following formulation 6 was provided thereon with a gelatin amount of 0.8 g / m 2. ^Two
200m / with the emulsion layer side and curtain coating method
After the simultaneous coating of the emulsion layer side and the cooling setting, the backing layer side was simultaneously coated by -1.
The sample was obtained by cooling and setting at the same temperature and drying both sides simultaneously.

[0203] «layer (1)» Formulation 1 (gelatin subbing layer composition) Gelatin 0.45 g / m ² Saponin 56.5 mg / m ² sodium polystyrenesulfonate (average molecular weight 500000) 15 mg / m ² fungicides z 0. 5 mg / m ² solid disperse dye illustrative AD-8 (those were dispersed in ZrO beads and powdered dispersion of particle size 0.1 [mu] m) 15 mg / m ² «layer (2)» formulation 2 (a silver halide emulsion Layer composition) Silver halide emulsion A1 3.2 g / m ² equivalent of silver hydrazine compound H-27 2 × 10 ⁻³ mol / Ag 1 mol Illustrative nucleation accelerator Na-3 7 mg / m ² 2-pyridinol 1 mg / m ² polymer latex L1 (particle size 0.25 [mu] m) 0.25 g / m ² sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² sodium naphthalene sulfonate 8m / M ² Saponin 20mg / m ² of hydroquinone 20mg / m ² 2-mercapto-6-hydroxy-purine 2 mg / m ² 2-Merukafu ° topics lysine 1 mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 150 mg / m ² of ascorbic acid 20mg / M ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / m ^{2 The} coating solution had a pH of 5.2.

<< Layer (3) >> Formulation 3 (Emulsion protective layer composition) Gelatin 0.6 g / m ² amino compound AM-1 14 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 35 mg / m ² mat Agent: Spherical polymethyl methacrylate having an average particle size of 3.5 μm 25 mg / m ² Amorphous silica having an average particle size of 8 μm 12.5 mg / m ² Surfactant S1 26.5 mg / m ² Slip agent (silicone oil) 4 mg / m ² Colloidal silica (average particle size: 0.05 μm) 150 mg / m ² Dye f1 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m the amount «layer (4)» shown in hardener table 1 according to the ^two invention formulation 4 (backing layer composition) gelatin 0.6 g / m ² Sodium - Lee - amyl -n- decyl sulfosuccinate 5 mg / m ² Polymer latex L4 0.3 g / m ² Colloidal silica (average particle size 0.05μm) 100mg / m ² of sodium polystyrenesulfonate 10 mg / ^{m 2} Dye f1 65 mg / m
² dye f2 15 mg / m ² dye f3 100 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² hardener h3 100 mg / m ² zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² layer (5) ≫ Formulation 5 (backing protective layer composition) Gelatin 0.4 g / m ² matting agent: monodisperse polymethyl methacrylate having an average particle size of 5 μm 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 S1 1 mg / m ² dye f1 65 mg / m ² dye f2 15 mg / m ² dye f3 100 mg / m ² sodium-iso-acyl-n-decyl sulfosuccinate Nate 50 mg / m ² Hardener h1 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ²

[0205]

Embedded image

[0206]

Embedded image

[0207]

Embedded image

[0208]

Embedded image

[0209]

Embedded image

[0210]

Embedded image

The following were evaluated for the obtained samples.

(Evaluation of Sensitivity and Gamma) Exposure was performed with a laser sensitometer using a 633 nm He-Ne laser as a light source while performing step exposure while changing the light amount in 1.5 × 10 ⁻⁷ sec. Automatic developing machine GR-27
(Konica Corporation).

However, the replenishing amount of the developing solution was 200 ml / m ² , the replenishing amount of the fixing solution was 200 ml / m ^2, and the running after the forced running was performed until the replenishing amount was twice the developing tank capacity of the automatic developing machine. The liquid was used.

The developed sample thus obtained was measured with a PDA-65 (Konica Digital Densitometer).
o. The relative sensitivity was expressed assuming that the sensitivity at a density of 1 was 2.5 at 100. Gamma is 0.1 or 3.0.
And that a gamma value of 10 or more in the table indicates that a super-high contrast image can be obtained.

(Evaluation of storage stability with time and black spots) Evaluation of storage stability was performed by using a sample prepared by coating the emulsion at 23 ° C. and a relative humidity of 6 ° C.
After the humidity was controlled at 0% for 24 hours, the package was sealed in a wrapping paper that shuts out the passage of moisture and air, stored at 55 ° C. for 7 days, and the developed sample obtained by the above method was evaluated for the occurrence of black pot.

The evaluation method was such that an unexposed portion was visually evaluated using a magnifying glass with a magnifying power of 40, and no black spots were generated. The highest rank was "5", and the rank "4" was determined according to the degree of black spots generated. , "3", "2", and "1", and ranks were sequentially reduced. Ranks “2” and “1” are levels that are not practically desirable.

(Evaluation of Drying Properties) The drying temperature of the sample for one week after the application and the sample subjected to the heat treatment were changed by changing the drying temperature of the automatic developing machine, and the drying property when the sample came out of the automatic developing machine was evaluated to five ranks by touch. did. A level of 2 or less was undried and not practical, and a level of 3 to 5 was practical and 5 was the best level that was completely dry.

The composition of the processing solution used is shown below.

(Developer composition) Diethylene triamine 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 such an amount that the pH of the working solution became 10.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per liter of used 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 Sulfuric acid Aluminum (27% aqueous solution) 25 ml sulfuric acid was used to adjust the pH of the working solution to 4.9.

(Processing conditions) (Step) (Temperature) (Time) Development 35 ° C. for 15 seconds Fixing 35 ° C. for 15 seconds Rinse with water Normal temperature 15 seconds Squeeze / Dry 50 ° C. for 15 seconds Total 60 seconds The results obtained are shown in Table 1.

[0222]

[Table 1]

As is clear from Table 1, the sample of the present invention did not deteriorate in sensitivity and gamma (γ) during storage over time (heat treatment), and generated less black spots than the comparative sample. . Further, the sample of the present invention was superior to the comparison in drying property in an automatic processor.

Example 2 Example 1 was repeated except that the compounds (I) and (III) were used instead of the compounds (I) and (II) of the hardener in Example 1.
A light-sensitive material was prepared in the same manner as in
Shown in

[0225]

[Table 2]

As is clear from Table 2, the sample of the present invention shows less deterioration in sensitivity, gamma (γ) and generation of black spots during storage over time than the comparative sample. Further, the drying property in the automatic developing machine was superior to the comparison.

Example 3 A light-sensitive material was prepared in the same manner as in Example 1 except that the compounds (IV) and (II) were used instead of the compounds (I) and (II) of the hardener in Example 1. Table 3 shows the results of the evaluation.

[0228]

[Table 3]

Example 4 Example 1 was repeated except that the compounds (IV) and (III) were used in place of the compounds (I) and (II) of the hardener in Example 1.
A photosensitive material was prepared in the same manner as in
Shown in

[0230]

[Table 4]

As is clear from Tables 3 and 4 in the above table,
It can be seen that the sample of the present invention has less sensitivity and less deterioration of gamma (γ) even with a storage test by heat treatment, and the occurrence of black spots is smaller than that of the comparative sample. Further, the drying property in the automatic developing machine was superior to the comparison.

[0232]

As demonstrated in the examples, according to the present invention, a silver halide for printing plate making, which has improved storage stability with time, black spot generation, and dryness in rapid processing of a photosensitive material hardened with a hydrazine derivative. A photographic light-sensitive material and a processing method thereof were 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 5/395 5/395

Claims (7)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer comprises a sensitizing dye represented by the following general formula [S]. The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains at least two kinds of hydrazine derivatives, and at least one of the compounds represented by the following general formula [I]. A silver halide photographic light-sensitive material characterized by being hardened with a seed and at least one kind of a compound represented by the following general formula [II]: 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. 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
One group 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 V
¹ and V ² represent a group which forms a condensed ring together with an azole ring, and L ¹ , L ² , L ³ and L ⁴ each independently represent a substituted or unsubstituted methine group. n represents 1 or 2, and m represents 0
Or represents 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. Embedded image In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group or an aralkyl group which may be substituted, and may be the same or different. R ₁ and R ₂ may combine with each other to form a heterocyclic ring together with a nitrogen atom. R ₃ represents an alkyl group, an alkoxy group, an acyl group, or an acylamino group which may have a substituent. X ⁻ represents an anion, and n and m each represent 0 or 1. Embedded image In the formula, X ₁ is a halogen atom, an N-methylolamino group,
Represents a glycidoxy group or an ethyleneimine group. Y ₁ represents a hydrogen atom, a halogen atom (for example, a chlorine atom), —ON ₂ , an alkoxy group, a substituted or unsubstituted amino group (an alkyl group, a phenyl group, a sulfonated phenyl group, a carboxylated phenyl group, a hydroxyalkyl Group, sulfonated alkyl group), N-methylolamino group, glycidoxy group, ethyleneimine group, and substituted mercapto group. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein said silver halide emulsion layer comprises a sensitizing dye represented by formula (S). The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and is at least one of the compounds represented by the general formula [I]. A silver halide photographic light-sensitive material characterized by being hardened with a seed and at least one kind of a compound represented by the following general formula [III]. Embedded image In the formula, Y represents a vinyl group, A represents a divalent group, and p is 0 or 1. R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be the same or different. 3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer comprises a sensitizing dye represented by the general formula [S]. The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative, and is at least one of the compounds represented by the general formula [II]. A silver halide photographic light-sensitive material characterized by being hardened with a seed and at least one kind of a compound represented by the following general formula [IV]: Embedded image In the formula, R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may be substituted. q represents 0 or 1. 4. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer is formed of a sensitizing dye represented by the formula (S). The silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer contains a hydrazine derivative and at least one of the compounds represented by the general formula [III]. A silver halide photographic material characterized by being hardened with a seed and at least one of the compounds represented by the general formula [IV]. 5. A high contrast gamma of 10 to 40 by processing the silver halide photographic material of claim 1 with a developer having a pH of 9.0 to 11.0. A method for processing a silver halide photographic light-sensitive material, characterized by obtaining an image. 6. A method for subjecting a silver halide photographic material according to any one of claims 1 to 4 to at least development, fixing, washing with water or stabilization using an automatic development processor after exposure. The replenishing amount of the developing solution and / or the fixing solution is from 75 to 25 per m ^{2 of the} silver halide photographic material.
0 ml of a silver halide photographic light-sensitive material. 7. The method for processing a silver halide photographic material according to claim 5, wherein the total processing time (Dry to Dry) of the silver halide photographic material is 10 to 60 seconds.