JPH0990548A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a silver halide photographic sensitive material excellent in dot quality and dot reproducibility, high in sensitivity, high in density, having high γ and eliminating a generation of a black spot by incorporating a redox compd. satisfying a specified condition. SOLUTION: One kind redox compd. which restrains development by being oxidized and satisfies the conditions of (1)-(3) is incorporated in a silver halide emulsion layer and/or adjacent hydrophilic colloid layer, and a supporting body is a stretched film consisting of a syndiotactic polystyrene. (1) a development restrainer releasing ratio (%) under the condition A is <=4.5, (2) the development restrainer releasing ratio (%) under the condition B is <=15.0, (3) (the development restrainer releasing ratio (%) under the condition A)>(the development restrainer releasing ratio (%) under the condition B). Provided that the development restrainer releasing ratio is (a measured development restrainer concn./the concn. at the time of 100% releasing)×100.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art A light-sensitive material for printing plate making usually requires super-high contrast image reproduction because a halftone image is used. As ultra-high contrast technology in recent years, for example, U.S. Pat. No. 4,269,9
A photographic light-sensitive material containing a hydrazine derivative disclosed in No. 29 is known.

In printing plate making, in order to produce an excellent printed matter, it is necessary to faithfully reproduce desired halftone dots on the photosensitive material for plate making. In recent years, there has been an increasing demand for improvements in halftone dot quality. For example, high-definition printing of 600 lines / inch or more and a method called FM screening composed of a random pattern of uniform minimal dots have a fineness of 25 μ or less. It is required to reproduce such points.

These are image output machines equipped with a laser light source such as an argon laser, a He-Ne laser, and a semiconductor laser. The so-called plate-making scanner is used for exposure and the transmissive halftone image original is exposed by a printer. It is necessary that the target minute halftone dot be faithfully reproduced when the operation is performed.

The photoengraving process includes a process of converting a continuous tone original into a halftone dot image. There is a demand for a technique capable of reproducing an ultra-high contrast image in this step, and for that purpose, for example, JP-A-56-106244 discloses a method using a hydrazine derivative.

However, while this method can obtain super-high contrast and high-sensitivity photographic characteristics, the infectious developability is too strong.
The halftone dot has a defect that it is blackened even in the part that is removed as a white background, and as a result, the halftone is very short and the reproducibility of the original cannot be obtained.

In order to improve the reproducibility of the original, it is not enough that the light-sensitive material faithfully reproduces the optical information, and only the large dot portion or the portion where the thin line of the character is missing is selectively suppressed in development. It is necessary. Examples of such attempts include, for example, JP-A-61-213847 and JP-A-62-123847.
260153, hydrazine derivatives disclosed in JP-A-4-136839, and the like, or
No. 438, No. 4-563, No. 4-6548, No. 4-
There is known a method of releasing a development inhibitor like a silver image from a redox compound such as a hydroquinone derivative disclosed in JP-A-6551.

However, the redox reactivity of these compounds tends to depend on the pH of the developing solution, and when treated with a developing solution having a relatively low pH (for example, pH = 11 or less),
Although an ultra-high contrast image can be obtained by using a hydrazine derivative as a nucleating agent, the reproduction of minute halftone dots of 25 μm or less deteriorates the halftone dot reproducibility and causes unexposed areas called black spots. This is a technique that causes a problem that sand-like spots are likely to occur and has a problem in practical use, and further improvement has been desired.

[0009]

Therefore, the object of the present invention is to provide excellent dot quality and dot reproducibility, high sensitivity, high density and high gamma even when reproducing minute dots of 25 μm or less. And to provide a silver halide photographic light-sensitive material for plate making which does not generate black spots.

Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material capable of obtaining a stable and ultrahigh contrast image by using a developing solution having a relatively low pH (pH = 11.0 or less). To do.

[0011]

As a result of intensive studies, the present inventor has found that the above object of the present invention can be achieved by the following.

(I) In a silver halide photographic light-sensitive material having a silver halide emulsion layer on one surface of a support, the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto is oxidized. A stretched film containing at least one redox compound satisfying the following conditions (1) to (3), and the support containing syndiotactic polystyrene as a main component. A silver halide photographic light-sensitive material characterized by being present.

(1) Development inhibitor release rate (%) under the following conditions (A) ≧ 4.5 (2) Development inhibitor release rate (%) under the following conditions (B) <
15.0 (3) Development inhibitor release rate (%) under the following condition (A)>
Development inhibitor release rate (%) under the following condition (B) Condition (A): 50 μM methanol-acetonitrile (1: 1) which is a compound capable of releasing the development inhibitor at a constant temperature of 35 ° C.
1) 5 parts of the solution and 1 part of 100 mM hydrogen peroxide aqueous solution are mixed, 2 parts of carbonate buffer having a pH of 10.2 is added, and 30 seconds after the addition, 1 part of 100 mM acetic acid in methanol solution is added.

Condition (B): Under constant temperature of 35 ° C., 5 parts of a 50 μM methanol-acetonitrile (1: 1) solution of a compound capable of releasing a development inhibitor is mixed with 1 part of distilled water to adjust pH.
30 seconds after adding 2 parts of 10.2 carbonate buffer, 1 part of 100 mM acetic acid in methanol is added.

Development inhibitor release rate (%): (measured development inhibitor concentration / development inhibitor concentration at 100% release) × 100 (II) of a redox compound satisfying the following condition (4): The silver halide photographic light-sensitive material according to item (I), which contains at least one kind.

(4) The development inhibitor release rate (%) under the above condition (A) / the development inhibitor release rate (%) under the above condition (B) is 1.5 or more and 10 or less. .

(III) The silver halide photographic light-sensitive material according to item (I) or (II), wherein the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto contains a hydrazine derivative. .

(IV) The silver halide photographic light-sensitive material is exposed to light and then treated with a developer having a pH of 8.5 or more and 11.0 or less, any one of (I) to (III). 5. A method for processing a silver halide photographic light-sensitive material as described in the above item.

The present invention will be described in detail below.

In the present invention, a redox which can be added to an emulsion layer or a hydrophilic colloid layer adjacent thereto and oxidized by an oxidized product of a developing agent to release a development inhibitor through a nucleophilic reaction to a carbonyl group. The compound will be described.

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones, α-aminoketones and the like as redox groups.
Preferred redox compounds are -NH as a redox group.
Compounds having an NH- group and the following general formulas [I] and [I
The compound is represented by I], [III], [IV], [V] or [VI].

[0022]

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[0023]

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The compound having --NHNH-- as a redox group is represented by the following general formula [RE-a] or [RE-
b].

General Formula [RE-a] T-NHNHCOV- (Time) -PUG General Formula [RE-b] T-NHNHCOCOV- (Time) -PUG Of the General Formulas [RE-a] and [RE-b] In the formula, T and V each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. A preferable substituent is a linear or branched alkyl group (preferably Are those having 2 to 20 carbon atoms, such as methyl, ethyl, isopropyl group, dodecyl group, etc., alkoxy groups (preferably those having 2 to 21 carbon atoms, such as methoxy, ethoxy group, etc.), aliphatic acylamino groups (preferably carbon). Number 2 to 2
1 having an alkyl group such as acetylamino, heptylamino group), aromatic acylamino group and the like. In addition to these, for example, the above-mentioned substituted or unsubstituted aromatic ring is -CONH-,- _{O -, - SO 2 NH -} , -
NHCONH -, - including those attached with a linking group such as CH ₂ CHN-. As PUG, 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole,
5-nitrobenzotriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole and the like can be mentioned. These development inhibitor compounds are
It can be connected to the CO site of —NHNH—CO— either directly via a heteroatom such as N or S or via an alkylene, phenylene, aralkylene or aryl group and further via a heteroatom such as N or S. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2-
(Dodecylethylene oxide thiopropionamide) -5- (5-nitroindazol-2-yl) hydroquinone, 2- (stearylamide) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2-
(2,4-di-t-amylphenoxypropionamide) -5- (5-nitrotriazol-2-yl) hydroquinone, 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone, etc. Can be mentioned. These redox compounds are described in US Pat.
It can be synthesized with reference to the method described in No. 69,929.

The redox compound is contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer. Addition of redox compounds includes alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, esters such as ethyl acetate, acetone and methyl ethyl ketone, etc. It can be added after being dissolved in ketones. For those that are difficult to dissolve in water or organic solvents, the average particle size is 0.01 to 6μ by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, etc.
Can be dispersed in any particle size up to. For the dispersion, a surface active agent such as anion or nonion, a thickener, a latex and the like can be added and dispersed.

The redox compound may be added in an amount of from 10 ^-6 to 10 ^-1 mol, and preferably from 10 ^-4 to 10 ^-2 mol, per 1 mol of silver halide.

Among the compounds represented by the general formula [RE-a] or [RE-b], particularly preferable compounds are shown below.

[0029]

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[0030]

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Specific examples of other preferable redox compounds include 236 of JP-A-4-245243.
(8) page “0053” to 250 (22) page “0068”
R-1 to R-50 described in 1. The redox compounds represented by the general formulas [I] to [VI] will be described below.

In the general formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group.
R ₄ represents a hydrogen atom. R ₅ to R ₉ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃
Represents a substituent capable of substituting on the benzene ring. X ₁ and X ₂ are O
Or represents NH. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W is N (R ₁₀ ) R ₁₁ or O
Represents H, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and a star represents a coupling site of the coupler. Tm represents a timing group. m ₁ and p ₁ represent an integer of 0 to 3. q ₁ represents an integer of 0 to 4. n represents 0 or 1. PUG represents a development inhibitor.

The above general formulas [I] to [VI] (hereinafter, in the formula)
In the above, the alkyl group, aryl group and heterocyclic group represented by R ₁ and R _{5 to} R ₁₁ are preferably methyl group, p-
Examples include a methoxyphenyl group and a pyridyl group. R ₂
And an acyl group represented by R ₃ , a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group, and an aryloxycarbonyl group, preferably an acyl group, a carbamoyl group, It is a cyano group. The total number of carbon atoms in these groups is preferably 1 to 20. R _{1 to} R ₁₁ may further have a substituent, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, hydroxyethyl, methoxymethyl, trifluoro). Methyl, t-butyl group, etc.),
Cycloalkyl group (eg cyclopentyl, cyclohexyl group etc.), aralkyl group (eg benzyl, 2-phenethyl group etc.), aryl group (eg phenyl, naphthyl, p-tolyl, p-chlorophenyl group etc.), alkoxy group (eg methoxy, Ethoxy, isopropoxy, butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino, propionylamino group etc.), alkylthio group (eg methylthio, ethylthio, butylthio group etc.), arylthio Group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino, benzenesulfonylamino group etc.), ureido group (eg 3-methylureido, 3,3-dimethylureido, 1,3-dimethylureido group etc.), Sur Amoylamino group (such as dimethylsulfamoylamino group), carbamoyl group (such as methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl group and the like), sulfamoyl group (such as ethylsulfamoyl and dimethylsulfamoyl group), alkoxycarbonyl group (eg, Methoxycarbonyl, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl, butanesulfonyl, phenylsulfonyl group etc.), acyl group (eg acetyl, propanoyl,
Butyroyl group, etc.), amino group (methylamino, ethylamino, dimethylamino group, etc.), hydroxyl, nitro,
Examples thereof include an imide group (eg, phthalimide group) and a heterocyclic group (eg, pyridyl, benzimidazolyl, benzthiazolyl, benzoxazolyl group, etc.).

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

[0036]

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

[0038]

[Chemical 6]

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

[0040]

[Chemical 7]

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

[0042]

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

[0044]

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R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The 5- or 6-membered heterocycle represented by Z ₁ may be a monocycle or a condensed ring, and includes a 5- or 6-membered heterocycle having at least one of O, S, and N atoms in the ring. . You may have a substituent on these rings,
Specific examples thereof include the above-mentioned substituents.

The timing group represented by Tm is preferably --OCH2- or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
23, or 3,674,478, RD, No. Two
1228 (December 1981), or JP-A-57-5.
No. 6837, those described in JP-A-4-438, and the like. Preferred development inhibitors for PUG are, for example, U.S. Pat. No. 4,477,563 and JP-A-60-218644.
No. 60, No. 60-221750, No. 60-233650.
Or the development inhibitors described in JP-A No. 61-11743.

General formulas [I] used in the present invention are described below.
Specific examples of the compound represented by [VI] are listed below, but the present invention is not limited thereto.

[0048]

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[0049]

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[0050]

[Chemical 12]

[0051]

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[0052]

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[0053]

[Chemical 15]

[0054]

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[0055]

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General formula [I] preferably used in the present invention
The compound represented by [VI] is preferably contained in an amount of 1 × 10 ⁻⁶ to 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol per mol of silver halide. Is preferred.

The compounds represented by the above general formulas [I] to [VI] can be used by dissolving them in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide, methylcellosolve and the like. it can. Also, it can be added as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves by a method known as a solid dispersion method.

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

Low pH of the redox compound in the present invention
In order to confirm the effect of DIR at (pH = 11.0 or less), the release rate of the development inhibitor was measured under the above conditions.

Under the condition (A), hydrogen peroxide was used as the developing agent oxidant, and hydrogen peroxide was added to the solution of the compound of the present invention to make an alkaline solution having a pH of 10.2, and then 30
After a second, acetic acid was added to stop the reaction. The concentration of released inhibitor was quantified by high performance liquid chromatography. It was quantified by comparing the peak areas to inhibitor solutions of known concentration. The development inhibitor release rate A (%) under the condition (A) is (measured inhibitor concentration / 100%
The concentration of the inhibitor at the time of release) was calculated.

Under the condition (B), the measurement was performed in the same manner as in the condition (A) except that the buffer solution was used instead of the oxidized product of the developing agent, and the development inhibitor release rate B (%) under the condition (B). Was calculated. The development inhibitor release rate B (%) represents the rate at which the development inhibitor is released by the nucleophilic reaction without being oxidized by the oxidized developing agent.

When the development treatment is carried out with a developer having a pH of 11.0 or less, A (%) is preferably 4.5 or more, more preferably 10 or more. Also, B (%) is preferably 15 or less, 1
0 or less is more preferable. However, A (%) / B (%) is 1
It needs to be larger, and is preferably 1.5 or more.

The support of the silver halide photographic light-sensitive material in the present invention is a syndiotactic polystyrene (hereinafter referred to as S
It is a stretched film containing PS as a main component. Here, SPS means that the stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, a carbon-carbon bond and a phenyl group or a substituted phenyl group, which are side chains with respect to the main chain formed, are in opposite directions. A styrene-based polymer having a three-dimensional structure positioned in the main chain and a main chain of which is a racemo chain or a composition containing the same, and a homopolymer of styrene is disclosed in JP-A-62-117708.
It is possible to polymerize by the method described in JP-A No. 1-46912 and 1-1.
It can be polymerized by the method described in Japanese Patent No. 78505.

The tacticity is quantified by the nuclear magnetic resonance method (13C-NMR method) using isotope carbon.
The tacticity measured by the 13 C-NMR method can be represented by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. The styrene-based polymer having a syndiotactic structure of the present invention,
Usually 75% or more, preferably 85% in racemic diad
Or more, or 60% or more of racemic triad, preferably 75% or more, or 30% or more of racemic pentad,
It is preferably 50% or more.

Specific monomers of the polymer constituting the syndiotactic polystyrene composition are styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, vinyl. A single or a mixture containing benzoic acid ester as a main component.

Particularly, the copolymer of alkylstyrene and styrene is a preferable combination for obtaining a film having a film thickness of 50 μm or more.

The polystyrene resin having a syndiotactic structure according to the present invention uses the above-mentioned raw material monomers as a catalyst for polymerization, and is disclosed in JP-A-5-320448, pages 4 to 1.
(A), (a) transition metal compound and (b) described on page 0
Aluminoxane as a main component, or (b),
It can be produced by polymerization using a compound containing as a main component a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex.

To produce the styrenic polymer used in the support of the present invention, the styrenic monomer is first thoroughly purified and then polymerized in the presence of any of the above catalysts.

At this time, the polymerization method and the polymerization conditions (polymerization temperature,
The polymerization time), the solvent, etc. may be appropriately selected. Usually-
Polymerization is carried out at a temperature of 50 to 200 ° C., preferably 30 to 100 ° C. for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, a slurry polymerization method,
Any of a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used.

In the solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane and octane are used alone or in combination.
More than one species can be used in combination. in this case,
The monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like. Further, other monomers copolymerizable with these may be copolymerized to the extent that the effects of the present invention are not impaired.

The polymer used to form SPS (syndiotactic polystyrene) has a weight average molecular weight of 1
It is 50,000 or more, more preferably 30,000 or more. If the weight average molecular weight is less than 10,000, the film may not have excellent strength properties and heat resistance. The upper limit of the weight average molecular weight is not particularly limited, but if the weight average molecular weight is 1,500,000 or more, breakage may occur due to an increase in stretching tension.

The molecular weight of the SPS film of the present invention is not limited as long as it is formed, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 30,000 to 15,000,000.

The molecular weight distribution at this time (number average molecular weight /
The weight average molecular weight) is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights. Further, the syndiotactic polystyrene-based film of the present invention contains syndiotactic polystyrene-based pellets at 120 to 180 ° C.
Dry for 1 to 24 hours under vacuum or under normal pressure in an atmosphere of inert gas such as air or nitrogen. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less, and more preferably 0.005% or less from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis. . However, these methods are not particularly limited as long as the purpose is achieved.

<Polymerization Example> SPS pellets were prepared according to JP-A-3-131843. The process from the preparation of the catalyst to the polymerization reaction was carried out under a stream of dry argon.

In a glass container having an inner volume of 500 ml, 17.8 g (71 mmo) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) was added.
l), 200 ml of purified benzene and 24 ml of trimethylaluminum were added, and the mixture was stirred at 40 ° C. for 8 hours to prepare a catalyst.

This was subjected to No. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out, put in a stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C. 1 liter of purified styrene was added to this, and 70 ml of further purified p-methylstyrene was added, and the polymerization reaction was continued at this temperature for 8 hours.

After that, the mixture was cooled to room temperature, 1 liter of methylene chloride was added, and a methanol solution of sodium methylate was added with stirring to deactivate the catalyst. The contents were gradually dropped into 20 l of methanol, filtered through a glass filter, washed with methanol three times, and then dried.

The weight average molecular weight of this polymer was 1,2,4-trichlorobenzene as a solvent, and the weight average molecular weight of this polymer was determined from the result of GPC measurement with standard polystyrene at 135 ° C.
It was 415,000. The melting point of this polymer is 24
It was confirmed from the 13-NMR measurement at 5 ° C. that the polymer obtained also had a syndiotactic structure. This was pelletized with an extruder and then dried at 130 ° C.

The SPS film of the present invention is preferably SPS alone made from styrene, but further SPS
As a film containing styrene, a styrene-based polymer (IP having an isotactic structure whose main chain is a meso chain in SPS)
By mixing S), the crystallization rate can be controlled and a stronger film can be obtained. When SPS and IPS are mixed, the ratio depends on the stereoregularity of each other, but is 30: 70-9.
9: 1 is preferable, and 50:50 to 98: 2 is more preferable. In the support, inorganic fine particles, an antioxidant, and UV are added for the purpose of imparting functionality within a range not impairing the object of the present invention.
It is possible to contain an absorbent, an antistatic agent, a dye, a pigment, a dye, or the like.

A known method can be applied as a method for extruding during film formation, but it is preferable to extrude with a T-die, for example. 280 syndiotactic polystyrene pellets
It is melted and extruded at ˜350 ° C., and is cooled and solidified on a casting roll while applying static electricity to produce an unstretched film. Next, the unstretched film is biaxially stretched and biaxially oriented. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed,
Sequential biaxial stretching method of longitudinal stretching, horizontal / longitudinal / longitudinal stretching method, longitudinal / horizontal
A longitudinal stretching method, a longitudinal / longitudinal / horizontal stretching method, a simultaneous biaxial stretching method, or the like can be adopted, and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability.

In general, a sequential biaxial stretching method in which stretching is carried out first in the longitudinal direction and then in the width direction is preferred. In this case, the stretching ratio in the longitudinal and transverse directions is 2.5 to 6 times, and the longitudinal stretching temperature is that of the polymer. Although it depends on the glass transition temperature (Tg), it is usually stretched in the temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. In the case of a syndiotactic polystyrene film, it is preferably carried out at 110 to 150 ° C. The stretching temperature in the width direction is slightly higher than that in the longitudinal direction and is 115
It is preferably carried out at ˜160 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case can be appropriately changed depending on the application. For shrink-wrapping applications that require high shrinkage, 150 ° C or lower, and for photographic, printing, and medical applications that require dimensional stability, 150 to 2 depending on the purpose.
A temperature of 70 ° C is adopted. The heat treatment time is not particularly limited, but is usually 1 second to 2 minutes.

It goes without saying that longitudinal heat relaxation, horizontal heat relaxation treatment, etc. may be carried out as necessary.

After this, the film may be rapidly cooled and wound, but it is gradually cooled between Tg and the heat treatment temperature for 0.1 minute to 1500 hours and wound on a large diameter core, and further wound between 40 ° C. and Tg. It is preferable to cool at an average cooling rate of −0.01 to −20 ° C./min, because it has an effect of making it difficult to wind the support. Of course, it is preferable that the heat treatment at 40 ° C. to Tg is carried out in a constant temperature bath for 0.1 minutes to 1500 hours after winding the support to cutting the product after coating the emulsion.

In order to impart various characteristics such as slipperiness, adhesiveness and antistatic performance to the film forming method described above, an SPS support having the above-mentioned characteristics is laminated on at least one surface of the SPS support. It is also possible to produce the SPS laminated film. The lamination method is such that the resin is melted and laminated in a laminar flow, and then extruded from a die, or the melted SPS is extrusion-laminated on the cooled and solidified SPS unstretched support or SPS uniaxially stretched support, and then the longitudinal direction. -It is obtained by stretching in both the transverse directions or in the direction perpendicular to the uniaxial stretching direction and heat setting. SP
Although the extrusion conditions, the stretching temperature, the stretching ratio, the heat setting temperature, etc. of the S resin are slightly different depending on the combination of the SPS laminated supports, they may be finely adjusted so as to select the optimum conditions and do not make a great change. Needless to say, the laminate may be composed of two or more layers, and may be a combination of the same type of polymers (including a combination of copolymerized polymers) or a different type of polymers.

The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the thus-obtained syndiotactic polystyrene-based stretched film varies depending on the application, but is 0.3 μ for ultra-thin capacitors, and 6 μ and 12 μ for ordinary capacitors. The above film forming conditions are effective for those having a thickness of 0.3 to 500 μ, which are various, such as thickness, 100 μ for medical and printing sensitive materials, and 250 μ for electrical insulating material (slot liner etc.).

Next, the undercoating treatment of the support will be described. When applying the undercoat layer, it is preferable to perform chemical treatment, mechanical surface roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like. The surface tension of the surface is preferably 50 dyne / cm or more by these treatments.

The undercoat layer may be any one used in the art.

The subbing layer may be a single layer, but it is desirable that it is a multi-layer in order to obtain more functionality and enhance the adhesive strength. The first subbing layer in the multi-layer method preferably adheres well to the support, and the material is an unsaturated carboxylic acid such as methacrylic acid or acrylic acid or its ester, styrene, vinylidene chloride, vinyl chloride or the like. Polymers or copolymers obtained from the body, water-dispersed polyester, polyurethane, polyethyleneimine, epoxy resin and the like are preferable. Of these, particularly preferred are copolymers having a water-dispersible polyester and a styrene polymer as constituent elements.

The copolymer or composition containing the water-dispersible polyester and the styrenic polymer as constituent elements will be described. The water-dispersible polyester referred to here is a substantially linear polymer obtained by a polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. Polybasic acid components of this polymer include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-
Examples thereof include cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid and the like. Unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and p
A small proportion of hydroxycarboxylic acids such as -hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used.

Further, as the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglyceride, and Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water-dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol, etc. is an effective means. In particular, a dicarboxylic acid component having a sulfonic acid salt (a dicarboxylic acid having a sulfonic acid salt and / or
Or an ester-forming derivative thereof) in an amount of from 5 to 15 mol% based on all dicarboxylic acid components in the water-dispersible polyester.

As the dicarboxylic acid having a sulfonic acid salt and / or its ester-forming derivative used in the undercoat layer, one having an alkali metal sulfonate group is particularly preferable. For example, 4-sulfoisophthalic acid, 5- Sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid,
Although an alkali metal salt such as 5- (4-sulfophenoxy) isophthalic acid or an ester-forming derivative thereof is used, 5-sulfoisophthalic acid sodium salt or an ester-forming derivative thereof is particularly preferable. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of from 6 to 10 mol% based on all dicarboxylic acid components from the viewpoint of water solubility and water resistance.

As the monomer of the styrene polymer used for the undercoat layer, when styrene is used alone or when it is copolymerized, for example, alkyl acrylate or alkyl methacrylate (as the alkyl group, methyl, ethyl, n-propyl or isopropyl) is used. , N-butyl, isobutyl, t-
Butyl, 2-ethylhexyl, cyclohexyl, phenyl, benzyl, phenylethyl groups, etc.); hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacryl Amide group-containing monomers such as amide, N-methylmethacrylamide, N-methylacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide;
N, N-diethylaminoethyl acrylate, N, N-
Amino group-containing monomer of diethylaminomethacrylate; Epoxy group-containing monomer such as glycidyl acrylate and glycidyl methacrylate; Acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt), etc. Monomers containing sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof;
Monomers containing carboxyl groups such as itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt) or salts thereof; monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride And vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride and the like. The above-mentioned monomers can be copolymerized using one kind or two or more kinds. To modify the water-dispersible polyester into a vinyl-based polymer, a method of introducing an addition-polymerizable group at the terminal of the water-dispersible polyester and copolymerizing with a monomer of the vinyl-based copolymer for grafting, There is a method of introducing a reactive group at the time of polycondensation of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or an amino group as a monomer by polymerizing a system copolymer.

Further, the polymerization initiator is ammonium persulfate,
Examples thereof include potassium persulfate and sodium persulfate, and ammonium persulfate is preferably used. Furthermore, the polymerization does not require a surfactant, and the reaction can be carried out soap-free. However, for the purpose of improving the polymerization stability, a surfactant can be used as an emulsifier in the system, and any nonionic or anionic surfactant can be used.

The modification ratio of the water-dispersible polyester and the styrene copolymer is 99/1 to 5/95, preferably 97/3 to 50/50, and more preferably 95/5.
~ 80/20 is good.

In order to improve the coatability, it is preferable to add an activator or a cellulose compound such as methyl cellulose in the first subbing layer. The subbing treatment may be carried out after the film formation, but if the subbing composition is stretchable, before the longitudinal stretching which is in the process of film formation, between the longitudinal stretching and the lateral stretching, after the lateral stretching, It can be performed at any place such as in front. When stretching is not possible For example, when using a polymer having a hydrophilic group, the interaction between the hydrophilic polymers is strong, so stretching may not be possible, but stretching under steam or addition of polyglycerin or the like as a stretching aid By doing so, stretching becomes possible.

Among the monomers having a hydrophilic group, preferred examples are unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride. From the viewpoint of water resistance, the content is preferably 1 to 10% by weight, more preferably 1 to 8% by weight, more preferably 1 to 6% by weight, and most preferably 1 to 4% by weight. Further, as the fourth component of this copolymer, other copolymerizable monomers in the range of 0 to 15% by weight, preferably 0 to 10% by weight,
It can be copolymerized if necessary. Examples of this include alkyl-substituted styrenes such as methylstyrene, halogenated styrenes such as chlorostyrene and chloromethylstyrene,
Unsaturated nitrile compounds such as acrylonitrile, aliphatic such as methyl acrylate, methyl methacrylate, t-butyl acrylate, alicyclic such as cyclohexyl methacrylate,
Examples thereof include aromatic (meth) acrylic acid ester compounds such as benzyl acrylate, and rubber-modified compounds such as butadiene and isoprene.

The method for producing these copolymers is not particularly limited and can be usually obtained by radical polymerization using a generally known radical initiator. The weight average molecular weight of the copolymer composed of these monomers measured by GPC method in terms of standard polystyrene is 1,500 to 700,
000 is preferable, and 2,000 to 500,0
More preferably, it is 00.

The second subbing layer is preferably a hydrophilic resin layer that adheres well to the photographic emulsion layer. Binders that constitute the hydrophilic resin layer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch and polyvinyl. Examples thereof include alcohols, polyacrylic acid copolymers, water-soluble polymers such as carboxymethyl cellulose and hydroxyethyl cellulose, and combinations of sodium polystyrene sulfonate copolymers and hydrophobic latex, with gelatin being preferred. It is preferable to use a hardener in the undercoating second layer to enhance the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, and US Pat. No. 2,732,303. ,
No. 3,288,775, British Patent 974,723,
No. 1,167,207, etc., compounds having a reactive halogen, diacetyl, ketone compounds such as cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1, 3,5-
Triazine, divinyl sulfone, 5-acetyl-1,3
-Diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,232,763 and 3,635,7.
18, compounds having a reactive olefin described in British Patent 994,809, etc., US Pat. No. 3,539,644
No. 3,642,486, Japanese Patent Publication No.49-13568
No. 53-47271, No. 56-48860, No. 53-57257, No. 61-128240, No. 62-4275, No. 63-53541, No. 63-2.
Vinylsulfone compounds described in No. 64572, N-hydroxymethylphthalimide, US Pat. No. 2,732,3
16, N2,586,168, etc., N-methylol compounds, US Pat. No. 3,103,437, etc., isocyanate compounds, US Pat. No. 2,983,611.
And the aziridine compounds described in U.S. Pat. Nos. 2,725,294 and 2,725,2.
Acid derivatives described in US Pat. No. 3,100,7
No. 04, etc., carbodiimide compounds, U.S. Pat. No. 3,091,537, etc. epoxy compounds, U.S. Pat. Nos. 3,321,313, 3,543,292, etc. isoxazole compounds. , Organic hardeners such as halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-59625 and JP-A-62-26 are mentioned.
No. 2854, No. 62-264044, No. 63-184.
No. 741 N-carbamoylpyridinium salts,
It has two or more acyl-imidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, and two or more N-acyloxyimino groups described in JP-B-53-22089. Compounds, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113
A compound having a phosphorus-halogen bond described in No. 929,
JP-A-60-225148 and 61-240236.
Nos. 63-41580 and chloroformamidinium compounds are known.

Silicon dioxide is used as a slipping agent in the second undercoat layer.
It is preferable to contain inorganic fine particles such as titanium dioxide and an organic matting material (1 to 10 μm) such as polymethylmethacrylate. In addition to these, various additives such as an antistatic agent, an antihalation agent, and a coloring dye, if necessary.
A pigment and a coating aid can be contained. Among these, it is preferable to include an antistatic agent, and preferable antistatic agents include non-photosensitive conductors and / or semiconductor fine particles. The non-photosensitive conductor and / or semiconductor fine particles used in the undercoat layer means charge carriers existing in the particles, such as cations, anions, electrons,
It exhibits conductivity by holes and may be an organic material, an inorganic material, or a composite material of both. Preferably, it is a compound exhibiting electron conductivity, and if it is an organic material, for example, polymer fine particles such as polyaniline, polypyrrole and polyacetylene can be cited. Examples of the inorganic material include fine particles of a metal oxide that easily form a nonstoichiometric compound such as an oxygen-deficient oxide, a metal-excessive oxide, a metal-deficient oxide, and an oxygen-excessive oxide. If it is a charge transfer complex or an organic-inorganic composite material, a phosphazene metal complex or the like can be mentioned. Of these, the most preferable compound for the undercoat layer is metal oxide fine particles which can be manufactured by various methods. The conductor in the undercoat layer has a volume resistivity of 10 ³ Ω · cm or less, and is 1 for the semiconductor.
Those of 0 ¹² Ω · cm or less are defined as a conductor and a semiconductor, respectively. The preferred method for producing conductive fine particles will be illustrated below.

(Preparation of Semiconductor Fine Particle Solution) 65 g of stannic chloride hydrate was dissolved in 2000 ml of a water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was added dropwise to the washed distilled water to confirm that there was no chloride ion reaction, and then 1000 ml of distilled water was added to bring the total volume to 2000.
Set to ml. Further, add 40 ml of 30% ammonia water,
It was heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is designated as dispersion A-1.

(Preparation of Semiconductor Fine Particle Powder) 65 g of stannic chloride hydrate and 1.5 g of antimony trichloride were dissolved in 1000 g of ethanol to obtain a uniform solution. 1N- in this solution
An aqueous solution of sodium hydroxide was added dropwise until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was isolated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 100 g of the colloidal precipitate from which excess ions were removed was mixed with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water and sprayed in a firing furnace heated to 900 ° C. to give a bluish average particle size of 0.1.
A powder mixture A-2 consisting of 1 μ of stannic oxide and barium sulfate was obtained.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is 1 to 30 g in terms of coating liquid weight per 1 m ^{2 of} film.
And more preferably 5 to 20 g. As a coating method, various known methods can be applied. For example, a roll coating method, a gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method, a curtain coating method and the like can be applied alone or in combination.

The silver halide photographic light-sensitive material of the present invention exhibits a particularly remarkable effect when a hydrazine compound is used as a contrast adjusting agent in the constituent layers. The hydrazine compound that can be used in the present invention is preferably a compound represented by the following general formula [H].

[0106]

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

Of the compounds represented by the general formula [H], the compound represented by the following general formula [Ha] is more preferable.

[0109]

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In the formula, R ¹ is an aliphatic group (eg octyl group, decyl group), aromatic group (eg phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg pyridyl group, thienyl group, Represents a 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.

The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is an alkyl group having 8 or more carbon atoms which is relatively inactive to photographic properties. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. The silver halide adsorption promoting group is thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, or JP-A-64-9.
No. 0439, for example. In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and when m 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 both are preferably 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 is 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 is —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).

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

[0114]

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[0115]

[Chemical 21]

[0116]

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[0117]

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[0118]

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Specific examples of other preferable hydrazine derivatives include US Pat. No. 5,229,248, fourth column-
(1) to (252) described in the 60th column.

The hydrazine derivative according to the present invention can be synthesized by a known method, for example, the method described in US Pat. No. 5,229,248.

The addition amount may be any amount that makes the toner to have a high contrast (a high contrast amount). The optimum amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc. From 10 ^-6 to 10 ^-1 per mol of silver halide
It is in the range of moles, preferably in the range of 10 ^-5 to 10 ^-2 moles. The hydrazine compound used in the present invention can be used in any layer as long as it is on the silver halide emulsion layer side, but it is preferably used in the silver halide emulsion layer or its adjacent layer. The optimum addition amount varies depending on the grain 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 mol per mol of silver halide. Is preferable,
Particularly, the range of 10 ⁻⁵ to 10 ⁻² mol is preferable.

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

[0123]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorptive group in the molecule. Specific examples of these nucleation accelerators [Na] will be given below.

[0125]

[Chemical formula 26]

[0126]

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[0127]

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[0128]

[Chemical 29]

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group 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 of the general formula [Nb] include those shown below.

[0130]

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[0131]

[Chemical 31]

Specific examples of other preferable nucleation promoting compounds include compounds (2-1) to (2-20) exemplified in JP-A-6-258751 and 6-2587.
The compounds of (3-1) to (3-6) described in No. 51.
The nucleation accelerator 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 addition amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. A molar range is preferred, especially 10 ^-5 to 1
A range of 0 ^-2 mol is preferred.

The silver halide photographic light-sensitive material of the present invention can contain at least one solid disperse dye in its constituent layers. Conventionally, various dyes have been used in silver halide photographic light-sensitive materials for the purpose of improving sharpness and safelight property.

Since this dye is water-soluble and its diffusibility causes deterioration in photographic performance such as sensitivity and gamma, a fine particle solid dispersion method of dye has been recently used.

Compounds represented by the following general formulas [1] to [6] are preferably used as the dye in the solid fine particle dispersion method which can be used in the present invention.

[0136]

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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 represents 0, 1 or 2, and p ₂ represents 0 or 1. However, the dyes represented by the general formulas [I] to [VI] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The acidic nuclei represented by A and A'in the general formulas [1] to [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, Examples thereof 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 and the like. Is mentioned.

Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group and a naphthyl group. The heterocyclic groups represented by Q and Q'in the general formulas [1], [4] and [6] include, for example, pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, pyrazolyl group, imidazolyl group and indolyl group. , A furyl group, a thienyl group and the like. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include those exemplified as the substituents such as the amino group and the heterocyclic group of the compounds of the above general formulas [1] to [5]. In addition, these substituents may have two or more kinds in combination.

Preferred substituents are alkyl groups having 1 to 8 carbon atoms (eg, methyl, ethyl, t-butyl, octyl, 2-hydroxyethyl, 2-methoxyethyl groups, etc.), hydroxy groups, cyano groups, halogen atoms ( For example, a fluorine atom, a chlorine atom, etc., an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy, 2-hydroxyethoxy, methylenedioxy, butoxy group, etc.), a substituted amino group (eg, dimethylamino, diethylamino, di (n −
(Butyl) amino, N-ethyl-N-hydroxyethylamino, N-ethyl-N-methanesulfonamidoethylamino, morpholino, piperidino, pyrrolidino group, etc.), carboxy group, sulfonamide group (for example, methanesulfonamide, benzenesulfonamide) Group, etc.), a sulfamoyl group (eg, sulfamoyl, methylsulfamoyl,
Phenylsulfamoyl group), 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,
Substituent constant Hammett's σp value (Toshio Fujita eds., "Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs", 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, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl, 4-hydroxyphenoxycarbonyl group). Etc.), carbamoyl group (for example, carbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-carboxyphenylcarbamoyl group, etc.), acyl group (for example, methylcarbonyl, ethylcarbonyl, butylcarbonyl, phenylcarbonyl, 4-ethylsulfonamidocarbonyl group, etc.), Alkylsulfonyl group (eg methylsulfonyl, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg phenyl Ruhoniru group, 4-chlorosulfonyl group, etc.).

L ₁ , L ₂ and L _{3 of the} general formulas [I] to [V]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, hexyl group, etc.), an aryl group (eg, phenyl, tolyl, 4 -Hydroxyphenyl group),
Aralkyl groups (eg, benzyl, phenethyl groups, etc.), heterocyclic groups (eg, pyridyl, furyl, thienyl groups, etc.), substituted amino groups (eg, dimethylamino, diethylamino,
And an alkylthio group (eg, methylthio group).

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 the general formula [1]. A dye represented by the formula, and particularly preferably a dye in which Q is a furyl group in the general formula [1].
Specific examples of dyes that are preferably used are shown below, but the dyes are not limited to these.

[0144]

[Chemical 33]

[0145]

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[0146]

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Other preferable specific examples of the compounds represented by the general formulas [1] to [6] include Japanese Patent Application No. 5-27.
No. 7011, pages 19 to 30. I-1 to N
o. I-30, II-1 to II-12, III-1 to III-8,
Examples thereof include IV-1 to IV-9, V-1 to V-8, and VI-1 to VI-5, but are not limited thereto.

A method for producing a solid fine particle dispersion of a dye is described in JP-A Nos. 52-92716 and 55-15535.
No. 0, No. 55-155351, No. 63-197943
No. 3-182743, World Patent WO88 / 04
No. 794, etc. can be used. Specifically, it can be produced using a fine disperser such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disc impeller mill. When the compound in which the solid fine particles are dispersed is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, the compound is dissolved in a weak alkaline aqueous solution and then the pH is lowered to make it weakly acidic. A dispersion of the compound can be obtained by a method of precipitating a fine particle solid or a method of preparing a fine particle solid by simultaneously mixing a weak alkaline solution of the compound and an acidic aqueous solution while adjusting the pH.

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

When the solid fine particle dispersion used in the present invention is produced in the presence of an aqueous dispersion medium, it is preferable to allow a surfactant to coexist during or after the dispersion.
As such a surfactant, an anionic surfactant,
Any of nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates. , Sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-
Anionic surfactants such as acyl-N-alkyl taurines and nonionic surfactants such as saponins, 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-
The compounds 1 to 32 described in No. 277011, pp. 46 to 32 are mentioned, but not limited thereto.

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

The concentration of the dye in the dispersion is from 0.01 to
It is preferably used so as to be 50% by weight, and more preferably 0.1 to 30% by weight. The surfactant may be added at the position where it is added before the dispersion of the dye is started, and 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 or in combination of two or more.

The solid fine particle dispersion of the dye is preferably dispersed so that the average particle diameter is 0.01 to 5 μm,
It is more preferably 0.01 to 1 µ, and particularly preferably 0.01 to 0.5 µ. The coefficient of variation of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 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 dye solid fine particle dispersion used in the present invention is a hydrophilic colloid used as a binder in a photographic constituent layer before the start of dispersion or after the end of dispersion. Can be added.
It is advantageous to use gelatin as the hydrophilic colloid, but other than that, for example, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, and graft of gelatin with a monomer having a polymerizable ethylene group. Polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol,
Partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-
Synthetic hydrophilic polymers such as N-vinylpyrrolidone and polymethacrylic acid, 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 added to the solid fine particle dispersion of dye is from 0.1% to 12% by weight.
%, Preferably 0.5% to 8%. The dye solid fine particle dispersion can also be used in layers constituting a photographic material such as a silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer 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 on the side opposite to the emulsion layer. Further, in particular, in order to enhance the effect of improving the safelight property, it is preferably added to the layer above the emulsion layer.

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

In the present invention, photosensitive and non-photosensitive emulsion layers and non-emulsion layers (hydrophilic colloid layer, hydrophobic polymer layer)
It may also contain a dye dispersed in solid form.
It may be contained in any layer on the side opposite to the emulsion layer with respect to the support. A water-soluble dye may be contained in any layer. The addition amount of the dye dispersed in a solid state in the present invention is preferably an amount that can obtain an absorbance of 0.001 to 2.0 in at least a part of the wavelength region of the light source used for exposure, and particularly preferably. The above absorbance is 0.005
The amount is 1.5. Further, in the present invention, dyes having other absorption wavelengths can be used together in any layer.

The silver halide photographic light-sensitive material of the present invention is most effectively used as an output light-sensitive material, and the light source is an Ar laser, He-Ne laser, red laser diode, infrared semiconductor laser, red LED. Although a laser is typical, any other laser such as a blue laser such as a He—Cd laser can be used. Further, the effect of the present invention is not limited to the laser output sensitive material,
It is also effective in applications such as shooting sensitive materials and return sensitive materials.

After being exposed, the silver halide photographic light-sensitive material of the present invention is subjected to development treatment with a developer having a pH of 8.5 or more and 11.0 or less to form a high contrast image.

A particularly preferred pH is in the range of 8.5 to 11.0.

The developing agents that can be used in the processing method of the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-
Dimethylhydroquinone etc.), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-3-pyrazolidone, 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-
3-pyrazolidone), aminophenols (eg o
-Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines ( For example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3
-Aminopyrazoline, 1- (p-aminophenyl) -3
-Aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, etc.) Complex salts of these, as long as they have a reducing power for use as a developing solution, for example, Ti ³⁺ , V
^It takes the form of a complex salt of ²⁺ , Cr ²⁺ , Fe ^2+, etc., and the ligand is an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA) and its salt, hexametapolyline. Examples thereof include acids, phosphoric acids such as tetrapolyphosphoric acid, and salts thereof. ) Etc. can be used alone or in combination, but 3
-Pyrazolidones and dihydroxybenzenes or aminophenols and dihydroxybenzenes or 3-pyrazolidones and ascorbic acid, aminophenols and ascorbic acid, 3-pyrazolidones and transition metals It is preferable to use it in combination with a complex salt, or in combination with an aminophenol and a transition metal complex salt. The developing agent is usually 0.0
It is preferably used in an amount of 1 to 1.4 mol / l.

Sulfite used as a preservative in the developer,
Examples of metabisulfite 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 developer, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.), solubilizing agent (Eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, polyoxyethylene-containing nonionic surfactants, quaternary ammonium compounds, etc.), surfactants, defoamers, antifoggants (Eg, potassium bromide, halides such as sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or alkali metal salts thereof, Nitrilotriacetate, polyphosphate, etc., development accelerator (eg rice Patent 2,304,025
, A compound described in JP-B-47-45541), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent.

The silver halide photographic light-sensitive material of the present invention may be developed with a developer containing no dihydroxybenzene compound. In this case, it is preferable to contain a compound represented by the following general formula (A).

[0164]

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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 is -CO-
Or represents -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

In this case, a compound represented by the following general formula (Aa) in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0167]

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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. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

The alkyl group in the general formula (A) or the general formula (Aa) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (A) or the general formula (Aa) are shown below.

[0171]

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[0172]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

As the fixing solution, those having a generally used composition can be used. As the fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate can be used. In addition to thiocyanates such as the above, it is possible to use an organic sulfur compound capable of forming a soluble stable silver complex salt, which is known as a fixing agent. Water-soluble aluminum salt that acts as a hardener in the fixer,
For example, they may contain aluminum chloride, aluminum sulfate, potassium alum and the like, and if desired, preservatives (eg, sulfites, bisulfites), pH buffering agents (eg, acetic acid), pH adjusters (eg, sulfuric acid) And a compound such as a chelating agent having a water softening ability. In the development process, washing is performed after fixing, but the washing layer may be a system in which fresh water is supplied at a rate of several liters per minute depending on the treatment, or the washing water is circulated, chemicals, filters, ozone,
A method of treating with light or the like for reuse or a method of using a washing bath as a stabilizing bath to which a stabilizer is added and replenishing a small amount of a stabilizing solution according to the amount to be treated is used.

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

In the development processing of the present invention, the development temperature is set to 2
The temperature can be set to a normal temperature range of 0 to 50 ° C.
The silver halide photographic material of the present invention is preferably processed using an automatic processor. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. The development replenishment amount and the fixing replenishment amount are 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably it is 75 to 200 ml per m ² .

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) of 10 days from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when the processing is performed using the automatic developing machine. It is preferably -60 seconds.

The halogen composition of the silver halide photographic light-sensitive material of the present invention is preferably silver chlorobromide containing 60 mol% or more of silver chloride or silver chloroiodobromide containing 60 mol% or more of silver chloride. . The average grain size of the silver halide grains is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. Average particle size is a term that is commonly used by professionals in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or can be approximated to a sphere. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for obtaining the average particle size, see (C. E. K. Mees & T. H. James.
Written by: the theory of the photo
graphic process), 3rd edition, 36-4
See page 3 (1966 (published by Macmillan "Mcmillan")).

There are no restrictions on the shape of the silver halide grains.
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.
A so-called monodisperse emulsion containing 0%, preferably 95%, is preferable.

As the method for reacting the soluble silver salt of the silver halide emulsion with the soluble halogen salt, any one-side mixing method, simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is produced as one form of the double jet method
Can be kept constant, that is, a so-called controlled double jet method can be used. According to this method,
A silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. The silver halide grains may be grains having a laminated structure, and the laminated structure preferably has two or more layers and five or less layers.

For details of the silver halide emulsion and its preparation method, see RD, No. No. 17643, pages 22 to 23 (December 1978) or cited.

For the silver halide photographic light-sensitive material of the present invention, generally known sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization methods are appropriately selected and used alone or in combination. Can be sensitized. Note that chemical sensitization may not be performed.

As the sulfur sensitizer, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used. As the Se sensitizer, triphenylselenophosphine or the like is preferably used. A wide variety of selenium compounds can be used as the selenium sensitizer. 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 (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.) , Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (triphenylphosphine selenide,
Diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas,
These are selenoamides, selenoketones, and selenides.

The temperature for 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 preferable. Solid dispersion As a method of adding these sensitizers, if they are water-soluble, they can be added as they are, but if they are poorly 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. Among the noble metal sensitization methods, the gold sensitization method is a typical example of the noble metal sensitization methods in which a method of arbitrarily dispersing the average particle size from 0.01 to 6 μ by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like can be adopted. In this case, a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidinesulfinic acid, silane compounds and the like can be used. Further, an oxidizing agent for silver can be used in the manufacturing process of the light-sensitive material. Examples of the oxidizing agent that can be used include inorganic oxidizing agents such as hydrogen peroxide (water) and hydrogen peroxide adducts (for example, NaBO ₂ .H ₂ 0).
_{2 · 3H 2 O, 2NaCO 3} · 3H 2 O 2, Na 4 P 2 O 7 · 2
_{H 2 O 2, 2Na 2 SO} 4 · H 2 O 2 · 2H 2 O , etc.), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 4 P 2 O 8
Etc.), 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, etc.), permanganate (e.g., KMnO ₄
Etc.), oxyacid salts such as chromates (eg K ₂ CrO), halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), high valent metal salts (eg potassium ferricyanide). Etc.) and thiosulfonate. Examples of organic oxidants include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B, etc.). Can be mentioned. Particularly preferred oxidants are ozone, hydrogen peroxide and its adducts, inorganic oxidants of halogen elements, quinones and organic oxidants which release active halogens. The amount of oxidizing agent added is 10 ^-7 to 1 per mol of silver halide.
It is preferable to add 0 ^-1 mol. More preferred is 10
^-6 to 10 ^-2 mol, particularly preferably 10 ^-5 to 10
^-3 mol.

The silver halide photographic light-sensitive material of the present invention comprises
A dispersion of a water-insoluble or sparingly soluble synthetic polymer may be included for the purposes 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, etc., alone or in combination, or with acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used. 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 a primary to quaternary amino group,
Phosphonium groups, aliphatic, aromatic, -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, a carbamoyl group, an amino group, a sulfonyl group, a sulfoxy group, It may have an iminomethylene group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or the like), a cation group or the like. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

Various other additives can be used in the light-sensitive material of the present invention. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and colloidal silica. For these additives and the aforementioned additives,
Specifically, RD, No. 17643, pages 22-31,
And the like can be used.

The emulsion layer of the light-sensitive material used in the present invention 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 regulators (inhibitors or accelerators) contrast agents, physical property regulators, etc., dissolved in an aqueous solution or organic solvent, or dispersed as solid fine particles. It may be contained in a controlled form, which may or may not be oil protected.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention specifically means a photosensitive or substantially non-photosensitive silver halide emulsion layer, a protective layer, an undercoat layer, an intermediate layer, It refers to all the constituent layers of the silver halide photographic light-sensitive material such as a filter layer, an ultraviolet absorbing layer, an antihalation layer and an antistatic layer.

[0190]

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 Support) <Synthesis of SPS> 1 part of styrene was added to 200 parts by weight of toluene.
The reaction was carried out at 96 ° C. for 8 hours using 00 parts by weight, 56 g of triisobutylaluminum, and 234 g of pentamethylcyclopentane-diethyltitanium trimethoxide.
Then, the catalyst was removed with a methanol solution of sodium hydroxide and then washed with methanol three times to obtain 34 parts by weight of the target compound.

<Preparation of SPS Film> Obtained SPS
Was melt-extruded from a T-die at 330 ° C. into a film and quenched and solidified on a cooling drum to obtain an uncentrifuged film. At this time, the take-up speed of the cooling drum is set in two stages, and the thickness is 1370 μm, 1265 μm and 1054 μm.
The pre-stretched film was preheated to 135 ° C and longitudinally stretched (3.1
After that, the film was transversely stretched (3.4 times) at 130 ° C. and further heat-set at 250 ° C. As a result, the bending elastic modulus of 450 kg / mm ² was 130 μm and 100 μm as a support.
A biaxially stretched film of m was obtained. The bending elastic modulus of the comparative PET was 460 kg / mm ² .

<Undercoat of SPS film> A latex liquid of an undercoat latex (solid content: 20%) was obtained as S
0.5% after drying on PS and PET films
It was dried at 120 ° C. for 1 minute so as to have a film thickness of μm. Before coating, a corona discharge treatment of 0.5 kV · A · min / m ² was performed. After depositing silica on the SPS film, vinylidene chloride, styrene-butadiene, styrene-
An adhesive layer made of glycidyl acrylate and gelatin was provided at 0.3 μm. Furthermore, the average particle size of 0.1 μm
A 0.2 μm polymer layer containing a semiconductor fine particle mixture consisting of stannic oxide and barium sulfate was formed into an SPS film according to the present invention.

(Preparation of Silver Halide Emulsion A1) Silver chlorobromide core grains having an average diameter of 0.09 μm were prepared by using a double-blending method and containing 70 mol% of silver chloride and the rest being silver bromide. When this core particle was mixed, K ₃ Rh (N0) ₄ (H ₂ O) ₂ was added in an amount of 7 × 10 ^-8 per 1 mol of silver per 1 mol of silver.
Molar K ₃ OsCl ₆ in the presence of 8 × 10 ⁻⁶ molar addition,
An aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining 40 ° C., pH 2.0, and (EAg) 165 mV.
EAg was lowered to 80 mV with sodium chloride and shells were attached to the core particles by a double-mix method. At that time, K ₂ was added to the halide solution.
IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver, K ₃ RhCl ₆
^Was added in an amount of 9 × 10 ⁻⁸ mol. Further, KI conversion was performed using silver iodide fine particles. The obtained emulsion is a core / shell type monodisperse having an average diameter of 0.15 μ (variation coefficient 10%).
This was a cubic crystal emulsion of silver chloroiodobromide (70 mol% silver chloride, 0.2 mol% silver iodobromide, the rest being silver bromide). Then, it was desalted using the modified gelatin described in JP-A-2-280139 (Exemplary Compound G-8 in which the amino group in gelatin was substituted with phenylcarbamyl). EAg after desalination
Was 190 mV at 50 ° C. To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ⁻³ mol and potassium bromide in an amount of 8.5 × 10 ⁻⁴ mol per mol of silver. And citric acid to add pH
5.6, EAg123 mV was adjusted to 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added and reacted, and then inorganic sulfur compound dispersed in solid (S8) Using PM-1200 (manufactured by Seishin Enterprise Co., Ltd.), saponin was added to give an average of 0.
After being dispersed in 5 μm and 1.5 × 10 ⁻⁵ mol of chloroauric acid and chemically ripening for 120 minutes at a temperature of 55 ° C., 100 mg of sensitizing dye d-1 and trihexylamine were added at 50 ° C. 5 mg, and after further cooling to 40 ° C, 4
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol and potassium iodide in each mol of silver. After adding 5 × 10 ⁻³ mol, the pH was adjusted to 5.1 with citric acid to obtain a silver halide emulsion A1.

(Preparation of Silver Halide Emulsion A2) With respect to silver halide emulsion A1, the reaction temperature was raised to 50 ° C. to make the grain size 0.19 μ, and K ₃ RhCl ₆ in the shell portion was 6 × 10 ^−8.
Silver halide emulsion A2 was prepared in the same manner except that the mole ratio was changed.
Was prepared. When the same chemical sensitization was performed, the emulsion of A2 was 40% faster than the emulsion of A1.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) A gelatin subbing layer of the following Formulation 1 was prepared on a support with a gelatin content of 0.
The silver halide emulsion layer 1 of Formulation 2 was further coated thereon with a silver amount of 1.5 g / m ² and a gelatin amount of 0. 45 g / m ² .
Such that 65 g / m ^2, further amount of silver 1.5 g / m ² of silver halide emulsion layers 2 of Formula 3 thereon, so that the amount of gelatin is 0.65 g / m ^2, further following formulation 4 Simultaneous multi-layer coating was performed so that the coating amount of the protective layer coating solution was 0.7 g / m ² . On the other side of the undercoat layer, the following formulation 5
The backing layer of No. 6 was coated with the emulsion layer side and the curtain coating method so that the amount of gelatin was 1.5 g / m ² and the backing protective layer of the following Formulation 6 was so that the amount of gelatin was 0.8 g / m ^2. A sample was obtained by simultaneously coating multiple layers on the emulsion layer side at a speed of 200 m / min and cooling and setting, then simultaneously coating multiple layers on the backing layer side, cooling set at -1 ° C., and drying both sides simultaneously.

The SPS which is the support according to the present invention and the polyethylene terephthalate (PET) used as the comparative support have a thickness of 100 μm.
As the adhesive layer, the one shown in Table 2 provided on the undercoat layer was used.

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.45 g / m ² saponin 56.5 mg / m ² solid disperse dye Ex. AD-8 50 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 15 mg / m ² Bactericide z 0.5 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A1 Silver amount 1.5 g / m ² equivalent redox compound Described in Tables 1 and 2 (dissolved in ethyl acetate Then, it was dispersed in a gelatin solution, and ethyl acetate was removed under reduced pressure to be precipitated in the form of solid fine particles. 25 mg / m ² Sensitizing dye d-1 150 mg / Ag 1 mol Hydrazine compound H-1 1 × 10 ^-3 mol / Ag1 mol Amino compound AM-1 7 mg / m ² Compound a 100 mg / m ² 2-Pyridinol 1 mg / m ² Polymer latex L1 (particle size 0.25 μ) 0.2 5 g / m ² Hardener h1 5 mg / m ² Sodium-iso-amyl-n-decyl sulfosuccinate 0.7 mg / m ² Sodium naphthalene sulfonate 8 mg / m ² Saponin 20 mg / m ² Hydroquinone monosulfonate 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² colloidal silica (average particle size 0.05 μ) 150 mg / m ² ascorbic acid 20 mg / m ² EDTA 25 mg / m ² polystyrene sulfonic acid The coating solution pH of sodium 15 mg / m ² was 5.2.

Formulation 3 (composition of silver halide emulsion layer 2) Silver halide emulsion A2 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-2 100 mg / Ag 1 mol Hydrazine compound H-2 4 × 10 ⁻³ Mol / Ag 1 mol amino compound AM-1 7 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² nicotinic acid amide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg
/ M ² polymer latex L2 (JP-A-5-66512 Example 3 Type Lx-3 composition (9)) 0.25 g / m ² colloidal silica (average particle size 0.05 μ) 150 mg / m ² Gelatin is phthalated gelatin The coating solution pH was 4.8.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Amino compound AM-1 14 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Average particle size 3 0.5 μ spherical polymethylmethacrylate 25 mg / m ² matting agent: average particle size 8 μ indeterminate silica 12.5 mg / m ² surfactant S1 26.5 mg / m ² lubricant (silicone oil) 4 mg / m ² compound a 50 mg / M ² polymer latex L3 (particle size 0.10 μ) 0.25 g / m ² colloidal silica (average particle size 0.05 μ) 50 mg / m ² dye f1 20 g / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² hardener h2 30 mg / m ² sodium polystyrenesulfonate 10 mg / m ² fungicide z 0.5 mg / m ² formulation 5 (fines Layer composition) Gelatin 0.6 g / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 .mu.m) 100 mg / m ² of polystyrene Sodium sulfonate 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 Formulation 6 (Backing protective layer) Gelatin 0.4 g / m ² matting agent: monodisperse polymethylmethacrylate having an average particle size of 5 μ 50 mg / m ² matting agent: average particle size 3 μ Indeterminate 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 dye SF2 (solid dispersion) 20 mg / m ² compound a 50 mg / m ² hardener h2 20 mg / sodium m ² of polystyrene sulphonic acid 10 mg / m ² solid disperse dye illustrative A After dissolving -8 alkaline was acid precipitation by addition of citric acid 1.2 volume equivalents with respect to acid groups.

[0201]

[Chemical 40]

[0202]

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[0203]

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[0204]

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(Developer composition) Diethylenetriamine pentaacetic acid 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 to adjust the pH of the working solution to 10.4.

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

(Processing conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 sec Fixing 35 ° C. 20 sec Water washing 20 ° C. normal temperature 20 sec Squeeze / dry 50 ° C. 30 sec Total 100 sec (evaluation of development inhibitor release rate) Conditions (A): 50 μM methanol: acetonitrile (1: 1) of the compound of the present invention or the comparative compound at a constant temperature of 35 ° C.
1) 5 parts of the solution and 1 part of 100 mM hydrogen peroxide aqueous solution are mixed, 2 parts of carbonate buffer having a pH of 10.2 is added, and 30 seconds after the addition, 1 part of 100 mM acetic acid in methanol solution is added.

Condition (B): Under constant temperature of 35 ° C., 5 parts of a 50 μM methanol: acetonitrile (1: 1) solution of the compound of the present invention or the comparative compound was mixed with 1 part of distilled water to adjust pH.
30 seconds after adding 2 parts of 10.2 carbonate buffer, 1 part of 100 mM acetic acid in methanol is added.

The concentration of the development inhibitor released was quantified by high performance liquid chromatography (manufactured by Shimadzu Corp.) by comparing the peak area with a development inhibitor solution having a known concentration. The results obtained for the comparative and inventive compounds are shown in Table 1.

[0210]

[Table 1]

[0211]

[Table 2]

From Table 1, the compounds according to the present invention have a release rate A
It can be seen that / B is 1.5 or more, which is excellent.

(Evaluation of sensitivity and gamma) An optical wedge was used for the obtained sample, and a light source equipped with an interference filter of 633 nm was used as a substitute for the He-Ne laser light source.
High-intensity exposure for ⁵ seconds was performed, and development processing was performed under the above conditions. The obtained developed sample is used as a digital densitometer PDA-6.
5 (manufactured by Konica Corporation) was used to measure sensitivity, fog and gamma. The sensitivity in the table is the sample charge No. It was expressed as a relative sensitivity when the sensitivity at a density of 1 was 2.5 and the sensitivity was 100. Gamma is expressed by the tangent of density 0.1 and 3.0, and it cannot be used when the gamma value in the table is less than 7, and 7 or more and 1
Even less than 0 is still insufficient. Only when the gamma value is 10 or more, a very high contrast image is obtained, indicating that the material is a sufficiently practicable photosensitive material.

(Evaluation of Black Spots) The obtained developed sample was visually evaluated using a magnifying glass of 100 times, and was classified into 5 grades of 5, 4, 3, 2, 1 in the order of less black spots. It was ranked. Ranks 1 and 2 are levels that are not practically desirable.

(Evaluation method of halftone dot quality) SG-747RU
16μ random pattern halftone dot (FM screen)
The halftone dot quality (sharpness) was evaluated by using a magnifying glass 100 times the midpoint (target 50%) of the light exposed in (1). The highest rank was set to 5, and the rank was lowered to 4, 3, 2, and 1 according to the halftone dot quality, and evaluated. Ranks 1 and 2 are levels that are not practically desirable. New liquid level No. The halftone dot qualities of 101 and 102 were both 5.

[0216]

[Table 3]

As is apparent from Table 3, the sample according to the present invention was able to obtain a high-sensitivity and high-gamma silver halide photographic light-sensitive material in which generation of black spots was remarkably suppressed and halftone dot quality was excellent.

Example 2 The sensitizing dye of Example 1 was replaced by d- instead of d-1 and d-2.
Sample No. 3 was used in the same manner as in Example 1 except that the solid disperse dye was replaced with the exemplified AD-6 by using D-3 and d-4. 201
To 210, and the exposure machine is an infrared semiconductor laser light source recorder MT-R1120 (Dainippon Screen Co., Ltd.)
Was manufactured in the same manner as in Example 1. Table 4 shows the obtained evaluation results.

[0219]

[Table 4]

As is clear from the results shown in Table 4, the sample according to the present invention has excellent halftone dot characteristics, high sensitivity, high gamma, and suppressed generation of black dots even when an infrared semiconductor laser light source was used. It can be seen that a silver halide photographic light-sensitive material having a high density can be obtained. All of the above are p of the developing solution.
Although H was adjusted to a relatively low pH of 10.4 and treated, according to the present invention, it had a high concentration and no deterioration of halftone dot quality was observed. In addition, pH outside the present invention (for example, p
In the case of processing with a developer adjusted to H11.5), many black spots were observed, which was not preferable.

[0221]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material for plate-making having a high sensitivity and a high halftone dot property and suppressing the generation of black spots was obtained.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on one surface of a support, which is oxidized in the silver halide emulsion layer and / or a hydrophilic colloid layer adjacent thereto. Is a stretched film containing at least one redox compound satisfying the following conditions (1) to (3), and the support containing syndiotactic polystyrene as a main component. A silver halide photographic light-sensitive material characterized by the above. (1) Development inhibitor release rate (%) ≧ under the following condition (A):
4.5 (2) Release rate (%) of the development inhibitor under the following condition (B) <
15.0 (3) Development inhibitor release rate (%) under the following condition (A)>
Development inhibitor release rate (%) under the following conditions (B) Condition (A): 50 μM methanol: acetonitrile (1: 1) of a compound capable of releasing a development inhibitor at a constant temperature of 35 ° C.
1) 5 parts of the solution and 1 part of 100 mM hydrogen peroxide aqueous solution are mixed, 2 parts of carbonate buffer having a pH of 10.2 is added, and 30 seconds after the addition, 1 part of 100 mM acetic acid in methanol solution is added. Condition (B): 50 μM methanol: acetonitrile (1: 1, a compound capable of releasing a development inhibitor at a constant temperature of 35 ° C.).
1) Mix 5 parts of the solution with 1 part of distilled water, add 2 parts of carbonate buffer of pH 10.2, and 100 mM after 30 seconds
Add 1 part of acetic acid in methanol. Development inhibitor release rate (%): (Measured development inhibitor concentration / 100% development inhibitor concentration at release) × 100 2. The silver halide photographic light-sensitive material according to claim 1, which contains at least one redox compound satisfying the following condition (4). (4) Development inhibitor release rate (%) / under the above condition (A)
The development inhibitor release rate (%) under the above condition (B) is 1.5.
Must be 10 or more. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto contains a hydrazine derivative. 4. After exposing a silver halide photographic light-sensitive material,
4. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed with a developer having H of 8.5 or more and 11.0 or less.