JP2000066331A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material for daylight that faithfully reproduces dots and undergoes a slight reduction in density. SOLUTION: At least two silver halide emulsion layers are formed on a substrate. The sensitivity of the silver halide emulsion layer closer to the substrate is 70-600% of that of the upper silver halide emulsion layer. A dye-contg. layer having an optical density of 0.2-1.0 at 365 μm is disposed on the upper silver halide emulsion layer and a layer contg. a dye solidly dispersed as fine particles is interposed between the lower silver halide emulsion layer and the substrate to obtain the objective silver halide photographic sensitive material having substantially no sensitivity at >=450 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material suitable for use in a process called "return" in a photolithography process, and more particularly, to a bright room reverse halogenation exhibiting improved photographic characteristics. It relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, in the field of printing, there has been a demand for improvement of work efficiency in a printing plate making process in order to cope with the variety and complexity of printed matter. In particular, in the work of plate collecting and turning processes, work efficiency has been improved by working in a brighter environment, and as a result, for plate making that can be handled in an environment that can be substantially called a bright room The development of silver halide photosensitive materials and the development of exposure printers have been advanced. Incidentally, the silver halide light-sensitive material for a bright room is a photographic light-sensitive material which can use light of 400 nm or more containing no ultraviolet light component as safelight light.

An important performance of the light-turned light-sensitive material is faithful reproducibility of halftone dots. In order to faithfully reproduce the halftone dots, it is better to keep the exposure low, but in that case it is likely to lead to a reduction in the overall density. To increase the maximum density after development, it is effective to reduce the grain size of silver halide and increase the covering power. However, in this case, silver sludge is easily generated, and the transmittance of light at the time of exposure is increased, so that halftone dots are spread due to halation and dot reproducibility is deteriorated.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material for a bright room, which faithfully reproduces a halftone dot and has a small density reduction.

[0005]

The object of the present invention is attained by adopting one of the following constitutions.

(1) At least two silver halide emulsion layers are formed on a support, and the sensitivity of the silver halide emulsion layer closer to the support is lower than that of the silver halide emulsion layer adjacent to the support. 70-600%, and 365 μm
Is provided with a dye-containing layer having an optical density of 0.2 to 1.0, and a layer containing a dye solid-dispersed in fine particles between the support and the support, and substantially 450 μm
A silver halide photographic material characterized by having no sensitivity as described above.

(2) At least two silver halide emulsion layers are formed on a support, and the sensitivity of the silver halide emulsion layer on the side closer to the support is lower than the sensitivity of the silver halide emulsion layer adjacent thereto. 70-600%, and 365 μm
Provided that a dye-containing layer having an optical density of 0.2 to 1.0 is provided, and a layer containing a redox DIR compound is further provided between the support and the support, and the sensitivity is not substantially 450 μm or more. Characteristic silver halide photographic material.

(3) At least two silver halide emulsion layers are formed on a support, and the sensitivity of the silver halide emulsion layer close to the support is lower than that of the silver halide emulsion layer adjacent to the support. 70-600%, and 365 μm
Is provided with a dye-containing layer having an optical density of 0.2 to 1.0, and further provided with a layer containing a redox DIR compound and a dye solid-dispersed in fine particles between the support, and substantially A silver halide photographic material characterized by having no sensitivity at 450 μm or more.

(4) The sensitivity of the silver halide emulsion layer on the side close to the support is 150 to 300% of the sensitivity of the silver halide emulsion layer adjacent thereto, and the upper layer has an optical density of 0.3 μm at 365 μm. The silver halide photographic material as described in (1), (2) or (3), further comprising a dye-containing layer of 4 to 0.8.

(5) The silver halide photographic material as described in (1), (2) or (3), wherein the amount of gelatin is 2.5 g / m ² or less.

[0011] In the present invention, the expression "having substantially no sensitivity of 450 µm or more" means that the sensitivity of 450 µm or more is 450 µm or more.
The sensitivity is less than 1/1000 compared to the sensitivity less than m.

In the present invention, the expression that the sensitivity of the silver halide emulsion layer on the side close to the support is 70 to 600% of the sensitivity of the silver halide emulsion layer adjacent to the support means that each emulsion is a single layer. Indicates that the sensitivity ratio in the case of coating was within this range. More preferably, the sensitivity ratio of both layers is 150 to 300%.

Further, 365 μm is formed on the upper layer of the silver halide emulsion layer.
The provision of a dye-containing layer having an optical density of 0.20 to 1.0 at m means that the difference in optical density at 365 μm between when a dye is dispersed in gelatin and applied and when only gelatin is applied is within this range. Indicates that there is. It is more preferable to provide a dye-containing layer having an optical density of 0.40 to 0.8. The layer to which the dye is added may be an upper silver halide emulsion layer, but a protective layer or the like provided thereon is more preferable.

The silver halide light-sensitive material having the above structure has a maximum density higher than that of the conventional material and is a light-sensitive material having a wide appropriate exposure area.

In the silver halide photographic light-sensitive material of the present invention, it is preferable to add at least one known contrast agent such as a tetrazolium compound or a hydrazine derivative. A representative structure of the hydrazine derivative is shown below.

[0016]

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

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

[0019]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The anti-diffusion group is preferably a ballast group commonly used in immobile photographic additives such as couplers, and the ballast group is preferably an alkyl group having 8 or more carbon atoms which is relatively inert to photographic properties. Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

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

In the general formula [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and 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 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵⁾ groups (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group,
R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

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

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

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

The hydrazine derivative used in the present invention is
It is added to the silver halide emulsion layer or an adjacent layer.

In order to effectively promote the contrast enhancement by the hydrazine derivative, a quaternary onium compound having a quaternary nitrogen compound and / or a quaternary phosphorus compound in the structure, an amine compound, or an alcohol compound having a molecular weight of 120 or more is selected. It is preferable to use at least one nucleation accelerator,
Particularly, a quaternary onium compound is preferable.

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

[0042]

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

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

Examples of the ring which R _{1 to} R ₄ can form by linking each other include rings such as piperidine, morpholine, piperazine, quinuclidine and pyridine.

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

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

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

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

[0050]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

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

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

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

[0055] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt. Next, specific examples of the pyridinium compound according to the present invention are shown below, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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Next, representative amine compounds will be described.

[0067]

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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 the general formula [Na] are shown below.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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The redox DIR compound (compound capable of releasing a development inhibitor when oxidized) according to the present invention will be described.

The redox DIR compound of the present invention has, as a redox group, a partial structure of a hydroquinone, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a reductone, an α-aminoketone, or the like.

Preferred redox DIR compounds include:
A compound having an NHNH— group and the following general formula [3],
A compound represented by [4], [5], [6], [7] or [8].

[0078]

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

Formula [RE-a] T-NHNHCO- (Tm) _n -PUG Formula [RE-b] T-NHNHCOCO- (Tm) _n -PUG Formula [RE-a], [RE-b] In the formula, T represents an optionally substituted aryl group or an optionally substituted alkyl group. Examples of the aryl group include a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. As a preferred substituent, a straight-chain or branched alkyl group (preferably having 2 to 20 carbon atoms) Such as methyl, ethyl, isopropyl, dodecyl, etc.), an alkoxy group (preferably one having 2 to 21 carbon atoms, such as methoxy group, ethoxy group, etc.), an aliphatic acylamino group (preferably alkyl having 2 to 21 carbon atoms) Groups, such as an acetylamino group and a heptylamino group), an aromatic acylamino group, and the like. In addition, for example, the above-mentioned substituted or unsubstituted aromatic ring may be -CONH-, -O- , −
Also included are those linked by a linking group such as SO ₂ NH—, —NHCONH—, and —CH ₂ CHN—. Tm represents a timing group, and n represents 0 or 1. PUG is a compound that exhibits a development inhibiting property by being released, and as the development inhibiting compound, 5-nitroindazole,
4-nitroindazole, 1-phenyltetrazole,
1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole,
5-nitroimidazole, 4-nitroimidazole and the like. These development inhibiting compounds are T-NHN
The H-group is bonded directly to the -CO- or -COCO- site via a heteroatom such as N or S, or via an alkylene, phenylene, aralkylene or arylene group and further via a heteroatom such as N or S. This makes it possible to control the timing until the development suppression property is exhibited after the separation. In addition, those obtained by introducing a development inhibiting group such as triazole, indazole, imidazole, thiazole, and thiadiazole into a hydroquinone compound having a ballast group can also be used. For example, 2- (dodecylethylene oxide thiopropionamide) -5- (5-
Nitroindazol-2-yl) hydroquinone, 2-
(Stearylamide) -5- (1-phenyltetrazol-5-thio) hydroquinone, 2- (2,4-di-t)
-Amylphenoxypropionamide) -5- (5-
Nitrotriazol-2-yl) hydroquinone, 2-
Dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone;

The above redox DIR compound can be synthesized with reference to the description in US Pat. No. 4,269,929.

The above-mentioned redox DIR compound can be used in any of the photographic constituent layers on the side of the silver halide emulsion layer. Preferably, it is used for the silver halide emulsion layer closest to the support and / or the non-photosensitive hydrophilic colloid layer adjacent to the support side of the emulsion layer.

The addition of the redox DIR compound described above
Dissolves in alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, esters such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone. Can be added afterwards. Those hardly soluble in water or organic solvents can be arbitrarily dispersed from 0.01 to 6 μm in average particle diameter by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion, or the like. For dispersion, a surfactant such as an anion or nonion, a thickener, a latex, or the like can be added and dispersed.

The amount of the redox DIR compound added is
It is from 10 ^-6 mol to 10 ^-1 mol, preferably from 10 ^-4 mol to 10 ^-2 mol, per mol of silver halide.

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

[0086]

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[0087]

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Specific examples of other preferred redox DIR compounds are described in JP-A-4-245243.
“0053” on page 36 (8) to “006” on page 250 (22)
R-1 to R-50 described in "8."

Next, the general formulas [3], [4],
The redox DIR compound represented by [5], [6], [7] or [8] will be described.

The general formulas [3], [4], [5], [6],
In [7] or [8], R ₁₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₁₂ and R ₁₃ 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 ₁₄ represents a hydrogen atom. R _{15 to} R ₁₉ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ represent a substituent capable of substituting on a benzene ring. X ₄ , X
₅ represents O or NH. Z represents an atomic group necessary to form a 5- to 6-membered heterocyclic ring. W represents N (R ₅₀ ) R ₅₁ or OH, and R ₅₀ and R ₅₁ are a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group. COUP is aromatic first
Represents a coupler residue capable of causing a coupling reaction with an oxidized product of a secondary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group. m ₁ and p ₁ represent an integer of 0 to 3. q1 represents an integer of 0 to 4.
n represents 0 or 1. PUG represents a group which is released to become a development inhibiting compound.

The general formulas [3], [4], [5],
In [6], [7] or [8] (hereinafter, in the formula), R
_{As the} alkyl group, aryl group or heterocyclic group represented by ₁₁ , R _{15 to} R ₁₉ , R ₅₀ and R ₅₁ , a methyl group, a p-
Examples include a methoxyphenyl group and a pyridyl group. R ₁₂
And acyl group, a carbamoyl group represented by R _13, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group, preferably an acyl group among the aryloxy carbonyl group, a carbamoyl group, It is a cyano group. The total number of carbon atoms in these groups is preferably 1 to 20. R _{11 to} R ₁₉ , R ₅₀ ,
R ₅₁ may further have a substituent, for example, a halogen atom (a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group,
Hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group ( For example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc., alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.),
Cyano group, acylamino group (for example, acetylamino group,
Propionylamino group, alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group ( For example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc., sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group) Group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, Nonoxycarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group) , A dimethylamino group, etc.), a hydroxyl group, a nitro group, an imide group (eg, a phthalimido group), a heterocyclic group (eg, a pyridyl group,
Benzimidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.). The following can be mentioned as the coupler residue represented by COUP.
Examples of the cyan coupler residue include a phenol coupler and a naphthol coupler. 5 for a magenta coupler
-Pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like. Benzoylacetoanilide coupler as a yellow coupler residue,
Pivaloyl acetanilide coupler, malondianilide coupler and the like. Non-colored coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic diester, imidazolinone, oxazolinone, thiazolinone, etc.). More COUP
Among the coupler residues represented by formula (I), those preferably used in the present invention can be represented by formulas (Coup-1) to (Cup-8).

[0092]

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In the formula, R ₅₆ represents an acylamide group, anilino group or ureido group, and R ₅₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0094]

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In the formula, R ₅₈ and R ₅₉ represent a halogen atom, an acylamide group, an alkoxycarbonylamide group, a sulfoureido group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₆₀ and R ₆₁ each represent an aliphatic group. Represents an aromatic group, an aromatic group or a heterocyclic group. Further, one of R ₆₀ and R ₆₁ 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 ₅₈ may be the same or different, and R ₅₉ may be the same or different.

[0096]

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In the formula, R ₆₂ represents a tertiary alkyl group or an aromatic group, and R ₆₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₆₄ 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.

[0098]

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In the formula, R ₆₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₆₆ represents a hydrogen atom, a halogen atom, or a nitro group.

[0100]

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R ₆₇ and R _{68 each} represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.

5 to 6 represented by Z in the general formula [4]
The membered heterocyclic ring may be a single ring or a condensed ring;
5 to 6 having at least one of S and N atoms in the ring
Membered heterocycles. These rings may have a substituent, and specific examples include the aforementioned substituents.

In the general formulas [3] to [8], the timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat.
8,962, 4,409,323 or 3,6
No. 74,478, (RD) No. 21228 (1981
December, 1987) or JP-A-57-56837;
-438 and the like.

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

Specific examples of the compounds represented by the general formulas [3] to [8] are listed below, but the present invention is not limited thereto.

[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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The compounds represented by the above general formulas [3] to [8] can be used in any layer as long as it is a photographic constituent layer on the silver halide emulsion layer side. Preferably, it is used for the silver halide emulsion layer closest to the support and / or the non-photosensitive hydrophilic colloid layer adjacent to the support side of the emulsion layer.

Compounds represented by the above general formulas [3] to [8] may be used in a suitable water-miscible organic solvent, for example, alcohols,
It can be used by dissolving it in ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like. Further, 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 an ultrasonic wave by a method known as a solid dispersion method.

The amount of the compounds represented by the above general formulas [3] to [8] is from 10 ^-6 mol to 10 ^-1 mol, preferably from 10 ^-4 mol to 1 ^-1 mol, per mol of silver halide.
It is in the range of 0 ^-2 mol.

In the present invention, at least 2
A light-sensitive silver halide emulsion layer. It is desirable to have at least one non-photosensitive hydrophilic colloid layer thereon.

In the present invention, the hydrophilic colloid layer includes, as a hydrophilic colloid, gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, albumin,
Proteins such as casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, A variety of hydrophilic polymers such as homopolymers or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. Further, the non-photosensitive hydrophilic colloid layer according to the present invention may have a non-photosensitive silver halide emulsion.

It is particularly desirable that the amount of gelatin in these hydrophilic colloid layers is 2.5 g / m ² or less.

The black-and-white silver halide photographic light-sensitive material according to the present invention has a dried film thickness from the outermost surface on the emulsion layer side to the surface farthest from the support of the photosensitive silver halide emulsion layer closest to the support. Is desirably 2.5 to 8 μm. The film thickness can be measured by dry-cutting the photosensitive material and observing it with an electron microscope.

In the present invention, the film thickness is preferably
It is 2.5-5 μm.

The halogen composition of the silver halide grains used in the silver halide emulsion layer of the present invention is preferably a silver halide composition containing 90 mol% to 100 mol% of silver chloride. More preferably, a silver chlorobromide containing 90 mol% or more of silver chloride, silver chloroiodobromide containing 90 mol% or more of silver chloride or a silver halide emulsion having a silver halide composition of silver chloride is used.

The average grain size of silver halide is 0.6 μm.
m or less, especially 0.5 to 0.05 μm
m is preferred. The average particle size is commonly used by experts in the field of photographic science and is used in a meaning easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method of determining the average particle size, see Mies, James: The Theory of the Photographic Process (by CE Mees & TH James: Th).
e theoryof the photograph
ic process), 3rd edition, pp. 36-43 (19
66 (published by McMillan "Mcmillan").

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

Among the above-mentioned tabular grains, tabular grains having a (100) plane having 90 mol% or more of silver chloride as a main plane can be used, and these are described in US Pat. No. 5,264,264.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained.

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

In the present invention, silver halide grains are
It is desirable to contain at least one metal selected from Group VIII transition metals and rhenium. Examples of the Group VIII transition metal include iridium, rhodium, ruthenium, osmium and the like, with ruthenium and / or osmium being preferred. It is preferred to add in the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A-2-208.
No. 52, No. 2-20853, No. 2-20854, No. 2-20855, and as the hexadentate ligand and alkali complex, common sodium salts, potassium salts, cesium salts or primary salts are described. There are secondary and tertiary amine salts.
Further, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these include, for example, K ₂ [RuCl ₆ ],
(NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO) Cl
₄ (SCN)] and K ₂ [RuCl ₅ (H ₂ O)]. The Ru part can be represented by replacing it with Rh, Os and Ir.

These metals can be added at any time between silver halide grain formation and coating, but are preferably during silver halide grain formation, during physical ripening and / or during chemical ripening. More preferably, it is added during the formation of silver halide grains. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

Further, zinc is added during physical ripening or chemical ripening.
Metal salts such as lead, thallium, rhenium, palladium, platinum and the like can also be allowed to coexist.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Res).
(Earth Disclosure), No. 176, 17
643, pp. 22-23 (December 1978).

The silver halide emulsion is preferably chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, US Pat. No. 1,623,499, JP-A-50-71325,
The compounds described in JP-A-60-150046 can be preferably used. As the noble metal sensitizer, a gold compound, a platinum compound, a palladium compound and the like can be preferably used. Among them, a gold compound is more preferable.

Examples of the combination using these chemical sensitizers include a combination of a sulfur sensitizer and a noble metal sensitizer, a combination of a selenium sensitizer and a noble metal sensitizer, a reduction sensitizer and a noble metal sensitizer. And the like. In the present invention, it is preferable to sensitize by adding at least one gold compound.

These chemical sensitizers can be added at any time during the preparation of the silver halide emulsion, but are preferably added after the formation of silver halide grains and before coating.

The addition amount of these chemical sensitizers is preferably in the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

When a gold compound is used, it is preferably added in a molar amount of 0.1 to 1 times the salt of a metal selected from the group VIII transition metals and rhenium.

In the present invention, it is desirable that at least one of the non-light-sensitive hydrophilic colloid layers on the light-sensitive silver halide emulsion layer contains a matting agent having an average particle diameter of 4 to 10 μm. The matting agent used may be of a fixed or irregular shape.

As the matting agent used in the present invention, any known matting agents can be used. For example, silica described in Swiss Patent 330,158, glass powder described in French Patent 1,296,995, British Patent 1,
No. 173,181; inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc; US Pat.
Starch described in 22,037, Belgian Patent 625,4
No. 51 or British Patent No. 981,198, starch derivatives, polyvinyl alcohol described in JP-B-44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330,158, U.S. Pat. Organic particles such as polyacrylonitrile described in U.S. Pat. No. 3,257, and polycarbonate described in U.S. Pat. No. 3,022,169.

These matting agents may be used alone or in combination. The shape of the matting agent is preferably spherical as a regular matting agent, but may be another shape such as a flat plate shape or a cubic shape. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the mat particle size refers to the diameter converted into a sphere.

In order to fulfill the basic function of the matting agent,
It is desirable that a part of the matting agent is exposed on the surface.
The matting agent exposed on the surface may be a part of the added matting agent or may be all. The matting agent is previously dispersed in a coating solution and applied.

Further, a matting agent having a regular size and / or an irregular shape having an average particle size of less than 4 μm can be also contained.

In the present invention, it is preferable that at least one layer on the side of the silver halide emulsion layer contains a dye dispersed in solid fine particles (hereinafter, also referred to as a solid fine particle dispersion of the dye). As the dye to be solid-dispersed into fine particles, it is preferable to use compounds represented by formulas (I) to (VI).

[0140]

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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, and L ₁ , L ₂ and L ₃ Each represents a methine group. m2 represents 0 or 1, t represents 0, 1 or 2, and p2 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 formulas (I), (II) and (III) are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thione Hydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidindione, hydroxypyridone,
Pyrazolopyridone.

The basic nucleus represented by B in the general formulas (III) and (V) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, indolenine, pyrrole , Indole.

Examples of the aryl group represented by Q in formulas (I) and (IV) include a phenyl group and a naphthyl group. The heterocyclic groups represented by Q and Q 'in the general formulas (I), (IV) and (VI) include, for example, pyridyl, quinolyl, isoquinolyl, pyrrolyl, pyrazolyl, imidazolyl, indolyl Group, furyl group,
And a thienyl group. The aryl group and the heterocyclic group include those having a substituent. Preferred examples of the substituent include an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a t-butyl group, an octyl group, -Hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, 2- Hydroxyethoxy group, methylenedioxy group, butoxy group, etc., substituted amino group (for example, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl- N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (for example, Tan sulfonamido group and a benzenesulfonamide group), a sulfamoyl group (e.g. a sulfamoyl group, methylsulfamoyl group, and phenyl sulfamoyl groups),
These substituents may be combined.

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

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

In the present invention, among the dyes represented by the general formulas (I) to (VI), a dye having at least one carboxyl group in the molecule is preferably used, and more preferably a dye having the general formula (I) And particularly preferably a dye in which Q in the formula (I) is a furyl group.

Specific examples of preferably used dyes are shown below, but are not limited thereto.

[0149]

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[0150]

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[0151]

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

The method for producing the solid fine particle dispersion of the dye according to the present invention is described in JP-A-52-92716, JP-A-55-155350, JP-A-55-155351 and JP-A-55-155351.
The methods described in JP-A-3-197943, JP-A-3-182743, and World Patent WO88 / 04794 can be used. Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound to be dispersed in solid fine particles is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, dissolve the compound in a weakly alkaline aqueous solution and then lower the pH to make it weakly acidic. A dispersion of the compound can be obtained by a method of depositing a particulate solid by a method of preparing a particulate solid by simultaneously mixing a weakly alkaline solution of the compound and an aqueous acidic solution while adjusting the pH. The solid fine particle dispersion of the present invention may be used alone, or may be used as a mixture of two or more kinds, or may be used by mixing with a solid fine particle dispersion other than the present invention. 2
When a mixture of more than one species is used, they may be dispersed separately and then mixed, or they may be dispersed simultaneously.

In the case where the solid fine particle dispersion of the dye according to the present invention is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant is co-present during or after the dispersion. Such surfactants include anionic surfactants,
Any of a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used, but preferably, for example, an alkyl sulfonate, an alkylbenzene sulfonate, an alkyl naphthalene sulfonate, an alkyl sulfate, a sulfosuccinate , Sulfoalkylpolyoxyethylene alkylphenyl ethers, N-
Anionic surfactants such as acyl-N-alkyltaurines 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 surfactants include, for example,
Compounds 1 to 32 described in 277001 No. 32 to 46 are exemplified, 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 of the dye, but it is usually 0.1 mg to 2000 mg per 1 g of the dye. , Preferably 0.5m
g to 1000 mg, more preferably 1 mg to 50 mg.
0 mg may be sufficient. The concentration in the dispersion of the dye is 0.0
It is used in an amount of 1 to 10% by weight, preferably 0.1 to 10% by weight.
1 to 5% by weight. The surfactant is preferably added before the start of the dispersion of the dye. If necessary, the surfactant may be further added to the dye dispersion after the completion of the dispersion. These anionic activators and / or nonionic activators may be used alone, respectively, or two or more kinds may be combined, and both activators may be combined.

The solid fine particle dispersion of the dye according to the present invention is preferably dispersed so as to have an average particle diameter of 0.01 μm to 5 μm, more preferably 0.01 μm to 5 μm.
1 μm, particularly preferably 0.01 μm to 0.5 μm
m. In addition, as the variation coefficient of the particle size distribution,
It is preferably 50% or less, more preferably 40% or less.
% 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 To the solid fine particle dispersion of the present invention, a hydrophilic colloid used as a binder for a photographic constituent layer is added before or after the start of dispersion. can do. As the hydrophilic colloid, it is advantageous to use gelatin.In addition, for example, phenylcarbamylated gelatin, acylated gelatin, gelatin derivatives such as phthalated gelatin, and gelatin having a polymerizable ethylene group-containing monomer. Graft polymers, carboxymethylcellulose, hydroxymethylcellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-
Synthetic hydrophilic polymers such as dimethylacrylamide, poly-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 the present invention is 0.1% by weight in percentage.
It is preferably added so as to be と 12%, more preferably from 0.5% to 8%.

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

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

The coating of the light-sensitive material is usually carried out by coating a support with a coating solution comprising a composition containing a hydrophilic colloid as a binder such as gelatin, and then drying in a low-temperature air generally having a dry-bulb temperature of -10 to 15 ° C. The solidification is carried out by cooling, and then the temperature is raised to evaporate and remove the water in the coating layer. At this time, the weight ratio between gelatin and water was 2 immediately after coating.
Around 0% is common.

The coating of the light-sensitive material is usually carried out by applying a coating solution comprising a composition containing a hydrophilic colloid as a binder, such as gelatin, to a support, and then in a low-temperature air having a dry-bulb temperature of generally -10 to 15 ° C. At this time, at least two hydrophilic colloid layers are provided on top of the silver halide emulsion layer in order to reduce sinking of the matting agent, and the gelatin concentration of the lower hydrophilic colloid layer adjacent to the uppermost layer is adjusted to 3%. It is preferable that the gelatin concentration is 0.5% or more, more preferably 1.0% or more than that of the uppermost hydrophilic colloid layer containing a matting agent. The weight ratio of water to the binder on the side containing the silver halide emulsion layer was 20%.
The coating surface wet bulb temperature at 0% or more is preferably 20 ° C. or less. It is more preferably 4 to 19 ° C.

It is preferred that the layer having the largest silver / gelatin weight ratio contained in the emulsion layer contains at least one hydrazine derivative. The silver weight of the layer having the largest silver weight / gelatin weight ratio is 1% of the gelatin weight.
Preferably it is 5 to 10 times. Further, the layer having the largest silver / gelatin weight ratio is preferably the emulsion layer closest to the support.

The light-sensitive material of the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7). -Tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added.

As one method for remarkably exhibiting the effects of the present invention, it is preferable that at least one constituent layer contains a hydrophilic polymer. Preferred hydrophilic polymers include starch, glucose, dextrin, dextran, cyclodextrin, sucrose, maltose, xanthan gum, carrageenan and the like. The molecular weight of the hydrophilic polymer can be appropriately selected from 600 to 1,000,000. The lower the molecular weight is, the better to elute into the processing solution quickly during the processing, but if it is too low, the film strength of the film is deteriorated. When a hydrophilic polymer is used, the film abrasion resistance deteriorates. Therefore, it is preferable to add inorganic colloidal silica, colloidal tin, colloidal zinc, colloidal titanium, colloidal yttrium, colloidal praseodymium, neodymium, zeolite, apatite, and the like. Examples of the zeolite include analsite, erionite, mordenite, shabasite, gmelinite, and levinite, and examples of the synthetic zeolite include zeolite A, X, Y, and L. Examples of apatite include hydroxyapatite, fluorospatite, and chlorapatite. Preferred addition amounts are from 1% to 80% by weight per hydrophilic binder.
% Can be added. The inorganic compound,
By treating with a silane coupling agent, even when added to the emulsion, it is difficult to aggregate and the coating solution can be stabilized. Further, cracking due to the inorganic compound can be prevented. As silane coupling agents, triethoxysilanovinyl, trimethoxysilanovinyl, trimethoxypropyl methacrylate, trimethoxysilanopropylglycidyl, 1-mercapto-3-triethoxysilanopropane, 1-amino-3-triethoxysilanopropane, Triethoxysilanophenyl, triethoxymethylsilane and the like. The properties of the silane coupling agent can be improved by performing a high temperature treatment together with the above-mentioned inorganic compound, compared to the simple mixing. The mixing ratio is 1:
It is better to select in the range of 100 to 100: 1.

In order to make the effect of the present invention more remarkable, at least one hydrophilic colloid layer is provided on the opposite side of the silver halide photographic emulsion layer, and at least one hydrophobic polymer layer is provided outside the at least one hydrophilic colloid layer. Is preferred. Here, the hydrophilic colloid layer on the opposite side of the silver halide photographic emulsion layer includes a so-called back layer. In the present invention,
A configuration having at least one hydrophobic polymer layer outside the back layer is preferable. In the present invention, the hydrophobic polymer layer is a layer using a hydrophobic polymer as a binder.
Specific examples of the binder of the polymer layer, polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene,
Fluorinated resins such as polyvinylidene fluoride, rubbers such as butadiene rubber, chloroprene rubber, and natural rubber; acrylic or methacrylic acid esters such as polymethyl methacrylate and polyethyl acrylate; polyester resins such as polyethylene phthalate; nylon 6; nylon 66
Such as polyamide resins, cellulose resins such as cellulose triacetate, water-insoluble polymers such as silicone resins,
Or their derivatives can be mentioned. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. Particularly preferred binders include alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid copolymers (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is Styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride -Acrylonitrile-methyl methacrylate-ethyl acrylate-acrylic acid copolymer (5 mol% or less of acrylic acid), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer and the like. These may be used alone or in combination of two or more.

In the hydrophobic polymer layer according to the present invention, if necessary, a matting agent, a surfactant, a dye, a sliding agent, a cross-linking agent, a thickener, a UV absorber, and a photograph of inorganic fine particles such as colloidal silica. May be added. These additives can also be referred to, for example, the descriptions in Research Disclosure Magazine, Vol. 176, Item 17646 (December 1978).

The method for applying the hydrophobic polymer layer according to the present invention is not particularly limited. After applying and drying the back layer,
A polymer layer may be applied on the back layer and then dried, or the back layer and the hydrophobic polymer layer may be applied simultaneously and then dried. The hydrophobic polymer layer may be dissolved in a binder solvent of the polymer layer and applied in a solvent system,
It may be applied in an aqueous system using an aqueous dispersion of a binder polymer.

In these layers, an inorganic filler such as colloidal silica for dimensional stability, silica or methyl methacrylate for preventing adhesion, a silicone-based slipping agent or a release agent for controlling transportability, etc. are included. It can be contained.
The backing layer may contain a backing dye, and a benzylidene dye or an oxonol dye is used as the backing dye. These alkali-soluble or decomposable dyes can be fixed as fine particles. The concentration for preventing halation is 0.1 at each photosensitive wavelength.
Preferably, the concentration is up to 2.0.

In the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide] and the like, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like) ), Mucohalogenic acids (mucochloric acid, phenoxymucochloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardener, etc., alone or in combination Can be used. These hardeners are available from Research Disclosure.
loss) 176, 17643 (issued in December 1978), page 26, paragraphs A to C. Among them, preferred are carboxyl group-activated hardeners, and compounds represented by formulas (1) to (7) described in JP-A-5-289219, pp. 3-5, are preferred. Is, for example, H-1 described on pages 6 to 14 of the publication.
To H-39.

In the light-sensitive material used in the present invention, various other additives are used. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

The support used in the present invention may be either permeable or non-permeable. For the purpose of the present invention, a permeable plastic support is preferred. For the plastic support, a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.),
A support made of a triacetate compound (for example, triacetate cellulose or the like), a polystyrene compound, or the like is used. Among them, a support (hereinafter, abbreviated as SPS) composed of a stretched film made of a styrene-based polymer having a syndiotactic structure or a composition containing the same is particularly preferable in order to significantly exert the effects of the present invention. S
PS refers to a homopolymer whose constituent units are composed of SPS units having syndiotactic stereoregularity, but in a small amount, for example, 20 mol% or less, preferably 1 mol% or less.
Also included are SPS modified with up to 0 mol%, more preferably up to 5 mol% of the second component. Examples of the second component include olefin monomers such as ethylene, propylene, butene and hexene, diene monomers such as butadiene and isoprene, cyclic olefin monomers and cyclic diene monomers, and polar vinyl monomers such as methyl methacrylate, maleic anhydride and acrylonitrile. And the like. In general, it is produced by polymerizing styrene or a derivative thereof under an appropriate reaction condition using an organometallic catalyst. Syndiotactic polystyrene is at least 75%, preferably at least 80%, of racemic diad, or at least 30% of racemic pentad,
Preferably, it has a stereoregularity of 50% or more. In this case, a general plastic plasticizer can be added as the second component within a range that does not degrade the flexural modulus, and this is performed to obtain an appropriate flexural modulus.

The SPS can be synthesized by polymerizing styrene or a derivative thereof at a suitable reaction temperature in the presence of a catalyst of a condensation product of a titanium compound and a trialkylaluminum. These can be referred to the methods described in JP-A-62-187708, JP-A-1-46912 and JP-A-1-178505. The polymerization degree of SPS is not particularly limited, but those having 10,000 to 5,000,000 are preferably used. In order to increase the flexural modulus of the SPS, it is necessary to select optimal stretching conditions. 30 ° C. ± 25 ° C. from the glass transition point of the unstretched film, ie, 120 ° C.
It is first stretched vertically at 3.3 ± 0.3 times at ± 25 ° C. Next, it is stretched transversely 3.6 ± 0.6 times under the same temperature conditions. Heat treatment after stretching is performed at 230 ± 18 ° C. Good results can be obtained by performing the heat treatment not only in one stage but also in two stages. Thus, an SPS film having a flexural modulus of 350 kg / mm ² or more is manufactured.

Such a film having a high flexural modulus is
It is difficult to apply the photographic layer as it is and adhere it firmly. There are many patents and literature on how to do this,
Reference is made to pages 3 and 4 of JP-A-3-54551, which can be referred to.

For example, as for the surface treatment, it is described that a corona discharge treatment is performed and that an undercoat layer is further provided. Examples of the undercoat layer include vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride.

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

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

In the present invention, the following compounds are preferably contained in the constituent layers of the silver halide photographic light-sensitive material, if necessary.

(1) Sensitizing dye JP-A-5-224330, page (3) [0017]-
(13) Compound described on page [0040] JP-A-6-194777 (11) page [0042]
Compounds described on page (22) to page [0094] JP-A-6-242533, page (2) on page [0015]
(8) Compound described on page [0034] JP-A-6-337492, page (3) [0012]-
(34) Compound described on page [0056] JP-A-6-337494, page (4) [0013]-
(14) Compound described on page [0039] (2) Supersensitizer JP-A-6-347938 (3) page [0011]-
(16) Compound described on page [0066] (3) Tetrazolium compound JP-A-6-208188, page (8) page [0059] to
Compounds described on page (10) [0067] The above-mentioned additives and other known additives are described in, for example, Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The following table shows the types and locations of the compounds shown in these three research disclosures.

[0179]

[Table 1]

The various photographic additives used in the present invention may be used by dissolving them in an aqueous solution or an organic solvent. However, when they are hardly soluble in water, they are converted into fine crystalline particles to form water, gelatin, hydrophilic or hydrophobic polymer. It can be dispersed and used. In order to disperse the dye, dye, desensitizing dye, hydrazine, redox compound, fogging inhibitor, ultraviolet absorber and the like of the present invention, a known dispersing machine can be used. Specific examples include a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, and a high-speed impeller disperser. These photographic additives dispersed in the present invention are fine particles having an average particle size of 100 µm or less, and are usually 0.02 to 10
Used with an average particle size of μm.

As a dispersion method, a method of mechanically stirring at high speed (JP-A-58-105141), a method of heating and dissolving with an organic solvent, and dissolving the same with a gelatin or hydrophilic polymer containing a surfactant or an antifoaming agent. A method of removing an organic solvent by dispersing while adding to an aqueous solution (JP-A-44-22948)
), A method of dissolving in an acid such as citric acid, acetic acid, sulfuric acid, hydrochloric acid, malic acid and the like, in which a crystal having a pH of 4.5 to 7.5 is precipitated and dispersed in a polymer (JP-A-50-80119). A method of dissolving in an alkali such as sodium, sodium bicarbonate, sodium carbonate and the like to precipitate and disperse crystals in a polymer such as gelatin having a pH of 4.5 to 7.5 (JP-A-2-1
No. 5252) can be applied. For example, hydrazine that is hardly soluble in water can be dissolved with reference to JP-A-2-3033, and this method can be applied to other additives. In addition, a dye having a carboxyl group, a sensitizing dye, an inhibitor, and the like can increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxyl group.
That is, calcium ions, magnesium ions, etc.
It is preferable to make the salt hardly soluble by adding 0 to 4000 ppm in the hydrophilic colloid layer. The use of other salts is not limited as long as a hardly soluble salt can be formed. The method of dispersing the fine particles of the photographic additive can be arbitrarily applied to a sensitizer, a dye, an inhibitor, an accelerator, a contrasting agent, a contrasting auxiliary, etc. in accordance with the chemical and physical properties thereof.

For simultaneous application of a plurality of constituent layers from 2 to 10 layers of the present invention at a high speed of 30 to 1000 meters per minute, US Pat. Nos. 3,636,374 and 3,50.
A known slide hopper type or curtain coating described in US Pat. No. 8,947 can be used. In order to reduce unevenness during coating, it is preferable to lower the surface tension of the coating solution or to use the above-mentioned hydrophilic polymer which can impart a thixotropic property in which the viscosity is reduced by a shearing force.

The light-sensitive material of the present invention may be provided with a crossover cut layer, an antistatic layer, an antihalation layer, and a back coat layer.

A known method is used for packaging the photographic light-sensitive material comprising the photographic element of the present invention.

Since the silver halide photographic light-sensitive material is susceptible to heat and humidity, it is preferable to avoid storing it under severe conditions. Generally, it is better to store at 5 ° C to 30 ° C.
The humidity should be between 35% and 60% relative humidity. It is common practice to package in polyethylene of 1-2000μ to protect from humidity. Polyethylene can suppress the permeation of water by improving the regularity of crystals by using a metallocene catalyst. Further, the surface of the polyethylene is 0.1 to 1000
Moisture permeation can be suppressed by coating the silica with a thickness of μ.

In the present invention, processing is preferably performed using a developing replenisher prepared from a solid processing agent.

The solid processing agents used in the present invention are powder processing agents, solid processing agents such as tablets, pills and granules, etc., which have been subjected to a moisture-proof treatment as required. Pastes and slurries are semi-liquid and inferior in storage stability.
These are not included in the solid processing agent of the present invention.

The powder as used in the present invention refers to an aggregate of fine crystals. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

Among the solid processing agents, tablets are preferred
It is preferably used because of high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated solution or a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted such as forming a coating layer by spraying.

A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Further, the particle size distribution is
% Is preferably within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pricketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-1.
No. 09043, No. 3-39735 and No. 3-3993
It can be produced by a general method described in the specification such as No. 9. Furthermore, powder processing agents are described, for example, in JP-A-54-13.
No. 3332, British Patent Nos. 725,892 and 729,8
No. 62 and German Patent 3,733,861, etc., it can be produced by a general method.

[0195] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0g
/ Cm ³ in terms of the strength of the solid material obtained,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

The solid processing agent used in the present invention is used at least for a developer and a fixing agent, but can be used for other photographic processing agents such as other rinsing agents. In addition, it is the developer and the fixing agent that can exclude the regulation of liquid dangerous substances.

According to the embodiments of the present invention, it is most preferable that all the processing agents are solidified, but it is preferable that at least the developer is solidified. That is, since the developer component contains a large number of components that cause a mutual chemical reaction and also contains harmful components, the effects of the present invention are most remarkably exhibited. More preferably, the fixing agent other than the developer is a solid processing agent. These have conventionally been regarded as having a problem in transportation in a liquid packaging kit.

The solid processing agent used in the present invention may include the solidification of only one part of a certain processing agent, but it is preferable that all the components of the processing agent are solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

In the case of solidifying the developer, it is preferred that all of the alkali agent and the reducing agent be solid processing agents, and in the case of tablets, at least three agents are used and most preferably one agent is used. It is a preferred embodiment of the agent. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

Examples of the package of the solid processing agent of the present invention include polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched, Non-stretched), polyvinylidene chloride, polystyrene, polycarbonate,
Vinylon, EVAL, polyethylene terephthalate (P
ET), other polyesters, hydrochloric acid rubber, acrylonitrile butadiene copolymer, epoxy-phosphate resin (polymer described in JP-A-63-63037, polymer described in JP-A-57-32952). Resin materials and pulp are mentioned.

These are preferably made of a single material. When used as a film, the films are laminated and adhered, but may be used as a coating layer or a single layer.

Further, it is more preferable to use various gas barrier films, for example, using an aluminum foil or an aluminum vapor-deposited synthetic resin between the above-mentioned synthetic resin films.

Further, in order to preserve the solid processing agent and prevent the generation of stain, the oxygen permeability of these packaging materials is 50 ml.
/ M ² 24 hr · atm or less (at 20 ° C. and 65% RH),
More preferably, it is preferably 30 ml / m ² 24 hr · atm or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
μm, more preferably 50 to 1000 μm.

The above synthetic resin film may be a one-layer (polymer) resin film or two or more laminated (polymer) films.
It may be a resin film.

When the treating agent is packaged or bound or covered with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, Hydroxypropyl cellulose type,
Film or binder composed of pullulan, dextran or gum arabic, polyvinyl acetate, hydroxyethylcellulose, carboxyethylcellulose, carboxymethylhydroxyethylcellulose sodium salt, poly (alkyl) oxazoline or polyethylene glycol base Agents are preferably used, and among these, polyvinyl alcohol-based and pullulan-based ones are more preferably used from the viewpoint of the effect of coating or binding.

The thickness of the water-soluble film is preferably from 10 to 120 μm in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film and the precipitation of crystals in an automatic developing machine. Is particularly preferred, and especially those having a size of 20 to 60 μm are preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

Furthermore, the tensile strength of the water-soluble film was 0.1.
5 × 106~50 × 106kg / m ² are preferred, especially 1 × one hundred and six to twenty-five preferably × 106 kg / m ^2, more especially is 1.5 × 106~10 × 106kg / m ² preferred. These tensile strengths are measured by a method described in JIS Z-1521.

The photographic processing agent packaged or bound or coated with a water-soluble film or binder can be used during storage, transportation, and handling to prevent atmospheric humidity such as high humidity, rain and fog, and water. It is preferable that the moisture-proof packaging material has a film thickness of 10 to 15 in order to prevent damage from sudden contact with water due to splashing or wet hands.
A film having a thickness of 0 μm is preferable, and the moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene, or polypropylene; kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, or polyvinyl chloride, which can have a moisture-proof effect with polyethylene. It is preferably at least one selected from a metal foil such as vinylidene chloride, polyamide, polycarbonate, acrylonitrile and aluminum, and a metallized polymer film, or a composite material using these.

In the practice of the present invention, it is also preferable that the moisture-proof packaging material is made of a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those made of natural polymers, microorganism-produced polymers, synthetic polymers having good biodegradability, and the incorporation of biodegradable natural polymers into plastics. And those in which a group which is excited by ultraviolet rays and is linked to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability can be used favorably.

[0213] These specific representative examples are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial polymers PHB-PHV (3-hydroxybutyrate and 3-hydroxyvale) Of “Bio”) as a component
pol ", microbial-produced cellulose, etc. Synthetic polymers with good biodegradability Polyvinyl alcohol, polycaprolactone, etc., or copolymers or mixtures thereof Mixing of biodegradable natural polymers into plastics As natural polymers with good biodegradability , Starch and cellulose, which have shape-degrading properties in addition to plastics.As photodegradable plastics, the introduction of carbonyl groups for photodegradability, etc. is there.

For such degradable plastics,
"Science and Industry", Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July, 1990, No. 23
~ 34 pages and the like can be used. Biopol (manufactured by ICI), E
co (eco) (manufactured by Union Carbide), E
colite (Eco Plastic)
Co., Ltd.), Ecostar (St. Law)
Commercially available decomposable plastics such as R. Starch (manufactured by Rence Starch) and Knuckle P (manufactured by Nippon Unicar) can be used.

The above moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

In the black-and-white silver halide photographic light-sensitive material of the present invention, it is preferable that at least one of the developer and / or the developing replenisher contains ascorbic acid or a derivative thereof.
As ascorbic acid or a derivative thereof, a compound represented by the following general formula (A) is preferable.

[0218]

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

[0220]

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In the general formula (Aa), R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, Represents a sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₁ represents O or S,
Y ₂ represents O, S or NR ₄ . R4 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Examples of the substituent of the alkyl group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group,
An aryl group having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), a heterocyclic group (eg, 2,2,6,6-tetramethylpiperidyl group, quinolizinyl group, N, N′-diethylpyrazolidinyl group) , A pyridyl group, etc.), having 1 to 2 carbon atoms
0 alkoxy group (for example, methoxy group, ethoxy group, etc.), aryloxy group having 6 to 20 carbon atoms (for example, phenoxy group, etc.), alkenyloxy group having 1 to 20 carbon atoms (for example, allyloxy group, etc.), 20 alkynyloxy groups (such as propargyloxy group), heterocyclic oxy groups (such as pyridyloxy group), and having 1 to 26 carbon atoms
(For example, acetylamino group, heptylamino group, propionylamino group, etc.), amino group (amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.) and the like.

Examples of the substituent of the amino group include a halogen atom (for example, Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (for example, phenyl group, naphthyl group and the like), and a C 1 to C 20 group. (E.g., methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl, etc.) and heterocyclic groups (e.g., 2,2
6,6-tetramethylpiperidyl group, quinolizinyl group,
N, N'-diethylpyrazolidinyl group, pyridyl group, etc.), C1-C20 alkoxy group (for example, methoxy group, ethoxy group, etc.), C6-C20 aryloxy group (for example, phenoxy group, etc.) An alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group),
20 alkynyloxy groups (eg, propargyloxy group), heterocyclic oxy groups (eg, pyridyloxy group), and acyl groups having 1 to 20 carbon atoms (eg, acetyl group, heptyl group, propionyl group, etc.).

Examples of the substituent of the alkylthio group include a halogen atom (for example, Cl and Br), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (for example, phenyl and naphthyl), a heterocyclic group (for example, 2,2,6,6
-Tetramethylpiperidyl group, quinolizinyl group, N,
N'-diethylpyrazolidinyl group, pyridyl group, etc.), an alkoxy group having 1 to 20 carbon atoms (eg, methoxy group, ethoxy group, etc.), an aryloxy group having 6 to 20 carbon atoms (eg, phenoxy group, etc.), carbon An alkenyloxy group having 1 to 20 carbon atoms (for example, allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (for example, propargyloxy group), a heterocyclic oxy group (for example, pyridyloxy group),
And 26 amino groups (for example, acetylamino group, heptylamino group, propionylamino group, etc.), and amino group (amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.).

Examples of the substituent of the aryl group include a halogen atom (eg, Cl, Br, etc.), a hydroxyl group,
An alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a butyl group, a cyclohexyl group, an isopropyl group, a dodecyl group, etc.), a heterocyclic group (eg, a 2,2,6,6-tetramethylpiperidyl group, a quinolizinyl group) , N, N'-diethylpyrazolidinyl group, pyridyl group, etc.)
20 alkoxy groups (e.g., methoxy group, ethoxy group, etc.), C6-C20 aryloxy groups (e.g., phenoxy group, etc.), C1-C20 alkenyloxy groups (e.g., allyloxy group, etc.), C1-C20 20 alkynyloxy groups (such as propargyloxy group), heterocyclic oxy groups (such as pyridyloxy group), and having 1 to 26 carbon atoms
(For example, acetylamino group, heptylamino group, propionylamino group, etc.), amino group (amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.) and the like.

Examples of the substituent of the above alkoxy group include:
A halogen atom (eg, Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (eg, a phenyl group,
A C1-C20 alkyl group (e.g., methyl, ethyl, butyl, cyclohexyl, isopropyl, dodecyl, etc.), a heterocyclic group (e.g., 2,
2,6,6-tetramethylpiperidyl group, quinolidinyl group, N, N'-diethylpyrazolidinyl group, pyridyl group, etc., aryloxy group having 6 to 20 carbon atoms (for example, phenoxy group, etc.), carbon number of 1 Alkenyloxy group (e.g., allyloxy group) having 1 to 20 carbon atoms, alkynyloxy group (e.g., propargyloxy group) having 1 to 20 carbon atoms, heterocyclic oxy group (e.g., pyridyloxy group), and 1 to 26 carbon atoms.
(For example, acetylamino group, heptylamino group, propionylamino group, etc.), amino group (amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.) and the like.

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

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

Formula (A)

[0230]

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[0231]

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Formula (Aa)

[0233]

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[0234]

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[0235]

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

In the present invention, ascorbic acid or a derivative thereof may be added to any processing agent such as a development replenisher, a fixing replenisher and a stabilizing replenisher, but is preferably contained in the development replenisher.

In the present invention, the developing solution and / or the developing replenisher includes a developing agent such as dihydroxybenzenes such as hydroquinone, chlorohydroquinone, methylhydroquinone and potassium hydroquinone monosulfonate;
Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4
-Hydroxymethyl-3-pyrazolidone, 3-pyrazolidones such as 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, aminophenols such as N-methyl-p-aminophenol and the like, or mixtures thereof),
Alkaline agents (sodium hydroxide, potassium hydroxide, etc.) and pH buffers (eg carbonates, phosphates, borates, boric acid,
Acetic acid, citric acid, alkanolamine, etc.) are preferably added. As the pH buffering agent, carbonate is preferable, and the amount of addition is 0.5 mol or more per liter.
It is preferably at most 5 mol, more preferably at least 0.75 mol and at most 1.5 mol. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers, surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide) , Nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazole, thiazole, etc.), chelating agent (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development acceleration Agents (eg, US Pat. No. 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.

In the present invention, the developer and / or the developing replenisher preferably contains a silver sludge inhibitor. Various silver sludge inhibitors are known, but preferably contain a compound represented by the following general formula (S).

Formula (S) Z ¹ -SM ^{1 In the} formula, Z ¹ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ² group, a —COOM ² group (M ² represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, at least one selected from the group consisting of a substituted or unsubstituted ammonium group, or selected from this group Substituted by at least one substituent represented by M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a salt with hydrohalic acid or sulfonic acid).

The alkyl group represented by Z ¹ is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, particularly 2 to 20 carbon atoms. May have. The aromatic group represented by Z ¹ is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ¹ is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and a heteroatom independently selected from nitrogen, oxygen and sulfur is preferably 1 to 6 in one ring. 5 or 6-membered ring, which may have a substituent other than the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent.

The above-mentioned ammonium group preferably has 20 or less carbon atoms, and the substituent is a substituted or unsubstituted linear, branched or cyclic alkyl group (eg, methyl, ethyl, benzyl, ethoxypropyl, cyclohexyl). , A substituted or unsubstituted phenyl group and a naphthyl group.

Of the compounds represented by the general formula (S), preferred is a compound wherein Z ¹ is a heterocyclic group having two or more nitrogen atoms.

Further, among the compounds represented by the general formula (S), more preferred are the compounds represented by the following general formula (Sa).

[0245]

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[0246] In the formula, Z is represents a non 5- or 6-membered saturated heterocyclic ring (pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine ring) group necessary to form a having a nitrogen atom, R ¹¹ And R ¹² are each a hydrogen atom, a —SM ¹ group, a halogen atom, an alkyl group (including a group having a substituent), an alkoxy group (including a group having a substituent), a hydroxyl group, a —COOM ² group, SO ₃
M ² groups, alkenyl groups (including those having a substituent),
Represents an amino group (including a group having a substituent), a carbamoyl group (including a group having a substituent), or a phenyl group (including a group having a substituent). Even when R ¹¹ and R ¹² form a ring, Good. The ring that can be formed is a 5- or 6-membered ring, and is preferably a nitrogen-containing heterocycle.

The formula (Sa) has at least one —S
A compound having an M ¹ group or a thione group, and selected from the group consisting of a hydroxyl group, a —COOM ² group, a —SO ₃ M ² group, a substituted or unsubstituted amino, or a substituted or unsubstituted ammonium group And at least one substituent. M ¹ and M ² each has the same meaning as M ¹ and M ² as defined in compounds represented by the above general formula (S).

Preferably, Z is a group forming a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the above-described SM ¹ group or thione group. Atoms (fluorine, chlorine, bromine), lower alkyl groups (including those having a substituent, preferably those having 5 or less carbon atoms such as methyl and ethyl) and lower alkoxy groups (including those having a substituent; methoxy, Examples thereof include those having 5 or less carbon atoms such as ethoxy and butoxy, lower alkenyl groups (including those having a substituent, and those having 5 or less carbon atoms), carbamoyl groups, and phenyl groups.

In the general formula (Sa), the following general formula A
To F are particularly preferred.

[0250]

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In the formula, each of R ²¹ , R ²² , R ²³ and R ²⁴ is a hydrogen atom, a —SM ¹ group, a halogen atom, a lower alkyl group (including those having a substituent. number 5 is preferably less), are preferred ones. 5 or less carbon atoms, including those having a lower alkoxy group (substituent), a hydroxyl group, -COOM ^2, -SO ^₃ M ₃
Group, lower alkenyl group (including those having a substituent, preferably having 5 or less carbon atoms), amino group, carbamoyl group or phenyl group, at least one of which is -SM.
^One . M ¹ , M ² and M ³ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. In particular, the substituent group other than -SM ^1, a hydroxyl group, -COOM ^2, -SO ^₃ M ₃ group, it preferably has a water-soluble group such as an amino group. R ²¹ ,
The amino group represented by R ²² , R ²³ and R ²⁴ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

The typical examples of the silver sludge inhibitor represented by formula (S) are shown below, but the invention is not limited thereto.

[0253]

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[0254]

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[0255]

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[0256]

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[0257]

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[0258]

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The amount of the compound represented by the general formula (S) is preferably 10 ^-6 to 10 ^-1 mol, more preferably 10 ^-5 to 10 ^-2 mol per liter of the developing solution. Is preferred.

To attain the object of the present invention, the pH of the developer is adjusted to 9 or more and less than 11. More preferably, the pH is 9.3 or more and 10.8 or less.

As the fixing solution and / or the fixing replenisher, those having a commonly used composition can be used. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

Examples of the fixing solution and / or fixing replenisher include water-soluble aluminum salts which act as hardeners, for example, aluminum chloride, aluminum sulfate, potassium alum, aldehyde compounds (for example, glutaraldehyde and glutaraldehyde sulfite adducts, etc.). ) Etc. can be added.

If desired, preservatives (eg, sulfites, bisulfites), pH buffering agents (eg, acetic acid and citric acid), pH adjusters (eg, sulfuric acid), A compound such as a chelating agent having a water softening ability can be contained.

The fixing replenisher preferably comprises a solid processing agent. Further, the fixing replenisher is preferably one agent containing all necessary components, and particularly preferably a granule containing a hardener. preferable.

The pH of the fixing solution is preferably 3 or more and less than 8.

After the fixing treatment, it is washed and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide,
Ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. are used in combination, aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid) Or an alkali metal salt thereof,
Nitrilotriacetate, polyphosphate, etc.), anti-binders (for example, phenol, 4-chlorophenol, cresol, o-
Phenylphenol, chlorophen, dichlorophen,
Formaldehyde, p-hydroxybenzoic acid ester,
2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium-chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxy Diphenyl ether, etc.), a color tone adjuster and / or a residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
-Sodium mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.) Is contained. Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

From the demand for reducing the amount of waste liquid, the replenishment amount for development is 1
It is preferably 30 ml or more and 200 ml or less per m ² , more preferably 30 to 1 per m ² respectively.
90 ml. The term "replenishment amount of development" as used herein indicates a replenishment amount. Specifically, it is the volume of a solution obtained by dissolving a replenisher for granule development in water.

The developing replenisher and the fixing replenisher may be the same as or different from the developing starter and the fixing starter in the tank of the automatic developing machine.

The developing start solution and the fixing start solution may be prepared from a granulating agent, a liquid concentrate, or a liquid in use.

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

In the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine to the emergence from the drying zone when processing using the automatic developing machine is 60 due to the demand for shortening the developing time. It is preferably 10 seconds or less and 10 seconds or more. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. This is a time including all the time of the process, that is, a time of Dry to Dry. Total processing time is 1
If the time is less than 0 second, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dr)
y) is 15 to 45 seconds. Further, in order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is preferably 22 seconds or less and 2 seconds or more.

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

As the heat transfer material of 60 ° C. or higher,
A heat roller is mentioned as an example. It is preferable that the outer periphery of the hollow roller made of aluminum is covered with silicone rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

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

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

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

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

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

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regenerating purifying agent and apparatus: JP-A-6-250352, page (3) "0011" to page (8), "0058" (3) Waste liquid treatment method: JP-A-2-64638, 388
(2) Lower left column of page 391 (5) Lower left column of page (4) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) Lower right column to page 501 (7) Lower right column and JP-A-2-10805
No. 1, page 588 (2), lower left column to page 589 (3), lower left column (7) Method for recovering fixing waste silver: JP-A-6-27623, page (4), "0012" to page (7), "0071".

[0281]

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

Example 1 (Preparation of Silver Halide Emulsion A) By controlling the potential to 90 mV using a double jet method, 100 g of silver chloride was prepared.
Silver chloride core particles having an average particle size of 0.12 μm consisting of mol% were prepared. At the time of mixing the core particles, 5 × 10 ⁻⁵ mol of K ₂ OsCl ₆ was added per mol of silver. The core particles were provided with a shell composed of 100 mol% of silver chloride by controlling the potential to 90 mV using a double jet method. At that time, 6.0 × 10 ⁻⁵ mol of K ₂ OsCl ₆ was added per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloride grain having an average grain size of 0.15 μm. Then, desalting is carried out by using a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, compound G-8 on page 287 (3) of JP-A-2-280139). did.
Also, before the desalting step, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻³ mol per mol of silver (hereinafter, unless otherwise specified, the amount per mol of silver). EAg after desalination is 5
It was 190 mV at 0 ° C.

The obtained emulsion was mixed with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 1 × 10 ^−3.
Mol and then potassium bromide and citric acid.
H5.6, EAg was adjusted to 123 mV, and chloroauric acid was adjusted to 1
3 × 10 ⁻⁶ mol of inorganic sulfur after adding × 10 ⁻⁵ mol,
2 x 10 diphenylpentafluorophenyl selenide
^-6 mol was added and the mixture was chemically ripened at a temperature of 60 ° C. for 60 minutes. After aging, 4-hydroxy-6-methyl-1,3,3
2 × 10 ⁻³ mol of 3a, 7-tetrazaindene, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and gelatin were added. The emulsion was set at a reduced temperature.

(Preparation of Silver Halide Emulsion B) Shell K
A silver halide emulsion B having the same sensitivity as that of the silver halide emulsion A was prepared except for the amount of ₂ OsCl ₆ added.

An antihalation (AHU) layer, a first emulsion layer, a second emulsion layer, and a protective layer were successively formed on one undercoat layer of the following support so that the coating rate was as follows per unit m ² , and the coating rate was changed per minute. Simultaneous multilayer coating was performed by a curtain coating method at 250 m.

After forming an antistatic layer having the following composition on the undercoat layer on the opposite side, a backing layer, a hydrophobic polymer layer, and a backing protective layer were successively laminated so that the following amounts per unit m ² were obtained. A sample was obtained by coating.

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

2-Hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) copolymer (numbers are by weight) 1.5 g / m ² Surfactant A 10 mg / M ² Hexamethylene-1,6-bis (ethylene urea) 15 mg / m ² (Antistatic layer) Corona discharge of 10 W / (m ² · min) was performed on a polyethylene terephthalate support provided with an undercoat layer, An antistatic layer having the following composition was applied at a speed of 70 m / min using a roll-fit coating pan and an air knife, dried at 90 ° C. for 2 minutes, and then dried at 140 ° C.
For 90 seconds.

Water-soluble conductive polymer B 0.6 g / m ² Hydrophobic polymer particles C 0.4 g / m ² Ethylene oxide compound D 0.1 g / m ² Hardener E 0.2 g / m ² (first emulsion Layer composition) Emulsion A (Amount of coated silver) 1.3 g / m ² Gelatin 0.7 g / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² Na polystyrene sulfonate 50 mg / m ² styrene Hydrophilic polymer of maleic acid copolymer 20 mg / m ² Compound S (sodium-iso-amyl-n-decylsulfosuccinate) 5 mg / m ² 5-methylbenzotriazole 10 mg / m ² Polymer latex 0.3 g / m ² (Composition of Second Emulsion Layer) Emulsion B (Amount of coated silver) 1.3 g / m ² Gelatin 0.7 g / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² Na polystyrene sulfonate 50 mg / m ² hydrophilic polymer of styrene-maleic acid copolymer 20 mg / m ² Compound J 5 mg / m ² 5-methylbenztriazole 10 mg / m ² Polymer latex 0.3 g / m ² (antihalation ( AHU) layer) A layer having the following composition was provided as a lower layer of the emulsion layer.

Gelatin 0.8 mg / m ² Polymer latex 0.3 mg / m ² Na polystyrene sulfonate 11 mg / m ² Ethyl acrylate latex 20 mg / m ² Solid dispersed fine particles of dye O (average particle size 0.1 μm) 30 mg / m ² (Protective layer upper layer composition) Gelatin 0.8 mg / m ² Water-soluble dye Q (shown in the table) Matting agent: amorphous silica (average particle size 1.63 μm) 15.0 mg / m ² Matting agent: amorphous silica ( average particle diameter 5.2μm) 21.0mg / m ² citric acid 4.5 mg / m ² of polystyrene sulphonic acid Na 11.0 mg / m ² hardener T 5 mg / all layers of gelatin 1g surfactant M 1 mg / m ² compound F 12 mg / m ² (composition of backing layer) Gelatin 0.8 g / m ² Compound F 5 mg / m ² Hydrophobic polymer particles C 0.3 g / m ² colloidal silica ( Average particle size: 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Hardener E 10 mg / m ² (hydrophobic polymer layer composition) Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² hardener L 6 mg / m ² (backing protective layer composition) gelatin 0.5 g / m ² water-soluble dyes Q 160 mg / m ² water-soluble dye R 30 mg / m ² styrene - hydrophilic polymer maleic acid copolymer 20 mg / m ² matting agent Monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant A 50 mg / m ² H (OCH ₂ CH ₂ ) ₆₈ OH 50 mg / m ² Hardener T 20 mg / m ² The structure of the compound used above is shown below.

[0291]

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[0292]

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[0293]

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[0294]

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After the coating and drying, the surface resistivity on the backing side was 6 × 10 ¹¹ at 23 ° C. and 20% RH, and the pH on the emulsion side was 5.5.

(Preparation of solid fine particle dispersion of dye) In Examples of the present invention, a solid fine particle dispersion prepared according to the following method was used as the dye.

In a 60 ml screw cap container, 21.7 ml of water and Triton X- as a surfactant were added.
6.7% solution 30 of 200 (Rohm & Haas)
Then, 1.0 g of a compound represented as a dye powdered in a mortar and a surfactant were added to the container, and 40 ml of zirconium oxide beads (2 mm in diameter) were added.
Close the cap, place in a ball mill, disperse at room temperature until the desired particle size is achieved, add 8.0 g of a 12.5% gelatin aqueous solution, mix well, filter out zirconium oxide beads, and remove solid fine particle dispersion. Obtained.

[0298] (treatment liquid formulations) developing starter (HAD-S) (using 1 liter minute) 31.8 g Sodium sulfite diethylenetriaminepentaacetic acid pentasodium 1.45g potassium sulfite 42.6g KBr 2.67g H ₃ BO ₃ 8g Potassium carbonate 112.2 g 2-mercaptoadenine 0.07 g diethylene glycol 40 g 5-methylbenzotriazole 0.21 g 1-phenyl-5-mercaptotetrazole 0.03 g dimezone S (1-phenyl-4-hydroxymethyl-4-methylpyrazoli Don 0.85 g Hydroquinone 20 g Compound A-39 of the general formula (A) 5.5 g Pure water and KOH were added to make up to 1000 ml, pH1
Adjust to 0.40.

Preparation of Development Replenishing Granules (KR) Preparation of Granulated A Parts (for 1 L of Working Solution) Diethylenetriaminepentasodium pentasodium 1.45 g Sodium carbonate (monohydrate) 76.27 g D-mannitol (trade name) 6.94 g Sorbitol 2.93 g LiOH 10 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the granulated product was fluidized. It was dried at 40 ° C. for 2 hours in a bath dryer to obtain a granulated A part having an average particle diameter of 3000 μm and a repose angle of 33 °.

Preparation of granulated B part (for 1 liter of used liquid) Sodium sulfite 56.58 g KBr 2 g H ₃ BO ₃ 4 g 2-mercaptoadenine 0.25 g 5-methylbenzotriazole 0.26 g 1-phenyl-5- Mercaptotetrazole 0.06 g Dimezone S 1.25 g Hydroquinone 20 g D-mannitol (trade name: manufactured by Kao Corporation) 4.77 g Compound A-39 of general formula (A) 5.5 g The above materials were mixed in a commercially available bantam mill for 30 minutes. Then, after granulating at room temperature for 10 minutes with a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized-bed dryer, and granulated with an average particle size of 4000 μm and a repose angle of 30 °. The object B part was obtained.

The above parts A and B were thoroughly mixed to obtain a replenisher for granule development HAD-KR. When using,
Dissolved in water to make 1 liter. The pH of the working solution is 10.
70.

Fixing start solution (HAF-S) (for 1 liter of used solution) Pure water 116 ml Ammonium thiosulfate 140 g Sodium sulfite 22 g Boric acid 9.8 g Tartaric acid 3 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Sulfuric acid Aluminum / 18-hydrate salt 18g Finish to 400ml with pure water.

When used, 600 ml of pure water and the above concentrated liquid are mixed and used. The pH of the working solution was 4.90.

Preparation of Fixing Replenishment Granules (HAF-KR) Preparation of Granulated Part A (for 1 L of Working Solution) Ammonium Thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium metabisulfite 7.5 g Sodium acetate 40 g Pine flow (trade name: manufactured by Matsutani Chemical Co., Ltd.) 11.8 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. It was dried at 40 ° C. for 2 hours in a fluidized-bed dryer to obtain a granulated A part having an average particle diameter of 4000 μm and a repose angle of 40 °.

Production of granulated B parts (for 1 liter of liquid used) 10 g of boric acid 3 g of tartaric acid 26.5 g of sodium hydrogen sulfate 15.8 g of aluminum sulfate / 18-hydrate D-mannitol (trade name: manufactured by Kao Corporation) 4.4 g N-lauroyl taurine (trade name: manufactured by Nikko Chemicals) 2 g Demol N (trade name: manufactured by Kao Corporation) 5 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further mixed with a commercially available stirring granulator at room temperature for 10 minutes. After granulation for minutes, the granulated product was dried in a fluidized-bed dryer at 40 ° C. for 2 hours to obtain a granulated product B part having an average particle size of 3300 μm and a repose angle of 28 °.

The above parts A and B were completely mixed to obtain HAF-KR, a fixing granule replenisher. When used, it was used by dissolving it in water so that the volume became 1 liter. The pH of the working solution was 4.20.

(Automatic developing machine) GR-26 manufactured by Konica Corporation
An automatic developing machine modified from SR was used. This automatic developing machine has a far-infrared heater in the drying zone, and has a cover that covers the entire surface of the processing tank so that the processing liquid is difficult to evaporate.

(Processing conditions) Temperature time Current image 38 ° C. 15 seconds Fixing 38 ° C. 9 seconds Washing 38 ° C. 8.5 seconds Squeeze 2.5 seconds Drying 40 ° C. 10 seconds Dry to Dry 45 seconds Line speed ( (Conveying speed) 3300 mm / min The fixing waste liquid is processed while returning the processing liquid after silver recovery using the silver recovery apparatus described in Example 1 of JP-A-6-27623 to the fixing tank again, Was subjected to a treatment using an anti-scalp device (water clean) manufactured by Konica Corporation.

<< Evaluation Method >> The above-mentioned photosensitive material was applied to a P627F manufactured by Dainippon Screen Co., Ltd.
Exposure was performed with an M printer (mercury lamp light source), and the following items were evaluated in the above-described processing.

1) Sensitivity and density: 50% halftone dot area (1
(75 L / in) is the sensitivity and density at the time of exposure to give a halftone dot area of 50% on the film sample.

In the actual measurement, the obtained developed sample was
It was measured with DA-65 (a digital densitometer manufactured by Konica Corporation). The sensitivities in the table indicate sample No. The sensitivity was expressed as a relative sensitivity when the sensitivity at a density of 2.0 was 100. The concentration showed the highest concentration.

In this case, if the sensitivity is a constant value in the present invention, there is no particular problem, and a maximum density of 3.0 or more is practically necessary.

2) Gradation variability: expressed by the difference between the exposure amount that results in a halftone dot area of 50% and the halftone area% of twice the exposure amount. From the exposure stability, 1.5 to 5% is a practically usable range, and 2 to 4% is preferable.

[0314]

[Table 2]

From the results in Table 2, it can be seen that, in the constitution of the present invention, the density is high even in the faithful repetition in which the halftone dot area of 50% (175 L / in) becomes 50% on the film sample, and the gradation is high. It can be seen that the influence on the photographic performance at the beginning and end of the variable running is small.

Example 2 In Example 1, the solid dispersion fine particles of the dye O in the antihalation (AHU) layer were removed, and the redox DIR compound No. 21 was added in an amount of 70 mg / m ² , and otherwise the same sample was prepared and evaluated.

[0317]

[Table 3]

According to the results shown in Table 3, in the same manner as shown in Table 2, in the structure of the present invention, the halftone dot area (175 L / i) was 50%.
It can be seen that the density is high even in the faithful repetition where n) is 50% halftone dot area on the film sample, and the influence on the photographic performance at the beginning and end of variable tone running is small.

[0319]

According to the present invention, it is possible to provide a silver halide light-sensitive material for a bright room, in which a halftone dot is faithfully reproduced and a decrease in density is small.

Claims (5)

[Claims] 1. A method according to claim 1, wherein at least two silver halide emulsion layers are formed on the support, and the sensitivity of the silver halide emulsion layer on the side close to the support is 70 times lower than that of the silver halide emulsion layer adjacent thereto. A dye-containing layer having an optical density of 0.2 to 1.0 at 365 μm is provided thereon, and a layer containing a dye solid-dispersed in fine particles is provided between the layer and the support. A silver halide photographic light-sensitive material, characterized in that the material has substantially no sensitivity at 450 μm or more. 2. The method according to claim 1, wherein at least two silver halide emulsion layers are formed on the support, and the sensitivity of the silver halide emulsion layer on the side close to the support is 70% lower than that of the silver halide emulsion layer adjacent thereto. A dye-containing layer having an optical density of 0.2 to 1.0 at 365 μm is provided thereon, and a layer containing a redox DIR compound is provided between the support and the support. A silver halide photographic light-sensitive material characterized by having no sensitivity at 450 μm or more. 3. A silver halide emulsion layer having at least two silver halide emulsion layers formed on a support, wherein the sensitivity of the silver halide emulsion layer closer to the support is 70 times lower than that of the silver halide emulsion layer adjacent thereto. ６００600%, and a dye-containing layer having an optical density of 0.2 to 1.0 at 365 μm was provided on the upper layer, and further contained a redox DIR compound and a dye solid-dispersed in fine particles between the support and the support. A silver halide photographic light-sensitive material comprising a layer and having substantially no sensitivity at 450 μm or more. 4. The sensitivity of the silver halide emulsion layer closer to the support is one of the sensitivity of the silver halide emulsion layer adjacent thereto.
4. A silver halide photographic light-sensitive material according to claim 1, wherein a dye-containing layer having a density of 50 to 300% and an optical density at 365 [mu] m of 0.4 to 0.8 is provided thereon. 5. The silver halide photographic material according to claim 1, wherein the amount of gelatin is 2.5 g / m ² or less.