JP2002351003A - Silver halide photographic sensitive material and image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in sharpness and smoothness of dots and less liable to generate black spots as a silver halide photographic sensitive material for a photomechanical process, particularly for a scanner or an image setter. SOLUTION: The silver halide photographic sensitive material has at least one silver halide emulsion layer on the base and contains at least one hydrazine derivative in the silver halide emulsion layer or at least one of other hydrophilic colloidal layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast negative image using the same, and particularly to a super-high contrast suitable for a silver halide photographic material used in a photomechanical process. The present invention relates to a negative photosensitive material and an image forming method using the same.

[0002]

2. Description of the Related Art One of the methods for exposing a photographic light-sensitive material is to scan an original drawing, and to expose the silver halide photographic light-sensitive material based on the image signal, thereby forming a negative image or a positive image corresponding to the image of the original drawing. There is known an image forming method by a so-called scanner method for forming. There are various types of recording apparatuses that use the image forming method based on the scanner system, but a so-called dot generator system using a halftone generator has been widely used at present. Glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have been used as recording light sources for these scanner recording apparatuses. However, each of these light sources has a practical disadvantage that the output is weak and the life is short. To compensate for these drawbacks, there is a scanner that uses a coherent laser light source such as a He-Ne laser, an argon laser, a He-Cd laser, or a semiconductor laser as a light source of a scanner system. Various characteristics are required for the photosensitive material used in these scanners,
In particular, since exposure is performed with a short exposure time of 10 ⁻³ to 10 ⁻⁸ seconds, high sensitivity and high contrast are essential conditions even under such conditions. It is also important that good halftone dot quality be obtained even when the output is reduced in order to keep the life of the laser tube long.

[0003] In recent years, nucleation systems containing hydrazine derivatives and capable of obtaining ultra-high contrast photographic characteristics from the viewpoint of high sensitivity and high contrast have become mainstream in this field. It is advantageous to use a hydrazine derivative having high activity in order to obtain a photosensitive material having high contrast and high sensitivity in order to obtain a photosensitive material having good halftone dot quality. However, sand-like fog (black spots) generated in unexposed areas is advantageous. ) Easily occurs and improvement has been desired.

Further, in the printing industry, there is a strong demand for reducing the amount of processing waste liquid due to the influence on the environment, and there is a wide-ranging need for a low replenishment of a developing solution and a fixing solution. In order to meet these needs in the printing field, there is a demand for the development of a developing solution, a fixing solution, and a light-sensitive material corresponding to a low replenishing amount, even if the replenishing amount is small, in which the composition fluctuation in the processing solution is small.

In the field of graphic arts, with the recent demand for low replenishment and rapid processing,
There is a demand for a reduction in the amount of silver applied, and technical development of finer silver halide grains and higher sensitivity has been energetically carried out by those skilled in the art. By making the particles fine, covering power (blackening density per unit silver amount) can be increased, and the amount of silver used can be reduced.

On the other hand, a system in which a photosensitive material supply cassette is automatically conveyed to an exposure machine and an automatic developing machine is becoming common. In this method, a film is detected by several optical sensors installed inside an exposure machine or the like. The optical sensor generally uses a light source in the infrared region that is outside the photosensitive wavelength of the photosensitive material, and is a method of detecting a film by scattering of silver halide particles or the like.

Optical sensors used for such purposes are roughly classified into two types, a "transmission type" for detecting transmitted light of light emitted from the light emitting element and a "reflection type" for detecting reflected light. There are types. In the case of the transmission type sensor, the detection power is higher than that of the reflection type, but since the light emitting unit and the light receiving unit are separate, two sensors are required, and there is a disadvantage that the cost is high. On the other hand, the reflection-type sensor has a feature that the light-emitting unit and the light-receiving unit can be integrated, so that the installation is simple and the cost is advantageous.

In general, a reflection type sensor used for a photosensitive material recognizes infrared light emitted from a light emitting portion of the sensor mainly by scattering of silver halide particles, and detecting the scattered light by a light receiving portion. ing. Therefore, when the coated silver amount is reduced for low replenishment or the like, or when the particle size of the silver halide particles is reduced, scattering at the silver halide particles is reduced, and the light reception amount of the sensor is reduced. There was a problem that the photosensitive material was difficult to recognize. Japanese Patent Application Laid-Open Nos. 63-131135 and 8-95198 also disclose a method for dealing with a reduction in sensor detection power due to an increase in film transmittance due to silver saving and small particle size in transmission type sensors. However, these methods are aimed at reducing the transmittance of infrared rays, and no study has been made on countermeasures for the reflective sensor. Japanese Patent Laid-Open No. 10-22180 discloses a method corresponding to the detection power of a reflective infrared sensor.
No. 9 is known.

[0009]

A first object of the present invention is to provide a silver halide photographic light-sensitive material for photoengraving, particularly for a scanner or an image setter, in terms of sharpness of halftone dots and smoothness. An object of the present invention is to provide a silver halide photographic material which is excellent and hardly generates black spots. The second problem to be solved by the present invention is:
An object of the present invention is to provide a silver halide photographic light-sensitive material free from sensor troubles in an image setter. A third object of the present invention is to provide a developing method capable of stably developing the silver halide photographic material.

[0010]

This problem has been solved by the following. (1) At least one silver halide emulsion layer is provided on a support, and at least one silver halide emulsion layer or another hydrophilic colloid layer is represented by at least one kind of general formula (D). Silver photographic light-sensitive material characterized by containing a hydrazine derivative. General formula (D)

Embedded image In the formula, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₁₀ has a σp value of 0.2 or more and 0.8 or less,
And π value is -5.0 or more, represents a 2.0 following blocking _{group, G 10} is -CO -, - C (= S ) -, - SO 2 -,
_{-SO -, - PO (R 30} ) - group _{(. R 30} has the same meaning as _{R 10,} may be different from _{R 10),} or an iminomethylene group. A ₁₀ and A _{20 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. (2) In the same layer as the photosensitive silver halide emulsion layer or in another hydrophilic colloid layer, 850 to 10
(1) The silver halide photographic light-sensitive material according to (1), which contains solid particles in an amount that increases the average value of the integrated value of the spectral reflectance at 00 nm by 1.5% or more. (3) The photosensitive silver halide photographic material as described in (2), wherein the solid particles have a refractive index of 1.54 or more. (4) The photosensitive silver halide photographic material as described in (2) or (3), wherein the solid particles are substantially non-photosensitive silver halide particles. (5) The solid grains are substantially light-insensitive silver halide grains, and the light-insensitive silver halide grains are tabular grains having an average grain thickness of 0.02 to 0.20 μm. 4. The photosensitive silver halide photographic material according to item 1. (6) The coated silver amount of the photosensitive silver halide emulsion is 3.0 g.
/ M ² or less (1) to (5) a light-sensitive silver halide photographic material according to any one. (7) The photosensitive silver halide photographic material as described in any one of (1) to (6) above, wherein at least one of the silver halide emulsion layer and the other hydrophilic colloid layer is
A silver halide photographic material comprising at least one compound represented by the general formula (1). General formula (1)

Embedded image In the formula, M represents a hydrogen atom, an alkali metal, or a protecting group that is cleaved by an alkali. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitro group, a substituted or unsubstituted group. Represents an alkoxy group or a cyano group. (8) An image characterized in that the photosensitive silver halide photographic material according to any one of (1) to (7) is subjected to development processing using a developer having a pH of 9.0 or more and less than 11.0. Forming method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION

The benzotriazole compound represented by the general formula (1) will be described in more detail. In the formula, M is a hydrogen atom, an alkali metal atom (for example, a sodium atom, a potassium atom, or the like) or a protecting group that can be cleaved by an alkali (for example, an acetyl group, a propionyl group, a pivaloyl group, a stearoyl group, a benzyl group, a p-toluenesulfonyl group, Dodecylcarbamoyl group, benzoyl group, cyclohexylcarbamoyl group, etc.). R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and each represents a hydrogen atom,
Substituted or unsubstituted alkyl group (preferably having up to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, hydroxyethyl group, chloropropyl group, benzyl group, cyanoethyl group, etc.), substituted or unsubstituted aryl Groups (preferably having 6 to 12 carbon atoms such as phenyl, naphthyl, p-tolyl, p-chlorophenyl), halogen atoms (such as chlorine and bromine), nitro, substituted or unsubstituted An alkoxy group (preferably having up to 12 carbon atoms such as a methoxy group, an ethoxy group, an n-butoxy group, a dodecyloxy group, a hydroxyethoxy group, etc.) and a cyano group.

Hereinafter, typical examples of the benzotriazole-based compound used in the present invention will be listed, but the present invention is not limited thereto. (1) 5,6-dimethylbenzotriazole (2) 5-butylbenzotriazole (3) 5-methylbenzotriazole (4) 5-chlorobenzotriazole (5) 5-bromobenzotriazole (6) 5,6-dichloro Benzotriazole (7) 4,6-dichlorobenzotriazole (8) 5-nitrobenzotriazole (9) 4-nitro-6-chloro-benzotriazole (10) 4,5,6-trichlorobenzotriazole (11) 5- Carboxybenzotriazole (12) 5-sulfobenzotriazole Na salt (13) 5-methoxycarbonylbenzotriazole (14) 5-aminobenzotriazole (15) 5-butoxybenzotriazole (16) 5-ureidobenzotriazole (17) benzo Triazole In the invention, 5-methyl benzotriazole is particularly preferred.

In the present invention, the benzotriazole compound represented by the general formula (1) is added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or any other hydrophilic colloid layer. Although it may be added, it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Further, two or more benzotriazole compounds represented by the general formula (1) can be used in combination. In the present invention, the addition amount is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, particularly preferably from 1 × 10 ^{−3 to} 7 × 10 ⁻² mol, per 1 mol of silver halide. In the present invention, the symbol “to (or)” represents a numerical range including numerical values described before and after it as a minimum value and a maximum value, respectively.

Next, the hydrazine represented by the general formula (D)
The derivative will be described in more detail. Where R₂₀Is
Represents an aliphatic group, an aromatic group, or a heterocyclic group;₁₀
Has a σp value of 0.2 or more and 0.8 or less and a π value of −
Represents a block group of 5.0 or more and 2.0 or less;₁₀Is
-CO-, -C (= S)-, -SO₂-, -SO-,-
PO (R₃₀) -Group (R₃₀Is R₁₀Same as the group defined in
Within the same range, R ₁₀May be different from
No. ) Or iminomethylene group. A₁₀, A
₂₀Are both hydrogen atoms, or one is a hydrogen atom and the other is
Is a substituted or unsubstituted alkylsulfonyl group, or
A substituted or unsubstituted arylsulfonyl group, or
Represents a substituted or unsubstituted acyl group.

In the formula (D), the aliphatic group represented by R ₂₀ is preferably a substituted or unsubstituted, linear or branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. is there. In the general formula (D), R
_The aromatic group represented by ₂₀ is a monocyclic or condensed-ring aryl group, such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂₀ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group such as a pyridine ring, a pyrimidine ring, an imidazole ring, and a pyrazole ring. Quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, triazine ring and the like. Preferred as R ₂₀ is an aryl group, and particularly preferred is a phenyl group.

The group represented by R ₂₀ may be substituted,
Representative substituents include, for example, halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl Group, heterocyclic group, quaternized nitrogen-containing heterocyclic group (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acyl group Rucarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy groups , A heterocyclic oxy group, Siloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfone Amide group, ureide group, thioureide group, isothioureide group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium, oxamoylamino, (alkyl or aryl) sulfonyluureido, acylureido, N-acylsulfamoylamino, nitro, mercapto, (alkyl, aryl, or heterocycle) thio, An alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an N-acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphate amide or a phosphate ester structure. Groups, and the like. These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group, a sulfonamide. Group, ureido group,
Sulfamoylamino group, imide group, thioureido group,
Phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocyclic ) Thio, sulfo (including its salts), sulfamoyl, halogen, cyano,
And a nitro group.

[0019] In general formula _{(D), R 10} is σp value of 0.2 or more, 0.8 or less, and π value is -5.0 or more,
Represents a block group of 2.0 or less. Preferably, the σp value is 0.3 or more and 0.6 or less, and the π value is -4.0 or more and 1.5
It is as follows.

The σ _p value of R ₁₀ was determined according to the following equation. σ _p value = log (k _R10 / k _H ) where k _H represents the proton dissociation equilibrium constant of benzoic acid at 25 ° C., and k _R10 represents the proton dissociation equilibrium constant of benzoic acid in which the para-position is substituted with R ₁₀ .

The π value (hydrophobic substituent constant) of R ₁₀ was determined according to the following equation. π value ₌ logP _{R10 -logP H} P R10 is the partition coefficient of a molecule containing the substituent _{R 10, P H} respectively represent the distribution coefficient of the reference material. For example, π _CF3 =
π _{PhSO2NHPhCOCF3} −π _PhSO2NHPhCHO . Here, P is a partition coefficient in the n-octanol / water system, and when the concentrations in the oil phase and the aqueous phase are C _o and C _w , respectively, P = C _o /
It is represented by C _w .

Specific examples of R ₁₀ include the following substituents.

[0023]

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The hydrazine derivative represented by the formula (D) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such an adsorbing group include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups, which are described in U.S. Pat. Nos. 4,385,108 and 4,459,347; Nos. 195233, 59-200231, 59-201045, 59-201046, and 5
Nos. 9-201047, 59-201048, 59
JP-201049, JP-A-61-170733, and JP-A-61-170933.
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

R _{20 in the} formula (D) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein.
In the present invention, the ballast group refers to a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group) having 6 or more carbon atoms,
Represents an alkylamino group (or an alkyleneamino group), an alkylthio group, or a group having these as a partial structure, and more preferably a linear or branched alkyl group (or an alkylene group having 7 to 24 carbon atoms) ), An alkoxy group (or an alkyleneoxy group), an alkylamino group (or an alkyleneamino group), an alkylthio group, or a group having any of these as a partial structure. Examples of the polymer include those described in JP-A-1-100530.

R _{20 in the} general formula (D) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (D) represents a polymer with respect to the hydrazino group, Specifically, for example, Japanese Patent Application Laid-Open No. 64-86134
JP-A-4-16938, JP-A-5-197091
No., WO95-32452, WO95-32453
JP-A-9-179229, JP-A-9-23526
4, JP-A-9-235265, JP-A-9-2352
No. 66 and compounds described in JP-A-9-235267.

In the general formula (D), R ₂₀ represents a cationic group (specifically, a group containing a quaternary ammonium group,
A group containing a quaternary group containing a phosphorus atom, or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom,) a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group,
(Alkyl, aryl, or heterocycle) a thio group, or a dissociable group (a group or partial structure having a low acidity proton that can be dissociated in an alkaline developer, or a salt thereof, and specifically, such as carboxy group / -COOH, sulfo group / _-SO 3 H, a phosphonic acid group /
—PO ₃ H, phosphate group / —OPO ₃ H, hydroxy group /
—OH group, mercapto group / —SH, —SO ₂ NH ₂ group,
N- substituted sulfonamide group / _-SO 2 NH- groups, -C
ONHSO ₂ — group, —CONHSO ₂ NH— group, —NH
CONHSO ₂ — group, —SO ₂ NHSO ₂ — group, —CO
An NHCO- group, an active methylene group, an -NH- group inherent in a nitrogen-containing heterocyclic group, or a salt thereof). Examples of those groups include, for example, JP-A-7-234471, JP-A-5-333466,
JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Patent No. 4,994,365, U.S. Patent No. 4,988,604, JP-A-7-259240,
The compounds described in JP-A-7-5610, JP-A-7-244348, German Patent 4006032, JP-A-11-7093 and the like can be mentioned.

In the general formula (D), A ₁₀ and A _{20 each} represent a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or a Hammett substituent having a sum of -0.5. A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; Alternatively, a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. ))). A ₁₀ and A ₂₀ are most preferably a hydrogen atom.

Next, in the present invention, particularly preferred hydrazine derivatives will be described. R ₂₀ is particularly preferably a substituted phenyl group. Examples of the substituent include a sulfonamide group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group,
An N-acylsulfamoylamino group or the like is particularly preferred,
Further, a sulfonamide group and a ureido group are preferred, and a sulfonamide group is most preferred. Hydrazine derivatives represented by the general formula (D), the R _20, a substituent, directly or indirectly, a ballast group, adsorptive group to silver halide,
A group containing a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, (alkyl, aryl, or heterocycle)
A thio group, a dissociable group that can be dissociated in an alkaline developing solution, or a hydrazino group (—NH
It is particularly preferred that at least one of which is substituted group) represented by _{NH-G 10 -R} 10. Furthermore, R
As ₂₀ substituents, directly or indirectly, preferably it has any one group described above, most preferably represents a phenyl group R ₂₀ is substituted by a benzene sulfonamide group, their benzenesulfonamide This is the case where any one of the aforementioned groups is directly or indirectly substituted as a substituent on the benzene ring of the group.

In the general formula (D), G ₁₀ is preferably a -CO- group.

Next, specific examples of the compound represented by formula (D) are shown below. However, the present invention is not limited to the following compounds.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The hydrazine derivatives of the present invention are described, for example, in JP-A-61-213,847 and JP-A-62-260,153.
No. 4,648,604; U.S. Pat.
379,529, 3,620,746, 4,3
Nos. 77,634 and 4,332,878;
-129,536, 56-153,336, 5
6-153,342, JP-A-1-269936, U.S. Pat. Nos. 4,988,604 and 4,994,365.
The compounds were synthesized by using the method described in No.

The hydrazine derivative of the present invention can be used in a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimenylformamide, dimethyl sulfoxide, methylcell It can be used by dissolving it in Solve or the like. Also, by an already well-known emulsification dispersion method, an oil such as diphthyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified. A dispersion can also be prepared and used. Alternatively, the hydrazine derivative powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

In the present invention, the hydrazine derivative may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support, or to any of the other hydrophilic colloid layers. It is preferably added to the silver emulsion layer or the hydrophilic colloid layer adjacent thereto.

Further, two or more of the above-mentioned hydrazine-based nucleating agents can be used in combination. In the present invention, the nucleating agent is added in an amount of 1 × 10 ⁻⁵ to 1 per mol of silver halide.
× 10 ⁻² mol is preferred, and 1 × 10 ^{−5 to} 5 × 10
^-3 mol is more preferred, and 2 × 10 ^{−5 to} 5 × 10 ^−3.
Molar is most preferred.

The average value of the integrated values of the spectral reflectances of the light-sensitive material of the present invention at 850 to 1000 nm can be easily measured using a spectrometer.
For example, using a spectrometer U3500 manufactured by Hitachi, Ltd. with an integrating sphere installed in the light receiving section, and applying a probe light to a black paper placed on the back surface of the photosensitive material, and reflecting light from the photosensitive material. Can be measured by integrating and measuring with an integrating sphere.

In the present invention, the addition of 850
The solid silver halide emulsion layer or other hydrophilic colloid layer contains solid grains whose average value of the integrated value of the spectral reflectance of １０００1000 nm is increased by 1.5% or more as compared with the case where no additive is added. It is preferably at least 2%, but is preferably at most 5% from the viewpoint of haze deterioration.

The solid particles used in the present invention, which increase the integrated value of the reflectance by adding, have no particular limitation on the material as long as they have the above-mentioned reflection characteristics, and do not affect the photographic performance. Any kind of inorganic particles and organic dispersions may be used as long as they have a refractive index of 1.54 or more. The refractive index in the present invention indicates a relative refractive index to air. The refractive index slightly changes depending on the wavelength, temperature, etc. of the light.
9.3 nm) and nD20 having a value of 20 ° C. was used.
In the case of a solid, when the refractive index is small depending on the direction due to the anisotropy of the crystal, the largest value is taken as the value of the substance.

Specific examples of the compound having a refractive index of 1.54 or more include silver halide, magnesium oxide, alumina, calcite, ZrO ₂ , SnO ₂ , ZnO, and Al ₂ O _3.
And various compounds such as metal oxides represented by TiO _{2 and the} like, barium sulfate, polystyrene, and vinylidene chloride resin.

The preferred range of the refractive index is 1.6 to
3.0, particularly preferably 1.7 to 3.0 or less.

The preferred range of the particle size of the solid particles varies depending on the refractive index, but is preferably 2 nm to 20 μm,
nm-10 μm is more preferred. Here, the particle diameter of the solid particles represents the particle diameter determined by the light scattering method, and specifically, the average particle diameter was determined using ELS-800 manufactured by Otsuka Electronics Co., Ltd.

The amount of the solid particles to be added is preferably 1
0 mg to 1 g / m ² , particularly preferably 20 to 500 m
g / m ² .

The position at which the solid particles are added is not particularly limited. The solid particles can be used in the emulsion layer, between the emulsion layer and the support, in the emulsion protective layer, the backing layer and the support. A protective layer may be provided on the uppermost layer of the surface directly exposed to the emitted light of the above or on the layer to which the solid particles are added.

These solid particles need to be in the form of particles in the light-sensitive material, and depending on the method of dispersing the fine particles,
Lower water solubility is preferred. Further, the property of dissolving in the processing solution is preferably used.

Further, in the present invention, it is preferable to use silver halide among the solid grains. Further, it is preferable to use substantially non-photosensitive tabular silver halide grains.

The non-photosensitive silver halide grains used in the present invention may have a halogen composition of silver chloride, silver bromide,
Any of silver chlorobromide, silver iodobromide, silver iodochloride, and silver iodochlorobromide can be used, but the AgBr content is 5%.
0 mol% or more is preferable.

The non-photosensitive silver halide grains used in the present invention are described in Chimie et Physique Photograp by P. Glafkides.
hique (Paul Montel, 1967), Pho by GFDufin
to-graphic Emulsion Chemistry (The Focal Press
Publishing, 1966), Making and Coati by VLZelikman etal
ng Photographic Emulsion (The Focal Press, 1964
Year)).

The substantially non-light-sensitive silver halide grains in the present invention are silver halides having a blue region sensitivity of 1/10 or less of the light-sensitive silver halide grains used in the light-sensitive material of the present invention. Refers to particles. Further, the non-photosensitive silver halide grains are preferably not spectrally sensitized. The non-photosensitive silver halide grains of the present invention can be subjected to surface modification such as metal complex dopant and chemical sensitization described in the section of photosensitive silver halide below.

The morphology of the silver halide grains which can be used in the non-light-sensitive silver halide emulsion of the present invention requires that most of them be tabular. Here, the tabular silver halide grains are a general term for silver halide having one twin plane or two or more parallel twin planes. The twin plane is (1
11) When the ions at all lattice points on both sides of the plane are in a mirror image relationship, this means the (111) plane. When the tabular grains are viewed from above, they have a triangular, square, hexagonal or rounded circular shape.The triangular grains are triangular, and the hexagonal grains are hexagonal. Square, circular ones have circular parallel outer surfaces.

The average particle thickness is calculated by evaporating a metal from a diagonal direction of particles together with a reference latex, measuring the shadow length on an electron microscope photograph, and referring to the shadow length of the latex. It is easily obtained by: In the light-insensitive emulsion of the present invention, 50% or more of the total projected area is occupied by tabular grains having a grain thickness of 0.02 to 0.20 .mu.m.

The coefficient of variation of the equivalent circle diameter in all grains of the non-photosensitive emulsion of the present invention is preferably 40% or less, more preferably 25% or less, and further preferably 15% or less.

Tabular silver halide emulsions are disclosed in
It can be easily prepared by referring to the methods described in JP-A-127927, JP-A-58-113927 and JP-A-58-11328. Further, in an atmosphere having a relatively low pBr value of pBr 1.3 or less, a seed crystal in which tabular grains are present at 40% or more by weight is formed, and silver and a halogen solution are added simultaneously while maintaining the same pBr value. Obtained by growing a seed crystal. In this growth process, it is desirable to add a silver and halogen solution so that no new crystal nuclei are generated. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

The halogen composition of the photosensitive silver halide emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide. May be.

The shape of each photosensitive silver halide grain used in the present invention may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular. The addition amount of the photosensitive silver halide is as follows:
In the present invention, it is 3.0 g or less, preferably 2.0 to 3.0 g.
It is.

The photographic emulsion used in the present invention is P. Glafki
des by Chimie et Physique Photo-graphique (Paul Mo
ntel, 1967), Photographic Emuls by GFDufin
ionChemistry (The Focal Press, 1966), VLZel
Making and Coating Photographic Emul by ikman et al
sion (The Focal Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. Is also good. 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 in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. Particle size to the type and purpose of the addition amount is used a compound of silver halide solvent varies depending halogen composition, 10 ^-5 to 10 ^-2 mol per mol of silver halide is preferred. Further, the particles may be formed in the presence of a nitrogen-containing heterocyclic compound which forms a complex with silver. preferable. The addition amount of these compounds varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but is preferably from 10 ⁻⁶ to 10 ⁻² mol per mol of silver halide. Is preferred. The addition of these compounds can be appropriately performed at each stage before, during, or after the formation of the particles, and is particularly preferably performed at the time of the formation of the particles.

In the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or an alkali halide in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm to 0.4 μm.

The photosensitive silver halide emulsion used in the present invention may be used alone or in combination of two or more. When two or more types are used, the particle sizes are preferably different. It is preferable that the difference between the particle sizes differs by 10% or more as the average particle side length.

The ratio of the combination of two or more silver halide emulsions used in the present invention is not particularly limited, but is preferably 1: 1 to 1:20, more preferably 1: 1 to 1 in terms of the amount of silver. :
It is 10.

It is also preferable to mix at least two types of emulsions having different addition amounts of a nitrogen-containing heterocyclic compound capable of forming a complex with silver as described in paragraphs 0020 to 0032 of Japanese Patent Application No. 2000-379706. Can be

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound and the like. Preferred as these heavy metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ^n- (where M is a heavy metal selected from Ir, Ru, Rh, Re, Cr and Fe. L is a bridging ligand. Y is oxygen or M = 0, 1, 2 and n = 0,
1, 2, and 3. Preferred specific examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanates Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. In order to increase the sensitivity, an iron compound is preferably contained, and a metal coordination complex having a cyan ligand as a ligand is particularly preferable. These compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the compounds, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid,
Hydrofluoric acid, etc.) or alkali halides (for example, K
Cl, NaCl, KBr, NaBr, etc.) can be used. It is also possible to add and dissolve another silver halide grain doped with these compounds in advance. Specific examples of the metal coordination complex are shown below. 1. _[Rh (H 2 O) Cl _5] ^2- 2. [RuCl _6] ^3- 3. [Ru (NO) Cl _5] ^2- 4. [RhCl _6] ^3- 5. _[Ru (H 2 O) Cl _5] ^2- 6. _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 7. ^{_{[Ru 2 Cl 10 O] 6- 8}} . [Re (NO) Cl _5] ^2- 9. [Ir (NO) Cl _5] ^2- 10. _[Ir (H 2 O) Cl _5] ^2- 11. _[Re (H 2 O) Cl _5] ^2- 12. [RhBr _6] ^3- 13. [ReCl _6] ^3- 14. [IrCl _6] ^3- 15. _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 16. [Cr (CN) ₆ ] ^3-17 . [Fe (CN) ₆ ] ^3-

Further, in addition to the compounds mentioned above, paragraphs 0027 to 005 of Japanese Patent Application No. 2000-95144 are also disclosed.
The compound described in 6 can also be preferably used.

The addition amount of these compounds is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver of the silver halide emulsion. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grains is not particularly limited, and may be a uniform distribution, a core-shell type having a different distribution between the surface and the inside, or a continuous distribution. The addition of these compounds can be appropriately performed during the production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them during emulsion formation and incorporate them into the silver halide grains. .

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, and sulfur sensitization, tellurium sensitization and gold sensitization are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer, for example,
In addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. Other U.S. Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,66
No. 8, No. 3,501, 313, No. 3,656, 9
No. 55, German Patent 1,422,869, JP-B-56-24937, JP-A-55-45016 and the like can also be used. Preferred sulfur compounds are thiosulfates and thiourea compounds. The addition amount of the sulfur sensitizer pH during chemical ripening, the temperature, but varies depending on various conditions such as the size of the silver halide grains, per mol of silver halide ^10-7
-2 mol, more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
No. 3489, JP-A-4-25832, JP-A-4-1092
It is preferable to use the compounds described in JP-A Nos. 40 and 4-324855. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropions, 2-
Selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphineselenides, colloidal metal selenium, and the like. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. For those skilled in the art, speaking of unstable selenium compounds as sensitizers for photographic emulsions,
As long as selenium is unstable, the structure of the compound is not critical, and the organic portion of the selenium sensitizer molecule carries selenium and has nothing to do with it being present in the emulsion in an unstable form. Is generally understood to have no role. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. The non-labile selenium compound used in the present invention is disclosed in JP-B-46-4553.
No., JP-B-52-34492 and JP-B-52-34
No. 491 can be used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. In particular, JP-A-4-324855
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in the above. Further, a low-decomposition active selenium compound can also be preferably used. The low-decomposition-active selenium compound includes 10 mmol of AgNO ₃ and 0.1 selenium compound.
5 mM, 2- (N-morpholino) ethanesulfonic acid buffer 40 mM water / 1,4-dioxane volume ratio 1/1 mixed solution (pH = 6.3) when reacted at 40 ° C. The selenium compound has a half life of 6 hours or more. The selenium compound can be analyzed by HPLC or the like to determine the half-life. This low-decomposition active selenium compound is disclosed in JP-A-9-166.
It is preferable to use the compounds of Compound Examples 84-1 to SE-8.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in No. 31284.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
3, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102
(1979), ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1980), S.M. S.Patai, The Chemistry of OrganicSerenium and Tellunium, The Chemistry of Organic Serenium and Tellunium
Compounds) The compounds described in Vol. 1 (1986) and Vol. 2 (1987) can be used. In particular, JP-A-5-313
Compounds represented by general formulas (II), (III) and (IV) in No. 284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably 10 ^-7 to 1
0 ^-3 mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, p
Ag is 6-11, preferably 7-10, and the temperature is 40-95 ° C, preferably 45-85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. As the gold sensitizer, the oxidation number of gold may be +1 or +3, and gold compounds generally used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate,
Examples thereof include potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and gold sulfide, and about 10 ^-7 to 10 ^-2 mol per mol of silver halide can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. The silver halide emulsion of the present invention can be prepared by the method described in European Patent Application (EP) -293,917.
A thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention, two or more in the same layer, the type, distribution, content of the metal complex is different,
Crystal habits, different shapes, types of chemical sensitizers, amounts added,
Different sensitization conditions, types of spectral sensitizing dyes, addition amounts,
Those having different spectral sensitization conditions and the like may be used in combination, and the layers may have a multilayer structure.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye depending on the use of the light-sensitive material. Good. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSUR
E Item17643IV-A (p.23, December 1978), I
tem 18341X (August 1979, p. 437). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected. For example, A) for an argon laser light source, (I) -1 described in JP-A-60-162247.
To (I) -8, compounds of I-1 to I-28 described in JP-A-2-48653, JP-A-4-3304
Compounds I-1 to I-13 described in No. 34, Examples 1 to E described in U.S. Pat. No. 2,161,331.
Xample 14 compounds, compounds 1 to 7 described in German Patent 936,071, B) For helium-neon laser and red laser diode light source, I-1 to I- described in JP-A-54-18726. Compound No. 38, I-1 to I- described in JP-A-6-75322
Compound No. 35 and compounds I-1 to I-34 described in JP-A-7-287338, and Patent Publication No. 282213.
No. 8 to 2-1 to 2-14, 3- (1) to 3-
(14) Compounds of 4-1 to 4-6; C) Dyes 1 to 20 described in JP-B-55-39818, and I-1 described in JP-A-62-284343 for LED light sources. Compound I-37 and compounds I-1 to I-34 described in JP-A-7-287338, Patent Publication No. 282
2) Compounds 2-1 to 2-14, 3- (1) to 3- (14), 4-1 to 4-6 described in JP-A No. 2138; Compounds of I-1 to I-12 described in JP-A-60-8
Compounds I-1 to I-22 described in JP-A-0841, Compounds I-1 to I-29 described in JP-A-4-335342, and I-1 described in JP-A-59-192242.
To I-18, E) Tungsten and xenon light sources for plate making cameras
(1) to (19) represented by the general formula [I] described in
A compound of 4-A to 4-S, a compound of 5-A to 5-Q, 6-A
To 6-T and the compounds of I-1 to I-97 described in JP-A-9-160185 are advantageously selected, but the present invention is not limited thereto.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Volume 176, 17643 (Issued December 1978), page 23, IV, J
Alternatively, the aforementioned Japanese Patent Publication Nos. 49-25500 and 43-49.
33, JP-A-59-19032 and JP-A-59-192242.
And so on.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any stage of the emulsion preparation which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Previous period, Japanese Patent Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. And 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ per 1 m ² of the surface area of the silver halide grain.
The molar amount is preferably 6.5 × 10 ^{−7 to} 2.0 ×.
An addition amount of 10 ⁻⁶ mol is more preferred.

In the present invention, the “other hydrophilic colloid layer” refers to a hydrophilic colloid layer having a water-permeable or water-impermeable relationship with the silver halide emulsion layer. Examples of the former include a protective layer and an intermediate layer, and examples of the latter include a back layer.

The support used in the present invention is, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Glass plate, cellulose acetate, cellulose nitrate, for example, polyester film such as polyethylene terephthalate, JP-A-7-234478, and US
A support comprising a styrenic polymer having a syndiotactic structure described in JP-A-5,558,979;
-538, US4,645,731, US4,93
A support obtained by coating a polyester film described in US Pat. No. 3,267, US Pat. No. 4,954,430 with a vinylidene chloride copolymer can be used. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

As the binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, gelatin is preferably used, but polymers described in paragraph 0025 of JP-A-10-268644 can also be used.
The coating amount of the binder is such that the binder amount of the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less (preferably 1.0 to 3.0 g / m ² ), and the silver halide emulsion The total binder amount of the entire hydrophilic colloid layer on the side having the layer and the entire hydrophilic colloid layer on the opposite side is 7.0 g / m ² or less, and preferably 2.0 to 7.0.
g / m ² .

In the present invention, for the purpose of controlling the surface roughness of the outermost layer surface of the silver halide light-sensitive material, fine particles of inorganic and / or organic polymer (hereinafter referred to as a matting agent) are contained in a hydrophilic colloid layer. ) Is used. The surface roughness of the outermost layer surface of the light-sensitive material having the silver halide emulsion layer and the outermost layer surface opposite to the emulsion layer should be controlled by variously changing the average particle size and the amount of the matting agent. Can be. The layer containing the matting agent may be any layer of the light-sensitive material constituting layer, but the side having the silver halide emulsion layer is preferably contained in a layer farther from the support to prevent pinholes, particularly The outermost layer is preferred.

The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic characteristics. Specifically, Japanese Patent Application Laid-Open No. 10-26846
No. 4, paragraphs 0009 to 0013. In the present invention, the average particle size of the matting agent is preferably 20 μm or less, and particularly preferably in the range of 1 to 10 μm. In the present invention, the preferable addition amount of the matting agent is 5 to 5.
400 mg / ^{m 2,} in particular from 10 to 200 mg / ^{m 2.} The surface roughness of the light-sensitive material of the present invention is at least one of the surface having the emulsion layer and the outermost layer surface opposite to the surface having the emulsion layer,
Preferably, both Beck smoothnesses are 4000 seconds or less, more preferably 10 seconds to 4000 seconds. Beck smoothness can be measured using Japanese Industrial Standard (JIS) P8119 and T
It can be easily determined by APPI standard method T479.

In the present invention, the matting agent sinks during coating and drying of the silver halide light-sensitive material, or the increase or decrease in pressure during handling during automatic conveyance, exposure, development, etc.
Colloidal inorganic particles can be used in a silver halide emulsion layer, an intermediate layer, a protective layer, a back layer, a back protective layer, and the like for the purpose of improving curl balance, scratch resistance, and adhesion resistance. Preferred colloidal inorganic particles include paragraphs 0008 and 001 of JP-A-10-268644.
4. Slender silica particles, colloidal silica, pearl-like (pearl necklace-shaped) colloidal silica manufactured by Nissan Chemical Industries, Ltd .: "Snowtex-P"
S "and the like.

The amount of the colloidal inorganic particles used in the present invention is 0.01 to 2.0, preferably 0.1 to 0.1 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added. ０．６0.6.

In the present invention, a polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5 is used for the purpose of improving the sense of pressure increase and decrease. Is preferred. In particular,
Compounds (III) -1 to 25 described in the publication are mentioned.

In the present invention, a polymer latex can be used for the purpose of improving the brittleness, the dimensional stability, the feeling of pressure change, and the like. As the polymer latex, U.S. Pat. Nos. 2,763,652, 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5-66512, JP-A-5-80449, Tokiko Sho 60-
No. 15935, No. 6-64058 and No. 5-450
Polymer latexes composed of various monomers such as alkyl acrylates and alkyl methacrylates described in JP-B No. 14 and No. Sho.
7, JP-A-50-73625, JP-A-7-1521
12, a polymer latex copolymerized with a monomer having an active methylene group and a monomer such as an alkyl acrylate described in JP-A-8-137060. Particularly preferably, JP-A-8-248548,
It is a polymer latex having a core / shell structure having a repeating unit composed of an ethylenically unsaturated monomer having an active methylene group in a shell portion described in JP-A-8-208767 and JP-A-8-220669. Polymer latexes having a core / shell structure having an active methylene group in the shell portion do not decrease the wet film strength of the photographic light-sensitive material, and are difficult to adhere such as brittleness, dimensional stability, and photosensitive materials. And the latex itself has improved shear stability. The amount of the polymer latex to be used is 0.01 to 4.0, preferably 0.1 to 2.0 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added.

In the present invention, in order to lower the pH of the coating film for the purpose of improving the storage stability of the silver halide light-sensitive material and improving the sensitivity to pressure fluctuation, the same method as described in JP-A-7-104413, p. It is preferable to use the acidic polymer latex described on line 30 on the right side of the page. Specifically, compounds II-1) to II-9) described on page 15 of the publication. JP-A-2-103
No. 536, page 18, lower right, line 6 to page 19, upper left, first line, compounds having an acid group. The pH of the coating film on the side having the silver halide emulsion layer is preferably from 6 to 4.

In the present invention, at least one of the constituent layers of the silver halide light-sensitive material has a surface resistivity of 25.degree.
It can have a conductive layer of 10 ¹² Ω or less under an atmosphere of H. Examples of the conductive substance used in the present invention include those described in JP-A-2-18542, page 2, lower left, line 13 to page 3, upper right, line 7. In particular,
The metal oxides described on page 2, lower right, line 2 to the lower right, line 10 of the same publication, and compounds P-1 to P-
7. The conductive polymer compound of 7. USP 5,575,957,
Paragraphs 0034 to 00 of JP-A-10-142938
43, paragraph 0013 of JP-A-11-223901
To 0019 can be used.

In the present invention, in addition to the above-mentioned conductive substance, JP-A-2-18542, page 4, upper right, second line to page 4, lower right, lower third line, JP-A-3-39948, No. 12 A better antistatic property can be obtained by using the fluorine-containing surfactant described in the sixth line from the lower left of the page to the fifth line on the lower right of page 13 of the publication.

In the present invention, the silver halide emulsion layer or other hydrophilic colloid layer may contain a coating aid, an additive dispersing / solubilizing agent, improvement in lubricity, prevention of adhesion and improvement in photographic properties (for example, development acceleration). Various surfactants can be used for the purpose of, for example, contrast enhancement, sensitization, and storage stability). For example, surfactants described in JP-A-2-12236, page 9, upper right line, line 7 to lower right line, line 3 of the same page. JP-A-2-103
No. 536, page 18, lower left line, line 4 to lower left line, line 7, the PEG surfactant. Specifically, compounds VI-1 to VI-15 described in the publication. JP-A-2-185
No. 42, page 4, upper right, second line to page 4, lower right, lower third line; JP-A-3-39948, page 12, lower left, line 6 to page 13, lower right, line 5 Fluorinated surfactant.

In the present invention, various slip agents can be used for the purpose of improving the transportability, scratch resistance, pressure increase / decrease sensitivity and the like of the silver halide photosensitive material in an automatic transporter.
For example, JP-A-2-103536, page 19, upper left 1
From the fifth line to the upper right line on page 19 of the publication, JP-A-4-21
A lubricant described in paragraphs 0006 to 0031 of No. 4551.

In the present invention, a compound described in JP-A-2-103536, page 19, upper left, line 12 to page 19, upper right, line 15 is contained as a plasticizer for the coating film of the silver halide photosensitive material. be able to.

In the present invention, as a crosslinking agent for the hydrophilic binder, from the right upper line, page 18 to the upper right line 17 of JP-A-2-103536, JP-A-5-297508 can be used.
The compounds described in paragraphs [0008] to [0011] of JP-A No. 1993-0011 can be used. The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is preferably in the range of 50 to 200%, more preferably 70%.
１８０180%. The swelling ratio of the hydrophilic colloid layer is determined by measuring the thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material,
The silver halide photographic material was immersed in distilled water at 25 ° C. for 1 minute, the swelled thickness (Δd) was measured, and the swelling ratio (%) was measured.
= △ d ÷ d0 × 100.

In the present invention, drying when coating and drying the silver halide light-sensitive material, the environment, processing, heat treatment and the like when the film is wound into a roll after drying are described in JP-A-10-26.
It is preferable to carry out the method described in paragraphs 0026 to 0032 of Japanese Patent No. 8464.

In the present invention, the coated photosensitive material is preferably subjected to a heat treatment at any time from coating to development. The heat treatment may be performed continuously immediately after the application or after a certain period has elapsed, but it is preferable to start the heat treatment within a short period, for example, within one day. The heat treatment is mainly for accelerating the hardening reaction to obtain a film strength that can withstand the development process, and the heat treatment conditions are appropriately determined according to the type of the hardener, the amount added, the film pH, the required film strength, etc. Although it has to be determined, it is preferably from 30 to 60C, more preferably from 35C to 50C. The period of the heat treatment is preferably 30 minutes to 10 days.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

The polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right line, line 11 to page 12, lower left line, line 5. Specifically, compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right line, line 19 to page 18, upper right line, line four.

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. A polymer latex having an active methylene group represented by the general formula (I) described in JP-A-9-179228, specifically, compounds I-1 to I-l described in the same specification.
I-16. Polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the same specification. JP-A-7-1
An acidic polymer latex described on page 14, left line 1 to page 30, right line of JP-A-04413, specifically, compounds II-1) to II-9) described on page 15 of the same.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardening agents described in JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right line.

Compounds having an acid group described on page 18, lower right, line 6 to page 19, upper left, first line of JP-A-2-103536.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, right lower second line to page 10 lower right line, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right line, line 1 to line 18, upper right line.

Solid disperse dyes represented by general formula (FA), general formula (FA1), general formula (FA2) and general formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
(II-2) to (II-24) described in JP-A-7-152
No. 112, (III-5) to (III-18);
(IV-2) to (IV-7) described in US Pat. Solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication.

The following nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. JP-A-7-77783, page 48, line 2 to
Compounds described in line 37, specifically, compounds A-1) to A-73) described on pages 49 to 58. JP-A-7-843
(Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and Nb-1 to Nb-12. General formula (1) described in JP-A-8-27023,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1, compound 6-1 to 6-58 and 7-1 to 6-1
Compounds 7-38.

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

JP-A-2-18542, page 3, lower right 1
The binder described in the second to 20th lines.

Hereinafter, processing agents such as a developer and a fixing solution, a processing method, and the like in the present invention will be described. However, needless to say, the present invention is not limited to the following description and specific examples.

For the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonates, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene-based developing agent, and a combination of a dihydroxybenzene or an ascorbic acid derivative with 1-phenyl-3-pyrazolidone, or a dihydroxybenzene or the like. Examples include a combination of an ascorbic acid derivative and a p-aminophenol. As a developing agent used in the present invention, dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc., and hydroquinone is particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4 -Methyl-
4-hydroxymethyl-3-pyrazolidone and the like.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention;
There are o-methoxy-p- (N, N-dimethylamino) phenol and o-methoxy-p- (N-methylamino) phenol, among which N-methyl-p-aminophenol, Aminophenols described in JP-A-297377 and JP-A-9-297378 are preferred.

The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.10 mol / l. It is preferable to use 0.5 to 0.5 mol / l and the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / l to 0.5 mol / l, preferably 0.05 mol / l to 0.5 mol / l.
0.3 mol / l is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or less.
It is preferable to use 0.5 mol / l, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of buffer, especially carbonate, used is preferably 0.05 mol /
Liter or more, especially 0.08 to 1.0 mol / liter.

In the present invention, both of the developing solution and the developing replenisher are "the pH rise when 0.2 mol of sodium hydroxide is added to 1 liter of the solution is 0.2 to 1.5".
It preferably has the following properties. As a method for confirming that the developing solution or replenisher used has this property, the pH of the developing solution or replenisher to be tested may be determined.
Was adjusted to 10.5, and then 0.1 mol of sodium hydroxide was added to 1 liter of the solution, and the pH value of the solution at this time was measured. It is determined that it has the properties specified above. In the present invention, it is particularly preferable to use a development start solution and a development replenisher whose rise in pH value in the above test is 0.3 to 1.0.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde sodium bisulfite and the like. The sulfite is preferably at least 0.2 mol / l,
In particular, it is used in an amount of 0.3 mol / l or more, but if it is added in an excessively large amount, it causes silver contamination in the developing solution. Therefore, the upper limit is preferably 1.2 mol / l. Particularly preferably, it is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The addition amount is from 0.03 to 0.07 in molar ratio to the dihydroxybenzene-based developing agent.
The range of 0.12 is preferred, and particularly preferably 0.05 to
It is in the range of 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Examples of additives other than those described above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3-
(5-mercaptotetrazol-1-yl) sodium benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be used as an antifoggant or blackpe.
pper) may be included as an inhibitor. Specifically, 5
-Nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzo Imidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,
Sodium 3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole,
-Methylbenzotriazole, 2-mercaptobenzotriazole and the like. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As aminopolycarboxylic acids, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, etc.
Compounds described in 5-67747, 57-102624 and JP-B-53-40900 can be mentioned.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591 and German Offenlegungsschrift 2227369, and Research Disclosure, Vol. 181, Item 18170 (1979). May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. , 55-2
9883, 56-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-112127, JP-A-55-4024, and JP-A-55-40.
25, 55-126241, 55-65555, 55-65556, and the compounds described in Research Disclosure 18170 described above.

The organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ per liter of developer.
Mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-465.
85, JP-B-62-2849, JP-A-4-36294
2. In addition to the compounds described in JP-A-8-6215, triazines having at least one mercapto group (for example,
-23830, JP-A-3-282457, JP-A-7-1
75178), the same pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4, 6
-Trimercaptopyrimidine, JP-A-9-274289
Pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,
5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-248587, and the like pyrazines (for example, 2-mercaptopyrazine,
2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, and the like pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimer Mercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177,
A polyoxyalkyl phosphonate described in US Pat. No. 5,457,011 can be used. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, a color tone agent, a surfactant, an antifoaming agent, a hardener and the like may be contained as necessary.

The preferred pH of the developer is from 9.0 to 12.0.
And particularly preferably in the range of 9.0 to 11.0, more preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

If the specific gravity of the developer used is too high, the density of the blackened portion of the exposed photosensitive material tends to decrease. The preferred specific gravity of the developer used is 1.1
00 or less, more preferably 1.020 or more and 1.1
00, and more preferably 1.040 or more.
100 or less.

As cations in the developer, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around the blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, it is preferable that the molar ratio of potassium ion and sodium ion in the developer is between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishing amount of the developing solution is 390 ml or less, preferably 325 to 130 ml, and most preferably 250 to 120 ml per 1 m ² of the photosensitive material. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration than the start solution.

As the fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution of the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as an aluminum ion concentration in the working solution.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts having a hardening agent and the like as separate parts, or may be a one-part composition containing all components.

If necessary, a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc.) may be used in the fixing treatment agent.
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), compounds having aluminum stabilizing ability or water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and salts and saccharides thereof in an amount of 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol. / Liter), but it is better not to include a boron-based compound from the viewpoint of environmental protection in recent years.

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be used, and known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681 and JP-B-45-35754, JP-A-58-122535, and JP-A-58-1.
Thiourea derivatives described in 22536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-1
-4739, 1-159645 and 3-1017
28, a mesoionic compound described in 4-170539, and a thiocyanate.

The pH of the fixing solution in the present invention is preferably 4.0 or more, more preferably 4.5 to 6.0. The fixing solution is mixed with a developer to increase the pH due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less for the non-hardened fixing solution. Is 6.7 or less.

The replenishing amount of the fixing solution is 500 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml per 1 m ² of the photographic material. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, FS-200 manufactured by Fuji Photo Film Co., Ltd.
0 and so on. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid, it is preferable to store it in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even if the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained, but the solid processing agent will be described below. As the solid preparation in the present invention, known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, stick, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 48, line 48 to column 3, line 13 can be referred to.

In the case of forming a plurality of layers, components that do not react even if they come into contact with each other may be sandwiched between components that react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921,
16841, 4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferable, and especially, the tablet is 1.0 to 5.0 g / c.
m ³ is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As a method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-7884.
8, 5-93991, JP-A-4-85533, 4-
85534, 4-85535, 5-134362,
5-197070, 5-204098, 5-22
4361, 6-138604, 6-138605,
8-286329 and the like can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt coagulation, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, Japanese Patent Laid-Open No. 6-242 is disclosed.
585 to 6-242588, 6-247432, 6-247448, 6-301189, 7-566
4. A foldable shape as disclosed in 7-5666 to 7-5669 is also preferable for reducing the storage space of the waste packaging material. For these packaging materials, a screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and the limitation is particularly limited. do not do. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in JP-A-9-80718. A method of dissolving and replenishing from a stock part, JP-A-5-119454,
6-19102 and 7-261357. A processing agent is introduced into a circulating system of an automatic developing machine as described in
There are a replenishing method, a method of adding and dissolving a processing agent in accordance with the processing of the photosensitive material in an automatic developing machine having a dissolution tank therein, and any other known methods can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolution apparatus having an opening mechanism or an automatic developing machine as described in JP-A-9-138495. From the viewpoint of the latter, the latter is preferable. More specifically, a method of breaking through the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method described in JP-A-6-19102 and JP-A-6-9-9
5331.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, this is referred to as washing including the stabilization processing, and the liquid used for these is water or washing water. ). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. These replenishing amounts are generally 1 m ² of photosensitive material.
From about 17 liters to about 8 liters per volume, although lower replenishment rates can be used. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. Also, various oxidizing agents (eg, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

[0156] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example, two stages, three stages, etc.) than the old are the known water washing replenishment rate photosensitive material 1 m ² per 200-5
0 ml is preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation, but a method of adding a sunscreen (a so-called scale inhibitor), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. As a water-saving scale device, an apparatus AC-1000 manufactured by Fuji Photo Film Co., Ltd. and AB-5 manufactured by Fuji Photo Film Co., Ltd. as an anti-scale agent may be used.
231485 may be used. The protective agent is not particularly limited, and known agents can be used. Other than the above-mentioned oxidizing agents, there are, for example, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (eg, 2-mercaptopyridine-N-oxide and the like). But good. As a method of energizing, Japanese Patent Application Laid-Open No.
4885, 3-224687, 4-162280, 4-18980, and the like.

In addition, a known water-soluble surfactant or defoaming agent may be added to prevent water bubble unevenness and stain transfer. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, Al, etc., a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a deodorant, an alkanolamine or a surfactant may be used in this stabilizing bath. Agents can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents can be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste of the developing solution, the fixing solution, the washing water and the stabilizing solution used in the present invention is incinerated. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5, 439, 560, etc. before disposing.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and oxidation of the air. U.S. Pat. No. 3,025,779 and U.S. Pat.
1 and the like, and are simply referred to as a roller transport type automatic developing machine in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stopping step), but most preferably follows these four steps. Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, the time from the start of processing to after drying (dry to dry) is preferably 25 to 160 seconds, and the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds. 25 to 50 ° C. is preferred, and 3
0-40 ° C is preferred. The temperature and time of washing are 0-5
It is preferably 40 seconds or less at 0 ° C. According to the method of the present invention,
The developed, fixed and washed photosensitive material may be dried by squeezing washing water, that is, passing through a squeeze roller.
Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation. However, hot air drying, JP-A-4-15534, JP-A-5-2256, and JP-A-5-256-2 can be used.
There are heat roller drying and drying by far infrared rays as disclosed in US Pat. No. 89294, and a plurality of methods may be used in combination.

[0165]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1

<Preparation of Emulsion A> 1 solution Water 750 ml Gelatin 20 g Sodium chloride 3 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium benzenethiosulfonate 10 mg Citric acid 0.7 g 2 solutions Water 300 ml Silver nitrate 150 g 3 solutions Water 300 ml sodium chloride 38 g potassium bromide 32 g potassium hexachloroiridate (III) (0.005 mass% KCl 20 mass% aqueous solution) 5 ml ammonium hexachlororhodate (0.001 mass% NaCl 20 mass% aqueous solution) 7 ml hexachloro used for three liquids Potassium iridate (III) (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass)
20% by mass aqueous NaCl solution) were prepared by dissolving the powders in a 20% by mass aqueous solution of KCl and a 20% by mass aqueous solution of NaCl, respectively, and heating at 40 ° C. for 120 minutes.

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were each added in an amount corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Subsequently, the following liquids 4 and 5 were added over 8 minutes, and the remaining 10% of the liquids 2 and 3 were added over 2 minutes to grow to 0.21 μm. further,
0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. Fourth liquid 100 ml Silver nitrate 50 g Five liquid 100 ml Sodium chloride 13 g Potassium bromide 11 g Yellow blood salt 5 mg After that, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.2
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled.
Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and the pAg to 7.5,
Sodium benzenethiosulfonate (10 mg), sodium benzenethiosulfinate (3 mg), sodium thiosulfate (15 mg) and chloroauric acid (10 mg) were added and chemically sensitized at 55 ° C. to obtain an optimum sensitivity.
100 mg of 3a, 7-tetraazaindene, proxel as a preservative (trade name, manufactured by ICI Co., Ltd.)
100 mg was added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.22 μm and a variation coefficient of 9% was obtained. (Finally, pH = 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 to 1.25 × 10 ³ as an emulsion.
kg / m ³ and viscosity = 50 mPa · s. )

<Preparation of Emulsion B> 1 solution water 750 ml gelatin 20 g sodium chloride 1 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 10 mg citric acid 0.7 g 2 solutions water 300 ml silver nitrate 150 g 3 solutions water 300 ml Sodium chloride 38 g Potassium bromide 32 g Potassium hexachloroiridate (III) (0.005 mass% KCl 20 mass% aqueous solution) 5 ml Ammonium hexachlororhodate (0.001 mass% NaCl 20 mass% aqueous solution) 15 ml Hexachloro used for 3 liquids Potassium iridate (III) (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) each convert KCl 2 into powder. It was prepared by dissolving in a 0% by mass aqueous solution and a 20% by mass aqueous solution of NaCl and heating at 40 ° C. for 120 minutes.

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were each added in an amount corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Thereafter, 500 mg of 1,3,3a, 7-tetraazaindene was added, followed by the following solution 4 and solution 5 over 8 minutes, and then the remaining 10% amount of solution 2 and solution 3 over 2 minutes. , 0.18 μm. Further, 0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. 4th liquid 100ml Silver nitrate 50g 5th liquid 100ml Sodium chloride 13g Potassium bromide 11g Yellow blood salt 2mg Thereafter, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.2
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled.
Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and the pAg to 7.5,
10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide and 1 mg of chloroauric acid were added, and the mixture was subjected to chemical sensitization at 55 ° C. so as to obtain an optimum sensitivity. 100 mg of 3a, 7-tetraazaindene and 100 mg of proxel as a preservative were added. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 μm and a variation coefficient of 10% was obtained. (Finally, pH = 5.
7, pAg = 7.5, conductivity = 40 μS / m, density =
1.2 × 10 ³ kg / m ³ and viscosity = 50 mPa · s. )

<Preparation of Non-Light-Sensitive Silver Halide Particles Z> 1 solution 1 liter water 1 liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 solutions water 400 ml silver nitrate 100 g 3 liquids water 400 ml sodium chloride 13.5 g potassium bromide 45.0 g potassium hexachlorodimate (III) (0.001% by mass aqueous solution) 860 ml

Solution 1, Solution 2 and Solution 3 maintained at 70 ° C. and pH 4.5 were simultaneously added over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated.
(PH was in the range of 3.2 ± 0.2) Next, about 3 liters of the supernatant liquid was removed (first washing with water). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. 45 g of gelatin was added to the emulsion after water washing and desalting, pH 5.7 and pAg were adjusted to 7.5, phenoxyethanol was added as a preservative, and finally, the average silver chloride was 30 mol% and the silver iodide was 0%. A dispersion of unripe silver iodochlorobromide cubic milk particles Z having an average particle diameter of 0.45 μm and a coefficient of variation of 10%, containing 0.08 mol%, was obtained. (Finally, as an emulsion, pH = 5.7, pAg
= 7.5, conductivity = 40 μS / m, density = 1.3-1.
35 × 10 ³ kg / m ³ and viscosity = 50 mPa · s. )

[0173]

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Preparation of Coated Samples Coating was performed on a polyethylene terephthalate film support having both surfaces shown below having a moisture-proof layer containing vinylidene chloride and a UL layer / emulsion layer / protective layer lower layer / protective layer upper layer. To prepare a sample. The preparation method, application amount and application method of each layer are shown below.

<Emulsion Layer> Emulsion A and Emulsion B were Ag-converted.
The mixture was mixed at a ratio of 1: 2, and sensitizing dye (SD-1) 5.7 ×
10^-4Mole / mol Ag was added for spectral sensitization. Sa
And KBr 3.4 × 10^-4Mol / mol Ag, compound
(Cpd-1) 2.0 × 10^-4Mol / mol Ag, compound (C
pd-2) 2.0 × 10^-4Mol / mol Ag, compound (Cpd-
3) Add 8.0 × 10-4 mol / mol Ag and mix well
did. Then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene 1.2 × 10^-4Mol / mol
Ag, hydroquinone 1.2 × 10^-2Mol / mol A
g, citric acid 3.0 × 10^-4Mol / mol Ag, as shown in Table 1.
The hydrazine derivative shown, or the following comparative compound A,
1.5 × 10 for B and C^-4Mol / mol Ag, nucleation accelerator
(Cpd-4) 6.0 × 10 ^-4Mol / mol Ag, 2, 4
-Dichloro-6-hydroxy-1,3,5-triazine
90 mg / m of sodium salt²15 for gelatin
% By mass of colloidal silica having a particle size of 10 μm, aqueous latex
Box (Cpd-5) 100mg / m², Polyethylacry
Rate latex 150mg / m², Methyl acryle
And 2-acrylamide-2-methylpropanesulfo
Acid salt and 2-acetoxyethyl methacrylate
Of latex copolymer (weight ratio: 88: 5: 7)
0mg / m², Core-shell latex (core: polystyrene
/ Butadiene copolymer (weight ratio 37/63), shell
: Styrene / 2-acetoxyethyl acrylate (heavy
Quantity ratio 84/16), core / shell ratio = 50/50) is 1
50mg / m², 4% by mass of compound (Cp
d-6) was added, and the pH of the coating solution was adjusted to 5.6 using citric acid.
Was adjusted. The emulsion layer coating solution thus prepared is
2.5 g / m of Ag theoretically on the support², Gelatin 1.
1g / m²It was applied so that

[0176]

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[0177] <upper protective layer> Gelatin 0.3 g / ^{m 2} non-photosensitive silver halide grains Z 0.05 g / ^{m 2} Average 3.5μm of amorphous silica matting agent 25 mg / ^{m 2} Compound (Cpd-7) ( Gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 nm (Snowtex C manufactured by Nissan Chemical Industries, Ltd.) 30 mg / m ² Compound (Cpd-8) 50 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m m ² compound ^{(Cpd-9) 20mg / m} 2 compound ^{(Cpd-10) 20mg / m} 2 preservative (Proxel (trade name, ICI Co., Ltd., Ltd.)) 1 mg / ^{m 2}

<Lower Layer of Protective Layer> Gelatin 0.5 g / m ² Non-light-sensitive silver halide grains Z 0.05 g / m ² Compound (Cpd-11) 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² Compound (Cpd-12) 3 mg / m ² Preservative (Proxel) 1.5 mg / m ²

[0179] <UL layer> Gelatin 0.5 g / ^{m 2} non-photosensitive silver halide grains Z 0.05 g / ^{m 2} of polyethyl acrylate latex 150 mg ^{/ m} 2 5-methylbenzotriazole (general formula of the present invention (1) Compound (Cpd-6) 40 mg / m ² Compound (Cpd-13) 10 mg / m ² Preservative (Proxel) 1.5 mg / m ²

The viscosity of the coating solution for each layer was adjusted by adding a thickener represented by the following structure (Z).

[0181]

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The sample used in the present invention has a back layer and a conductive layer having the following compositions. <Back layer> Gelatin 3.3 g / m ² Non-light-sensitive silver halide grains Z 0.1 g / m ² compound (Cpd-14) 40 mg / m ² compound (Cpd-15) 20 mg / m ² compound (Cpd-16) ) 90 mg / ^{m 2} compound ^{(Cpd-17) 40mg / m} 2 compound ^{(Cpd-18) 26mg / m} 2 1,3- divinyl sulphonyl-2-propanol 60 mg / ^{m 2} polymethyl methacrylate fine particles (average particle size 6.5μm 30 mg / m ² Liquid paraffin 78 mg / m ² Compound (Cpd-6) 120 mg / m ² Calcium nitrate 20 mg / m ² Preservative (Proxel) 12 mg / m ²

<Conductive layer> Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² Preservative (Proxel) 0.3 mg / m ²

[0184]

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[0185]

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[0186]

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<Support> A first layer and a second layer of an undercoat layer having the following composition on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were applied.

<One layer of undercoat layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Compound (Cpd) -20) 0.20 g Colloidal silica (Snowtex ZL: particle size 70-100 nm, manufactured by Nissan Chemical Co., Ltd.) 0.12 g 100 g by adding water Further, 10% by mass of KOH was added to adjust to pH = 6. The solution was applied at a drying temperature of 180 ° C. for 2 minutes so that the dry film thickness was 0.9 μm.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound (Cpd-21) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Proxel 3.5 × 10 ^{− 3} g Acetic acid 0.2 g Water was added and 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness became 0.1 μm.

[0190]

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<Coating method> On the support provided with the above-mentioned undercoat layer, four layers of an UL layer, an emulsion layer, a protective layer lower layer, and a protective layer upper layer were arranged in this order from the side closer to the support as the emulsion surface side. At the same time while adding the hardener liquid by the slide bead coater method while maintaining the temperature at ℃, the cold air set zone (5
° C), and from the side closer to the support opposite to the emulsion surface, from the side closer to the support, a conductive layer and a back layer are simultaneously coated in the order of a hardener solution by a curtain coater method and a cold air set zone ( 5 ° C.). At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time was 200 m / min.

<Drying conditions> After setting, the mixture was dried with a dry air at 30 ° C until the mass ratio of water / gelatin became 800%.
After drying 200 to 200% with a dry air at 35 ° C and 30% RH, the air is directly applied, and 30 seconds after the surface temperature reaches 34 ° C (assuming the drying is completed), 48 ° C and 2% RH.
For 1 minute. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800%.
It takes 35 seconds from 0% to 5 seconds from 200% to the end of drying.

This photosensitive material was wound up at 25 ° C. and 55% RH.
Heat treatment was performed at 35 ° C. and 30% RH for 72 hours.
Next, after cutting at 25 ° C. and 55% RH and humidity-controlling at 25 ° C. and 50% RH for 8 hours in a barrier bag conditioned for 6 hours,
Sealed with cardboard conditioned at 50 ° C 50% RH for 2 hours,
The samples shown in Table 1 were prepared. For comparison, a sample not subjected to heat treatment after winding was also prepared. When the humidity inside the barrier bag was measured, it was 45%. The film surface pH on the emulsion layer side of the obtained sample was 5.5 to 5.8, and the film surface pH on the back side was 6.0 to 6.5. The absorption spectra on the emulsion layer side and the back layer side were as shown in FIG. For the measurement of the absorption spectrum, a spectrophotometer U-3500 manufactured by Hitachi, Ltd. was used, and a sample whose surface on the side opposite to the measurement surface was removed was placed in a φ200 integrating sphere set in a sample chamber. Measurement.

The evaluation was performed by the following method. (Evaluation of photographic properties) The obtained sample was exposed to xenon flash light having an emission time of ^10-6 seconds through an interference filter having a peak at 667 nm and a step wedge. Using a developing solution (A) and a fixing solution (B) having the following formulations, the film was processed at 35 ° C. and 25 ″ using an FG-680AG automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.).

Developer (A) The composition per liter of the concentrated solution is shown. Water 600 ml potassium hydroxide 105.0 g diethylenetriamine-pentaacetic acid 6.0 g potassium carbonate 120.0 g sodium metabisulfite 120.0 g potassium bromide 9.0 g hydroquinone 75.0 g 5-methylbenzotriazole 0.24 g 4-hydroxymethyl- 4-methyl-1-phenyl-3-pyrazolidone 1.35 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.432 g 4- (N-carboxymethyl-N-methylamino-2,6-dimercaptopyrimidine 0 .18 g 2- (N-carboxymethyl-N-methylamino-4,6-dimercaptopyrimidine 0.06 g Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g Add potassium hydroxide, and add water to make 1 liter. p
Adjust H to 10.7. As a start solution (mother solution), water 3 is added to the above solution 1 (pH is 10.40). As a replenisher, water 2 is added to the above solution 1 (pH is 10.4
5). The replenishment amount is 100 ml per Daizen (50.8 × 61.0 cm) or 323 ml per m ² .

Fixing Solution (B) Formulation The formula per 1 L of the concentrated solution is shown. Ammonium thiosulfate 360 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Aluminum sulfate 25.2 g pH 4.85 When used, 1 part of the above concentrated liquid is diluted with 2 parts of water. The pH of the working solution is 4.8.

(Gamma) Gamma (hard contrast) is expressed as a density of 0.1 obtained by subtracting the _Dmin part from the logarithm of the exposure amount.
It was represented by the slope of a straight line connecting the points 3.0 and 3.0. In practice,
Gamma is preferably 12 or more, and more preferably 16
More preferably, it is the above.

(Black pots) The unexposed photosensitive material was treated with the above-mentioned developer at 35 ° C. and 40 ″, and the number of generated black pots was visually evaluated. (Bad) 5 points method, practically 3 points or more are required.

(Dot dot quality) Using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd., 175 lines /
A 50% flat screen was output in inches, and development was performed under the above conditions. With respect to this sample, the sharpness of halftone dots and the smoothness were visually evaluated with a 200-fold loupe. The evaluation results were shown by a five-point scale of (good) 5 to 1 (bad). Practically, three or more points are required.

(Evaluation of Photographic Properties with Fatigue Developing Solution) The above-mentioned developing solution (A) was used to replenish each film sample of 80% blackening per day with 50 cc of a working solution per large size (50.8 cm × 61 cm). By processing 300 sheets of large total size, and performing this process continuously for 4 days, a large number of films were processed to obtain a developer in which the pH was lowered to 10.2 and the bromine ion concentration was increased.

The same evaluation as above was performed using the above-mentioned fatigue developing solution.

[0202]

[Table 1]

Table 1 shows that the sample of the present invention has high gamma, good dot quality, hardly generates black spots, and has good processing stability.

Example 2 The following light-insensitive silver halide grains were prepared. Example 1
A light-sensitive material was prepared in the same manner as in Example 1, except that the following non-light-sensitive silver halide grains were used in place of the non-light-sensitive silver halide grains Z. However, 5-methylbenzotriazole is UL
40 mg / m ^{2 was} added to the layer.

Preparation of Non-Photosensitive Silver Halide Grain-I 1 solution 1 liter of water 1 liter of gelatin 20 g of potassium bromide 0.9 g of citric acid 0.2 g of NH ₄ NO ₃ 20 g of hydrogen peroxide 3.5 g of sodium benzenethiosulfonate 15 mg 2 Liquid water 400 ml Silver nitrate 200 g 3 Liquid water 400 ml Potassium bromide 140.0 g Potassium hexachlorodimate (III) (0.001% by mass aqueous solution) 4000 ml

While stirring one solution maintained at 60 ° C.,
40 ml of OH (1N) was added, and 0.7 g of an aqueous silver nitrate solution was further added. After that, 1 /
Add two each by the control double jet method over a period of 20 minutes while keeping the silver potential at +24 mV, and after physical ripening for 2 minutes, use the same control double jet method for the remaining half of the second and third solutions. For 20 minutes to form particles.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the anionic precipitant-1 used in Example 1 was added, and the pH was lowered using sulfuric acid until the silver halide precipitated. (PH was in the range of 3.1 ± 0.2) Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. To the emulsion after washing and desalting, 45 g of gelatin was added, and pH 5.7, pA
g was adjusted to 7.5, and phenoxyethanol was added as a preservative. Finally, it contained 30 mol% of average silver chloride and 0.08 mol% of silver iodide. The average particle diameter was 0.8 μm, and the coefficient of variation was 10%. To obtain a dispersion of unripe silver bromide tetrahedral emulsion grains. (Finally, as an emulsion, pH = 5.7, pAg =
7.5, conductivity = 40 μS / m, density = 1.3 × 10 ³
kg / m ³ and viscosity = ³⁰ mPa · s. )

Preparation of Non-Photosensitive Silver Halide Grain-II By appropriately changing the conditions for forming the above non-photosensitive silver halide grain-I, an average particle size of 0.5 μm and a variation coefficient of 10% were obtained. A dispersion of unripe silver bromide tetradecahedral emulsion grains was obtained.

Preparation of Non-Photosensitive Silver Halide Grains In an aqueous solution of the following X-1 to X-4, 1 mol per mol of KBr
× 10 ⁻⁵ mol of hexachlorodium (II
I) Particle formation was performed by adding potassium acid.

(Preparation of 1st solution) An aqueous solution 1 containing 0.6 g of KBr and 1.1 g of gelatin having an average molecular weight of 15,000.
300 mL was kept at 35 ° C. and stirred.

(Addition 1) 24 mL of an aqueous solution of Ag-1 (containing 4.9 g of AgNO ₃ in 100 mL) and X-1
Aqueous solution (containing 4.1 g of KBr in 100 mL) 2
4 mL and 24 mL of an aqueous G-1 solution (containing 1.8 g of gelatin having an average molecular weight of 15,000 in 100 mL) were added by a triple jet method at a constant flow rate over 30 seconds.

Thereafter, 1.3 g of KBr was added, and the temperature was raised to 75 ° C. After an aging step for 12 minutes after the temperature rise, an aqueous solution of G-2 aqueous solution (100 ml of an alkali-treated ossein gelatin aqueous solution was added to trimellitic anhydride at 50 ° C. and pH 9.0) to cause a reaction. 300 mL (containing 12.7 g of gelatin obtained by removing trimellitic acid) was added, and then disodium 4,5-dihydroxy-1,3-disulfonate monohydrate was added.
1 g and 0.002 g of thiourea dioxide were sequentially added at intervals of 1 minute.

(Addition 2) Next, an Ag-2 aqueous solution (100
157 mL containing 22.1 g of AgNO ₃ in mL)
And an X-2 aqueous solution (15.5 g of KBr in 100 mL)
Was added by the double jet method over 14 minutes. At this time, the addition of the Ag-2 aqueous solution accelerates the flow rate so that the final flow rate becomes 3.4 times the initial flow rate, and the addition of the X-2 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 3) Next, an Ag-3 aqueous solution (10
(Containing 32.0 g of AgNO ₃ in 0 mL) 329 m
L and X-3 aqueous solution (21.5 KBr in 100 mL)
g, 1.6 g of KI) by the double jet method.
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 4) Further, an Ag-4 aqueous solution (10
(Containing 32.0 g of AgNO ₃ in 0 mL) 156 m
L and X-4 aqueous solution (22.4 KBr in 100 mL)
g) was added over 17 minutes by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate, and the X-3 aqueous solution was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.3.

Thereafter, 0.0025 g of sodium benzenethiosulfonate and a G-3 aqueous solution (containing 12.0 of alkali-treated ossein gelatin in 100 mL) 12
5 mL was added sequentially at one minute intervals.

Next, 43.7 g of KBr was added, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.0.
73.9 g of AgI fine particles (containing 13.0 g of AgI fine particles having an average particle size of 0.047 μm in 100 g) were added.

(Addition 5) Two minutes later, 249 mL of an aqueous solution of Ag-4 and an aqueous solution of X-4 were added by a double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 16 minutes, and the X-4 aqueous solution was added so as to keep the pAg at 9.10.

(Addition 6) Subsequently, addition was carried out for 10 minutes so that the pAg of the bulk emulsion in the reaction vessel became 7.5.

Thereafter, desalting is carried out by a usual flocculation method, and then water, NaOH and alkali-treated ossein gelatin are added with stirring.
It adjusted so that it might be set to 5.8 and pAg8.9.

The obtained particles had a circle-equivalent diameter of 1.2 μm, a particle thickness of 0.20 μm, and an average AgI content of 3.94.
Mole%, tabular silver halide grains whose parallel main plane was the (111) plane, and the coefficient of variation of the equivalent circle diameter of all grains was 24%.

Preparation of Non-Light-Sensitive Silver Halide Grains Tabular emulsions having different circle-equivalent diameters / grain thicknesses as shown in the table by appropriately changing the grain growth conditions and the like of the non-light-sensitive silver halide grains. Was prepared.

The evaluation was performed by the following method. (Evaluation of photographic properties) Exposure and development were performed in the same manner as in Example 1, and the dot quality was evaluated. (Evaluation of Spectral Reflectance) For the evaluation of the spectral reflectance, a spectrophotometer U-3500 manufactured by Hitachi, Ltd. was used. The measurement was performed by irradiating a probe light to the sample on which the paper was placed, and integrating the light reflected from the measurement surface with an integrating sphere. (Evaluation of sensor suitability) Samples were loaded into the following image setters, and an operation of actually performing exposure processing was performed to evaluate whether or not there was a sensor detection defect.・ Dolev450 manufactured by Nippon Cytex Co., Ltd. ・ F9000 manufactured by Fuji Photo Film Co., Ltd. ・ Lux setter RC56 manufactured by Fuji Photo Film Co., Ltd.
If the 00V sensor detection failure occurs, “NO FIL
An error such as "M" is displayed. 0.3 on sensor surface
The sensor suitability was evaluated by the error display frequency through an ND filter having a density of. It shows how many times a "NO FILM" error has occurred during the 10 tests.

[0224]

[Table 2]

From Table 2, it can be seen that by using the solid particles of the present invention, a photosensitive material having improved sensor suitability and good dot quality can be obtained.

Example 3 In the same experiment as in Examples 1 and 2, based on the formulation of Example 1, the solid developer (C) and the solid fixing agent which were closely packed in a polyethylene container in the following order of lamination were used. When the test was performed using (D), the sample having the configuration of the present invention showed good performance as in Examples 1 and 2.

[0227] Solid developer (C) Formulation first layer hydroquinone second layer other components third layer KBr Fourth layer Na ₂ S ₂ O ₅ fifth layer potassium carbonate sixth layer KOH pellets

As the fixing agent, the following formulation was used in the same manner as the developer. Formulation of solid fixing agent (D) First layer (NH ₄ ) ₂ S ₂ O ₃ / Na ₂ S ₂ O ₃ / SS 160.0 g Second layer Na ₂ S ₂ O ₅ 15.0 g Third layer Sodium acetic anhydride 32.7 g Fourth layer Ethylenediaminetetraacetic acid 0.03 g Succinic acid 3.3 g Tartaric acid 3.0 g Sodium gluconate 1.8 g Fifth layer Ammonium ban 23.0 g pH in 1 liter of working solution 4.80

Example 4 The same experiment as in Examples 1 and 2 was performed using the following developer (E) in place of the developer (A) in Examples 1 and 2, and Similarly, the light-sensitive material having the constitution of the present invention showed good performance.

The composition per liter of the concentrated solution of the developer (E) is shown below. Water 600 ml potassium hydroxide 96.0 g diethylenetriamine-pentaacetic acid 6.0 g potassium carbonate 48.0 g sodium metabisulfite 120.0 g potassium bromide 9.0 g hydroquinone 70.0 g 5-methylbenzotriazole 0.24 g 1-phenyl-3 -Pyrazolidone 1.7 g 2-mercaptobenzthiazole 0.18 g 1-phenyl-5-mercaptotetrazole 0.06 g sodium erythorbate 9.0 g diethylene glycol 40.0 g Potassium hydroxide was added, and water was added to make 1 liter.
Adjust H to 10.8. As the working liquid, water 2 is added to the above liquid 1 (pH is 10.45). The replenishment amount is Taizen (5
0.8 × 61.0cm) 100ml per sheet or 1
m ² per 323ml.

Example 5 In Examples 1 to 4, the developing temperature was 38 ° C. and the fixing temperature was 37.
When the processing was carried out at a temperature of 20 ° C. and a developing time of 20 seconds, the same results as in Examples 1 to 4 were obtained, and the effects of the present invention were not lost.

Example 6 In Examples 1 to 5, the automatic machine was replaced by FG-680AS manufactured by the company.
, The same processing was performed with the photosensitive material transporting speed set to a linear speed of 1500 mm / min to obtain similar results.

Example 7 Luxsetter RC-5 manufactured by Fuji Photo Film Co., Ltd.
Instead of using 600V, Dainippon Screen Co., Ltd.
Setter FT-R5055 manufactured by Agfage Balt Co., Ltd. Select set 5000, Avantra 2
5, or AccuSet 1000, Dreb 450 or Dreb 800, manufactured by Cytex Co., Ltd., Rhino 630, Quasar, Hercules Elite, or Signa Setter, manufactured by Heidel Co., Ltd., or Laxel F-9000, or Prepress Co., Ltd. When the same evaluation as in Examples 1 to 5 was performed using any one of the Panther Pro 62 models, the same effect was obtained with the sample of the present invention.

[Brief description of the drawings]

FIG. 1 shows absorption spectra of an emulsion layer side and a back side in Examples of the present invention.

[Explanation of symbols]

The vertical axis indicates absorbance (0.1 interval), and the horizontal axis is 350 nm.
From 950 to 950 nm. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/29 G03C 5/29 (72) Inventor Yama ▲ Saki ▼ Kazuki 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo F-term in Film Co., Ltd. (reference) 2H016 AA01 AE00 AG01 2H023 BA00 CC04 CD15 FD00

Claims (8)

[Claims] 1. A support having at least one silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer or another hydrophilic colloid layer is represented by at least one kind of formula (D). Silver photographic light-sensitive material characterized by containing a hydrazine derivative. General formula (D) In the formula, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₁₀ has a σp value of 0.2 or more and 0.8 or less,
And π value is -5.0 or more, represents a 2.0 following blocking _{group, G 10} is -CO -, - C (= S ) -, - SO 2 -,
_{-SO -, - PO (R 30} ) - group _{(. R 30} has the same meaning as _{R 10,} may be different from _{R 10),} or an iminomethylene group. A ₁₀ and A _{20 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. 2. An 850 layer of a light-sensitive material in the same layer as the light-sensitive silver halide emulsion layer or in another hydrophilic colloid layer.
The average of the integrated values of the spectral reflectances of
2. The silver halide photographic light-sensitive material according to claim 1, which contains solid grains in an amount increasing by at least%. 3. The light-sensitive silver halide photographic material according to claim 2, wherein said solid particles have a refractive index of 1.54 or more. 4. A light-sensitive silver halide photographic material according to claim 2, wherein said solid particles are substantially light-insensitive silver halide particles. 5. The method according to claim 1, wherein the solid grains are substantially light-insensitive silver halide grains, and the light-insensitive silver halide grains are tabular grains having an average grain thickness of 0.02 to 0.20 μm. Item 6. The photosensitive silver halide photographic material according to item 4. 6. The light-sensitive silver halide photographic material according to claim 1, wherein the coated silver amount of the light-sensitive silver halide emulsion is 3.0 g / m ² or less. 7. The light-sensitive silver halide photographic material according to claim 1, wherein at least one of said silver halide emulsion layer and another hydrophilic colloid layer has the general formula (1): A silver halide photographic material comprising at least one compound represented by the formula: General formula (1) In the formula, M represents a hydrogen atom, an alkali metal, or a protecting group that is cleaved by an alkali. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, a nitro group, a substituted or unsubstituted group. Represents an alkoxy group or a cyano group. 8. The photosensitive silver halide photographic material according to claim 1, which has a pH of 9.0 or more.
An image forming method, wherein development processing is performed using a developing solution of less than 0.