JP3051896B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which can be handled in an environment which can be substantially called a bright room. .

[0002]

2. Description of the Related Art In the field of print duplication, there is a demand for an improvement in the work efficiency of a photomechanical process in order to cope with the variety and complexity of printed matter. In particular, in the work of plate collecting and reversing processes, work efficiency has been improved by working in a brighter environment, and for this reason it is necessary to handle in an environment that can be substantially called a bright room. Development of a silver halide photographic light-sensitive material for plate making and development of an exposure printer have been promoted. A silver halide photographic light-sensitive material for a light room described in this patent is a material containing no ultraviolet light component.
It is a photographic material in which light having a wavelength of 0 nm or more can be used as safelight light. The silver halide photographic light-sensitive material for bright rooms used in the plate collection and reversing processes is composed of a developed film on which characters or halftone images are formed as a document, and a silver halide photographic light-sensitive material for reversal. This is a photosensitive material used to perform negative image / positive image conversion or positive image / negative image conversion by contact exposure. Halftone images and line drawings, and character images are each used for their halftone dot area and line width, It has the ability to convert negative / positive images according to the width of the character image. It is required to have the ability to adjust the tone of halftone images and the line width of characters and line images. Silver halide photographic light-sensitive materials have been provided. However, in the tone adjustment of a halftone dot image in a light room reversing process using a silver halide photographic light-sensitive material for a light room, if underexposure occurs, the image is developed entirely over the entire surface, and the density of the portion to be blackened is liable to be significantly reduced. Had the drawback.

As a method for obtaining a high contrast and an increase in Dmax, a method in which a developing agent is contained in a silver halide photographic light-sensitive material is disclosed in US Pat. No. 4,617,258;
Nos. 171947 and 59-206828;
262533, etc., but safelights,
It does not satisfy both the storage stability over time and the performance of Dmax. In addition, those in which an impurity (heavy metal) is contained in a silver halide crystal are disclosed in EP 336427,
Although it is disclosed in JP-A-336689, the storage stability is poor and fogging occurs, and the above-mentioned performance and the performance of Dm cannot be stably maintained.

[0004]

Accordingly, a first object of the present invention is to use a silver halide photographic light-sensitive material for a bright room which can be handled in a bright room environment and to stably reduce the density during underexposure. An object of the present invention is to provide a silver halide photographic light-sensitive material which gives a small excellent reversing performance. It is a second object of the present invention to provide a silver halide photographic light-sensitive material which exhibits excellent reversing performance without any change in photographic performance due to natural aging.

[0005]

The above objects of the present invention are as follows.
In a silver halide photographic material having a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion layer on a support, each emulsion layer has at least one layer per mole of silver.
× A silver halide containing a transition metal selected from the V~VIII group elements of the periodic table having a ^10-6 mole of nitrosyl or thionitrosyl ligand, silver chloride content of 90 mol% A silver halide photographic material comprising the above silver halide, wherein the hydrophilic colloid layer contains at least one compound represented by the following general formula [I], [II] or [III]. Achieved by

[0006]

Embedded image

[0007]

Embedded image

In the formula, R ^{1 to} R ⁴ may be the same or different, and each represents a hydroxy group, a hydroxylamino group, an amino group, an alkylamino group, an arylamino group,
Represents an aralkylamino group, an alkoxy group, a phenoxy group, an alkyl group, an aryl group, an alkylthio group, a phenylthio group or a hydrazino group. General formula [III] X ₁ -AX _{2 In the} formula, X ₁ and X ₂ represent —OR ₁ or —NR ₂ (R ₃ )
Wherein (R ₁ represents a hydrogen atom or a group that can be converted to a hydrogen atom by hydrolysis, and R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylsulfonyl group, an arylsulfonyl group, Heterocyclic sulfonyl group, alkylcarbonyl group, arylcarbonyl group,
Represents a heterocyclic carbonyl group, a sulfamoyl group or a carbamoyl group. ) A represents an arylene group, X ₁ , X
_In at least one of ₂ and A, a hydrogen atom contained in the group may be replaced by a group which promotes adsorption to silver halide grains.

The transition metal coordination complex which achieves the object of the present invention is preferably a hexacoordination complex represented by the following general formula. [M (NY) L ₅ ] ^m (where M is a transition metal selected from elements of Groups 5 to 10 of the periodic table of elements, L is a bridging ligand, and one (NY) Y is oxygen or sulfur, m = 0, -1, -2, -3.) Preferred specific examples of L other than nitrosyl and thionitrosyl bridging ligands include halogen. Fluoride ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanate ligands, acid ligands And aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. Particularly preferred specific examples of M are rhodium, ruthenium, rhenium, osmium and iridium.

The following are specific examples of the transition metal coordination complex. 1 [Ru (NO) Cl ₅ ] ^-22 [Ru (NO) ₂ Cl ₄ ] ^-13 [Ru (NO) (H ₂ O) Cl ₄ ] ^-14 [Rh (NO) Cl ₅ ] ^-2 5 [Re (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl _5] ^-2 14 [Cr (NO) Cl _5] ^-3 15 [Re (NO) Cl _5] ^-1 16 _{[Os (NS) Cl 4 (TeCN} ) ] ^-2 17 [Ru (NS) I _5] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The above metal complex can be added to silver halide during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10 ^-6 mol, preferably 10 ^{-6 to} 5 × 10 ^-4 mol, particularly 1 × 10 ^-5 mol per mol of silver halide. 5 × 10 ^-4
Is a mole. There is no particular limitation on the distribution of the transition metal in the silver halide grains, but it is preferable that the transition metal be present more outside the grains.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is preferably a silver halide comprising 90% by mole or more of silver chloride, and silver chlorobromide containing 0 to 5% by mole of silver bromide or It is silver chloroiodobromide. An increase in the ratio of silver bromide or silver iodide is not preferable because the safelight safety in a bright room deteriorates or γ decreases. The silver halide used in the present invention is preferably a so-called core / shell type silver halide, and particularly preferably a core / shell type silver halide having a higher metal content of the shell than the core.
When the water-soluble metal complex salt is present in the silver halide grains using a water-soluble metal complex salt, when the water-soluble silver salt and the water-soluble halide solution are simultaneously mixed, a method in which the water-soluble silver salt is added to the water-soluble silver salt or the halide solution is used. preferable. Alternatively, when a silver salt and a halide solution are simultaneously mixed, silver halide grains may be prepared as a third solution by a three-solution simultaneous mixing method. The grain size of the silver halide emulsion of the present invention is preferably 0.20 μm or less.

In the present invention, silver halide fine grains are prepared by mixing at a reaction temperature of 50 ° C. or lower, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, and a sufficiently high stirring speed for uniform mixing. 70m silver potential below
Good results can be obtained by adjusting the voltage to V or more, preferably 80 mV to 120 mV. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodispersion” as used herein means at least 9 parts by weight or number of particles.
5% is composed of particles having a size within ± 40% of the average particle size, more preferably within ± 20%. The silver halide grains of the present invention preferably have regular crystals such as cubes and octahedrons, and particularly preferably cubes.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. A specific example is U.S. Pat.
8,060 and British Patent 618,061. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a first tin salt, an amine, formamidinesulfinic acid, a silane compound and the like can be used.

Next, the compounds of the general formulas [I], [II] and [III] used in the present invention will be described in detail. The following general formula (I) added in the present invention,
The compound represented by [II] or [III] may be used in any layer (emulsion layer, intermediate layer, protective layer, etc.) of a silver halide photographic material, but is preferably used in a silver halide emulsion layer. More preferred. First, general formulas [I] and [II] will be described.

[0016]

Embedded image

[0017]

Embedded image

In the formula, R ^{1 to} R ⁴ may be the same or different, and each represents a hydroxy group, a hydroxylamino group, an amino group, an alkylamino group (preferably a mono- or di-substituted amino group having an alkyl group having 1 to 5 carbon atoms). Group), an aralkylamino group (preferably having 7 to 11 carbon atoms), an arylamino group (preferably an amino group substituted by an aryl group having 6 to 10 carbon atoms), an alkoxy group (preferably having 1 carbon atom).
To 5), a phenoxy group, an alkyl group (preferably having 1 to 5 carbon atoms), an aryl group (preferably having 6 to 10 carbon atoms), an alkylthio group (preferably having 1 to 5 carbon atoms) , A phenylthio group, or a hydrazino group. The alkyl moiety in each of the above groups is a hydroxy group or an alkoxy group (preferably having 1 to 4 carbon atoms, particularly 1 to 4 carbon atoms).
2), an amino group, an alkylamino group (preferably a mono- or di-substituted amino group of an alkyl group having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms). In each of the groups represented by R ^{1 to} R ⁴ , the aryl or phenyl moiety is a hydroxy group, an amino group, or an alkylamino group (preferably a mono- or di-substituted amino group having 1 to 4 carbon atoms, particularly 1 to 2 alkyl groups) And an alkyl group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms) and an alkoxy group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms). The compounds of the general formulas [I] and [II] preferably used in the present invention are exemplified below.

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

These compounds are available in the Journal of the
Organic Chemistry, 27, 4054 (19
62), Journal of the American Chemical Society, 73, 2981 (1951), and JP-B-49-10692. These compounds form a photographic emulsion or a constituent layer other than the emulsion layer (for example, an overcoat layer, a filter layer, an intermediate layer, etc., preferably a layer adjacent to the emulsion layer) as an aqueous solution, a hydrochloric acid aqueous solution or a methanol solution. To the hydrophilic colloid solution. The timing of addition is not particularly limited, but when it is added to a photographic emulsion, it is convenient to add it during the second ripening and immediately before coating. The addition amount of these compounds varies depending on the type of the polymer used in combination, but is usually 0.01 g to 10 g, particularly 0.1 g to 1 g per mol of silver.
Set to the range.

Next, the compound represented by the general formula [III] used in the present invention will be described. In the general formula [III], A is a substituted or unsubstituted arylene group (for example, a phenylene group, a naphthylene group, etc.).
Halogen atom (fluorine, chlorine, bromine), alkyl group (preferably having 1 to 20 carbon atoms), aryl group (preferably having 6 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms) ), An aryloxy group (preferably having 6 to 20 carbon atoms), an alkylthio group (preferably having 1 to 20 carbon atoms), an arylthio group (preferably having 6 to 20 carbon atoms), an acyl group (preferably An acylamino group (preferably an alkanoylamino group having 1 to 20 carbon atoms, 6 to 20 carbon atoms)
Nitro group, cyano group, oxycarbonyl group (preferably alkoxycarbonyl group having 1 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms), carboxy group, sulfo group, hydroxy group, ureido Group (preferably an alkylureido group having 1 to 20 carbon atoms, an arylureido group having 6 to 20 carbon atoms), a sulfonamide group (preferably an alkylsulfonamide group having 1 to 20 carbon atoms, arylsulfone having 6 to 20 carbon atoms) Amide group), sulfamoyl group (preferably having 1 to 20 carbon atoms)
Alkylcarbamoyl group, arylcarbamoyl group having 6 to 20 carbon atoms), carbamoyl group (preferably alkylcarbamoyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms)
0 arylcarbamoyl group), acyloxy group (preferably having 1 to 20 carbon atoms), amino group (unsubstituted amino, preferably substituted with an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms) A secondary or tertiary amino group), a carbonate group (preferably having 1 to 2 carbon atoms).
0 alkyl carbonate group, C6-20 arylcarbonate group), sulfonyl group (preferably C1-20 alkylsulfonyl group, C6-20 arylsulfonyl group), sulfinyl group (preferably Alkylsulfinyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
0 arylsulfinyl group) and a heterocyclic group (pyridine, imidazole, furan, etc.).

When there are two or more substituents, they may be the same or different. When two substituents are substituted on adjacent carbon atoms of a benzene ring, they are linked to form a 5- to 7-membered ring. They may form carbocycles or heterocycles, and these rings may be saturated or unsaturated. Specific ring-forming compounds include cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexadiene, cycloheptadiene,
Examples thereof include indane, norbornane, norbornene, benzene, pyridine and the like, which may further have a substituent. The total number of carbon atoms of the substituent is 1 to 20
Are preferred, and more preferably 1 to 10.

Examples of the group represented by R ₁ that can be converted to a hydrogen atom by hydrolysis include —COR ₄ (R ₄ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents an amino group.

[0033]

Embedded image

(J represents —CO— or —SO ₂ —;
Represents a plurality of atoms necessary to form a heterocyclic ring having at least one 5- or 6-membered ring. ).

R ₂ and R _{3 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted group; Arylsulfonyl group, substituted or unsubstituted heterocyclic sulfonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted heterocyclic carbonyl group, substituted or unsubstituted sulfamoyl group Represents a substituted or unsubstituted carbamoyl group, and R ₂ and R ₃ may be the same or different;
Also, they may be linked to form a nitrogen-containing heterocycle. (For example, a morpholino group, a piperidino group, a pyrrolidino group, an imidazolyl group, a piperazino group, etc.) As the substituents for R ₂ and R ₃ , the same substituents as those described above for A can be mentioned.

The group for promoting adsorption to silver halide can be represented by the following formula: Y- (L) _m -Y is a group for promoting adsorption to silver halide, and L is a divalent linking group. m is 0 or 1. Preferred examples of the group for promoting adsorption to silver halide represented by Y include a thioamide group, a mercapto group, a group having a disulfide bond, and a 5- or 6-membered nitrogen-containing heterocyclic group.
The thioamide adsorption promoting group represented by Y is a divalent group represented by -CS-amino, and may be a part of a ring structure or an acyclic thioamide group.
Useful thioamide adsorption promoting groups are described, for example, in US Pat.
30,925, 4,031,127, 4,08
Nos. 0,207, 4,245,037, 4,25
Nos. 5,511, 4,266,013 and 4,2
No. 76,364, and "Research Disclosure", Volume 151, No. 1
5162 (November 1976), and Volume 176, No.
17626 (December 1978). Specific examples of the acyclic thioamide group include, for example, a thioureido group, a thiourethane group, a dithiocarbamate group, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione, 4-imidazoline-2. -Thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,
Examples include 3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, and benzothiazoline-2-thione, which may be further substituted.

The mercapto group of Y is an aliphatic mercapto group,
Aromatic mercapto group or heterocyclic mercapto group (when a carbon atom to which a -SH group is bonded is a nitrogen atom, it is synonymous with a cyclic thioamide group having a tautomeric relationship with the nitrogen atom. Specific examples of this group Is the same as listed above)
Is mentioned.

The 5- or 6-membered nitrogen-containing heterocyclic group represented by Y includes a 5- or 6-membered nitrogen-containing heterocyclic ring comprising a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like. These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for A. Of those represented by Y, preferred are cyclic thioamide groups (ie, mercapto-substituted nitrogen-containing heterocycles such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group,
5-mercaptotetrazole group, 2-mercapto-1,
3,4-oxadiazole group, 2-mercaptobenzoxazole group or the like), or a nitrogen-containing heterocyclic group (for example,
Benzotriazole group, benzimidazole group, indazole group, etc.). Two or more Y- (L) _m -groups may be substituted, and may be the same or different.

As the divalent linking group represented by L,
An atom or atomic group containing at least one of C, N, S, and O. Specifically, for example, an alkylene group, alkenylene group, alkynylene group, arylene group, -O-,-
S -, - NH -, - N =, - CO -, - SO 2 - ( these groups may also have a substituent) is made of a single or combination of such.

As specific examples, for example, -CONH-, -NHCO
_{NH-, -SO 2 NH-, -COO-,} -NHCOO -, - CH 2 -, - (CH 2) -
,-(CH ₂ ) _3- , -NHCONHCH ₂ CH ₂ CONH-, -CH ₂ CH ₂ SO ₂ NH-
, -CH ₂ CH ₂ CONH-,

[0042]

Embedded image

[0043]

Embedded image

And the like. These may be further substituted with a suitable substituent. Examples of the substituent include those described as the substituent of A.

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

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

Hereinafter, typical methods for synthesizing the compound of the general formula [III] will be described with reference to synthetic examples. Synthesis Example Synthesis of compound III-55 5-phenylbenztriazole carbonate 23.8
g (0.1 mol), 2- (4-aminophenyl) -ethylhydroquinone 25.2 g (0.11 mol), DMA
C in an oil bath at 120 ° C. (external temperature) under a nitrogen stream.
The mixture was heated and stirred for hours. Next, DMAC was distilled off under reduced pressure, and when 200 ml of methanol was added, trace amounts of black crystal by-products remained as insolubles. The insoluble matter was removed by suction filtration, and the reaction mixture obtained by distilling off methanol under reduced pressure was isolated and purified on a silica gel column (chloroform / methanol = 4/1). After washing with methanol, the target product I-11 was obtained. Obtained. Yield 1
4.4 (38.5%) Melting point: 256-7 ° C.
The compound represented by I] is 1 × per mole of silver halide.
The addition amount is preferably from 10 ^-5 mol to 1 × 10 ^-1 mol, and particularly preferably from 1 × 10 ^-4 to 5 × 10 ^-2 mol. When these compounds of the general formula [III] are contained in a photographic light-sensitive material, they are aqueous if they are water-soluble, alcohols (eg methanol, ethanol) esters (eg ethyl acetate), ketones if water-insoluble The solution may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as acetone (for example, acetone). When added to the silver halide emulsion solution, the addition can be performed at any time from the start of chemical ripening to coating, but is preferably performed after the completion of chemical ripening, especially the coating prepared for coating. It is preferably added to the solution.

The light-sensitive material prepared by using the present invention preferably contains a dye dispersed in a solid state as a filter dye in a hydrophilic colloid layer located above the emulsion layer. Next, specific examples of preferable dyes will be shown, but the present invention is not limited thereto. Dyes dispersed in a solid state are described in International Application Publication (WO) 88/04794, EP 0276566, and the like.

[0061]

Embedded image

[0062]

Embedded image

Further, a water-soluble dye may be used in combination with the hydrophilic colloid layer or the emulsion layer as a filter dye or for various purposes such as prevention of irradiation.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis- [β-
(Vinylsulfonyl) propionamide]), an active halogen compound (2,4-dichloro-6-hydroxy-
s-triazine, etc.), mucohalic acids (such as mucochloric acid), N-carbamoylpyridinium salts ((1-
Morpholi) carbonyl-3-pyridinio) methanesulfonate and the like, and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium and 2-naphthalenesulfonate) can be used alone or in combination. Among them, JP-A-53-41220, JP-A-53-57257, JP-A-59-162546, and JP-A-60-8
No. 0846 and US Pat.
The active halide described in No. 325,287 is preferred.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention, coating aids, antistatic, slipperiness improvement, emulsification dispersion, adhesion prevention and photographic property improvement (for example, development acceleration) For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( For example, nonionic surfactants such as alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and alkyl esters of sugars; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. In order to prevent charging, Japanese Patent Application Laid-Open No. Sho 60-80849
It is preferable to use the fluorinated surfactant described in the above item.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate for the purpose of preventing adhesion to the photographic emulsion layer or other hydrophilic colloid layers. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)
A polymer having a monomer component of acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or the like alone or in combination, or a combination of these with acrylic acid, methacrylic acid, or the like can be used. Gelatin is advantageously used as a condensing agent or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. Cellulose triacetate as a support of the light-sensitive material of the present invention,
Cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, and the like can be used.

The developing agent used in the developer used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes from the viewpoint of obtaining good halftone dot quality. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferred. 1-phenyl- used in the present invention
The developing agent for 3-pyrazolidone or a derivative thereof is 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,
1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3- And pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol and N-methylphenol.
-(Β-hydroxyethyl) -p-aminophenol,
There are N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The developing agent is preferably used in an amount of usually 0.05 mol / l to 0.8 mol / l. Also, dihydroxybenzenes and 1-phenyl-3-
When a combination with pyrazolidones or p-amino-phenols is used, the former is used in an amount of from 0.05 mol / l to
It is preferred to use 0.5 mol / l and the latter in an amount of 0.06 mol / l or less. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.3 mol of sulfite /
It is preferably at least liter, especially at least 0.4 mol / liter. The upper limit is up to 2.5 mol / l, especially 1.
It is preferably up to 2. Alkali agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic,
PH adjusters and buffers such as potassium tertiary phosphate, sodium silicate and potassium silicate are included. Compounds such as boric acid and borax as additives used in addition to the above components,
Development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide,
Organic solvents such as methyl cellosolve, hexylene glycol, ethanol, and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and indazole compounds such as 5-nitroindazole The compound may contain an antifoggant such as a benztriazole-based compound such as 5-methylbenztriazole, and further contains a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and the like, if necessary. May be. In particular, JP-A-56-1
No. 06244, Amino compounds described in JP-B-48-35
The imidazole compound described in No. 493 is preferred in terms of accelerating development or increasing sensitivity. In the developer used in the present invention, a silver stain inhibitor is disclosed in JP-A-56-24347.
Described in Japanese Patent Application Laid-open No. Sho 62 (1994)
-212,651), and the compound described in JP-A-61-267759 can be used as a dissolution aid. In the developer used in the present invention, boric acid described in JP-A-62-186259, saccharides described in JP-A-60-93333 (for example, saccharose), oximes (for example, acetoxime) may be used as a buffer. Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salts and potassium salts) and the like are used, and boric acid is preferably used.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or a salt thereof), if necessary, in addition to the fixing agent. , PH 3.8 or more, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1
~ 5 mol / l. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like. Examples of citric acid or a derivative thereof effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. The fixing solution may further contain a preservative (for example, sulfite or bisulfite), if desired.
It may contain a pH buffer (eg, acetic acid, boric acid), a pH adjuster (eg, ammonia, sulfuric acid), an image preserving agent (eg, potassium iodide), and a chelating agent. Here, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter, because the pH of the developer is high. The fixing temperature and time are the same as those for the development, and
Preferred is 0 seconds to about 50 degrees Celsius for 10 seconds to 1 minute. Further, the washing water may contain a fungicide (for example, a compound described in Horiguchi's "Bacterial Prevention and Prevention Chemistry", JP-A-62-115154), a washing accelerator (such as a sulfite), a chelating agent, and the like. May be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. The water washing is performed to almost completely remove the silver salt dissolved by the fixing, and is preferably performed at about 20 ° C. to about 50 ° C. for 10 seconds to 3 minutes. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but usually about 5 seconds to 3 minutes and 3 seconds. U.S. Pat. No. 3025 discloses a roller transport type automatic developing machine.
No. 779, No. 3,545,971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Here, in the rinsing step, water can be saved by using a two- or three-stage countercurrent rinsing method. The developer used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147.
The developer used in the present invention is described in JP-A-62-9193.
The replenishment system described in No. 9 can be preferably used. The silver halide photographic material of the present invention has a high Dma.
Since x is given, when the image is subjected to a reduction process after image formation, a high density is maintained even if the dot area is reduced. There are no particular restrictions on the reducer used in the present invention. For example, Meesz, The Theory of the Photographic Pro
cess ", pp. 738-744 (1954, Macmilla
n), Tetsuo Yano, Photo Processing Theory and Practice, 166-1
69 pages (1978, Kyoritsu Shuppan), and JP-A-50-27543, JP-A-52-68429, and JP-A-55-68429
Nos. -17123, 55-79444, and 57-10
No. 140, No. 57-142639, JP-A-61-61
No. 155 or the like can be used. That is, as an oxidizing agent, permanganate, persulfate, ferric salt, cupric salt, ceric salt, red blood salt, dichromate, or the like alone or in combination, and further if necessary A reducing solution containing an inorganic acid such as sulfuric acid or alcohol, or an oxidizing agent such as red blood salt or ferric ethylenediaminetetraacetate, and a halogen such as thiosulfate, rodane salt, thiourea or a derivative thereof. A reducing solution containing a silver halide solvent and, if necessary, an inorganic acid such as sulfuric acid is used. Representative examples of the reducer used in the present invention include so-called Farmer reducer, ferric ethylenediaminetetraacetate, potassium permanganate, ammonium persulfate reducer (Kodak R-5), ceric cerium Salt reducer. The conditions of the reduction treatment are generally 10 ° C to 40 ° C, particularly 15 ° C to 30 ° C.
It is preferable that the process can be completed at a temperature of ° C. within a period of several seconds to several tens of minutes, particularly within several minutes. If the photosensitive material for plate making of the present invention is used, a sufficiently wide reduction range can be obtained within the range of these conditions. The reducer acts on the silver image formed in the emulsion layer via the non-photosensitive upper layer containing the compound of the present invention.
Specifically, there are various methods, for example, immersing the plate making sensitizer in the reducer, stirring the liquid, or applying the reducer to the surface of the plate sensitizer with a brush, a roller, or the like. Method is available.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, a developer having the following formulation was used. -Potassium sulfite 67 g-Ethylenediamine-4-acetic acid-2-sodium 3.0 g-Hydroquinone 23 g-4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.4 g-2-mercaptobenzimidazole-5-sulfone Sodium acid 0.3g-Potassium hydroxide 11g-5-methylbenzotriazole 0.1g-Sodium carbonate 11g-Potassium bromide 3.0g Water is added to make 1 liter. (Adjusted to pH 10.7)

[0070]

EXAMPLE 1 Preparation of Emulsion An aqueous silver nitrate solution and silver 1 were added to an aqueous gelatin solution kept at 40 ° C.
As shown in Table 1, a sodium chloride aqueous solution containing 5 × 10 ⁻⁵ mol of metal per mol was simultaneously added in three and a half minutes, and the potential between them was controlled at 95 mV to prepare 0.11 μm of core particles. . Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 1.5 × 10 ^-4 mol of metal per mol of silver were simultaneously added for 7 minutes as shown in Table 1 and the potential between them was controlled at 95 mV to control the average particle size to 0 mV. .14 μm silver chloride cubic grains were prepared. Preparation of coating sample 1-phenyl-5-mercaptotetrazole was added to the above emulsion at 2.5 mg / m ² and ethyl acrylate latex (average particle size: 0.05 μm) at 770 mg / m ² , as shown in Table 1. The compound was added, and 126 mg / m ² of 2-bis (vinylsulfonylacetamide) ethane was added as a hardener, and the mixture was coated on a polyester support so that silver became 3.0 g / m ² . Gelatin was 1.5 g / m ² . On this, gelatin 0.8 g / m ² and lipoic acid 8 mg /
m ² , ethyl acrylate latex (average particle size 0.05
μm) of 230 mg / m ^2, and gelatin 0.7 g / m ² as the upper layer of the protective layer and the dye 11 described above were applied in a solid dispersion state. At this time, a matting agent (silicon dioxide, average particle size 3.5 μm) 55 mg / m ² , methanol silica (average particle size 0.02 μm) 135 mg / m ² , sodium dodecylbenzenesulfonate 25 mg / m
m ² , poly (degree of polymerization 5) oxyethylene nonyl phenyl ether sulfate 20 mg / m ² , N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3 mg / m ² were simultaneously coated to prepare a sample. did. The base used in this example has a back layer and a back protective layer having the following compositions. (The swelling ratio on the back side is 1
10%. ) (Back layer) Gelatin 170 mg / m ² Sodium dodecylbenzenesulfonate 32 mg / m ² Sodium dihexyl-α-sulfosacnate 35 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 318 mg / M ² (back protective layer) Gelatin 2.7 g Silicon dioxide matting agent (average particle size 3.5 μm) 26 mg / m ² Sodium dihexyl-α-sulfosacnate 20 mg / m ² Sodium dodecylbenzenesulfonate 67 mg / m ²

[0071]

Embedded image

[0072]

Embedded image

Ethyl acrylate latex (average particle size 0.05 μm) 260 mg / m ² 1,3-divinylsulfonyl-2-propanol 149 mg / m ²

Photographic performance The sample thus obtained was exposed through a light wedge with a P-627FM printer (mercury) manufactured by Dainippon Screen Co., Ltd., and a developer LD-835 manufactured by Fuji Photo Film Co., Ltd., an automatic developing machine FG800RA For 20 seconds at 38 ° C., followed by fixing, washing and drying. The following items were evaluated for these samples. 1) γ; (1.5-0.1) / − {log (exposure to give a density of 0.1) −log (exposure to give a density of 1.5)} 2) Dmax, Dmax (−1%) A film in which a halftone image is formed on a pasting base (halftone original) is fixed with an adhesive tape, and the protective layer of each film sample is brought into close contact with the halftone original such that the halftone original is overlapped face to face; The maximum blackening densities obtained when exposure was performed so that the halftone dot area was 50% and 49% on the film sample were Dmax and Dmax, respectively.
(-1%). 3) Storage stability with time (△ fog): After leaving the film at 60 ° C. and 30% for 5 days, the Dmi of five original samples was stacked.
n was evaluated as a rise in fresh performance. As is evident from Table 1, the sample of the present invention has little fogging with time, has a hard toe gradation, and has a high Dmax, and has excellent turning performance.

[0075]

[Table 1]

Example 2 Preparation of Emulsion Aqueous solution of silver nitrate and silver 1 in an aqueous solution of gelatin maintained at 38 ° C.
As shown in Table 2, a sodium chloride aqueous solution containing 5 × 10 ⁻⁵ mol of metal per mol was simultaneously added in 3 半 minutes, and the potential during that time was controlled to 95 mV to prepare 0.08 μm of core particles. . Thereafter, as shown in Table 2, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 1.5 × 10 ^-4 mol of metal per mol of silver were simultaneously added over 7 minutes, and the potential between them was controlled at 95 mV. 6-
Trimethylene-7-hydroxy-s-triazolo (2,
3-a) Pyrimidine was added in an amount of 5 × 10 ⁻³ mol per mol of silver. The obtained grains were silver chloride cubic grains having an average grain size of 0.10 μm. Preparation of Coated Sample 1-phenyl-5-mercaptotetrazole was added to the above emulsion at 2.5 mg / m ² , and 5,6-trimethylene-7-hydroxy-s-triazolo (2,3-a) pyrimidine was added at 12 mg.
/ M ² , ethyl acrylate latex (average particle size 0.0
5 [mu] m) to 770 mg / m ^2, and adding the compound of the present invention as shown in Table 2, as a hardener 2- bis (vinylsulfonyl acetamide) ethane 126 mg / m ² In addition, three silver on a polyester support It was coated so as to become a .0g / m ^2. Gelatin was 1.5 g / m ² . On top of this, 0.8 g / m ² of gelatin, 8 mg / m ^{2 of} lipoic acid, ethyl acrylate latex (average particle size: 0.05 μm) 230 as a lower layer of a protective layer
mg / m ^2, and gelatin 0.7 g / m ² as the upper layer of the protective layer and the dye 11 were applied in a solid dispersion state. At this time, a matting agent (silicon dioxide, average particle size 3.5 μm) 55 mg / m ² , methanol silica (average particle size 0.02 μm) 135 mg / m ² , sodium dodecylbenzenesulfonate 25 mg / m ² as a coating aid, Sodium sulfate sodium salt of poly (degree of polymerization 5) oxyethylene nonylphenyl ether 20 mg / m ² , N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3
mg / m ² was simultaneously applied to prepare a sample. The back layer is the same as in the first embodiment. The obtained sample was tested in the same manner as in Example 1, and the results are shown in Table 2. As is evident from Table 2, the sample of the present invention has a hard toe gradation, a high Dmax, a low fog over time, and an excellent turning performance.

[0077]

[Table 2]

Example 3 Preparation of Emulsion An aqueous solution of silver nitrate and silver 1 in an aqueous solution of gelatin maintained at 40 ° C.
As shown in Table 3, a sodium chloride aqueous solution containing 5 × 10 ⁻⁵ mol of a metal per mol was simultaneously added in 3 半 minutes, and the potential during that time was controlled to 95 mV, thereby preparing 0.11 μm of core particles. . Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 1.5 × 10 ^-4 mol of metal per mol of silver were simultaneously added for 7 minutes as shown in Table 1 and the potential between them was controlled at 95 mV to control the average particle size to 0 mV. .14 μm silver chloride cubic grains were prepared. Other conditions were the same as in Example 1, and each sample was prepared. Each sample was evaluated in the same manner as in Example 1, and the results shown in Table 3 were obtained. As is clear from Table 3, the sample of the present invention
It can be seen that there is little aging fog, the toe gradation is hard, and a high Dmax is obtained, indicating excellent reversing performance.

[0079]

[Table 3]

Example 4 Preparation of Emulsion An aqueous solution of silver nitrate and silver 1 in an aqueous solution of gelatin maintained at 38 ° C.
As shown in Table 2, a sodium chloride aqueous solution containing 5 × 10 ⁻⁵ mol of metal per mol was simultaneously added in 3 半 minutes, and the potential during that time was controlled to 95 mV to prepare 0.08 μm of core particles. . Thereafter, as shown in Table 4, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 1.5 × 10 ⁻⁴ mol of metal per mol of silver were simultaneously added over 7 minutes, and the potential between them was controlled at 95 mV. 6-
Trimethylene-7-hydroxy-s-triazolo (2,
3-a) Pyrimidine was added in an amount of 5 × 10 ⁻³ mol per mol of silver. The obtained grains were silver chloride cubic grains having an average grain size of 0.10 μm. Preparation of Coated Sample 1-phenyl-5-mercaptotetrazole was added to the above emulsion at 2.5 mg / m ² , and 5,6-trimethylene-7-hydroxy-s-triazolo (2,3-a) pyrimidine was added at 12 mg.
/ M ² , ethyl acrylate latex (average particle size 0.0
5 [mu] m) to 770 mg / m ^2, and adding the compound of the present invention as shown in Table 4, as a hardener 2- bis (vinylsulfonyl acetamide) ethane 126 mg / m ² In addition, three silver on a polyester support It was coated so as to become a .0g / m ^2. Gelatin was 1.5 g / m ² . On top of this, 0.8 g / m ² of gelatin, 8 mg / m ^{2 of} lipoic acid, ethyl acrylate latex (average particle size: 0.05 μm) 230 as a lower layer of a protective layer
mg / m ^2, and gelatin 0.7 g / m ² as the upper layer of the protective layer and the dye 11 were applied in a solid dispersion state. At this time, a matting agent (silicon dioxide, average particle size 3.5 μm) 55 mg / m ² , methanol silica (average particle size 0.02 μm) 135 mg / m ² , sodium dodecylbenzenesulfonate 25 mg / m ² as a coating aid, Sodium sulfate sodium salt of poly (degree of polymerization 5) oxyethylene nonylphenyl ether 20 mg / m ² , N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3
mg / m ² was simultaneously applied to prepare a sample. The back layer is the same as in the first embodiment. The obtained sample was tested in the same manner as in Example 1, and the results are shown in Table 4. As is clear from Table 4, the sample of the present invention has a hard toe gradation, a high Dmax, a low fog over time, and an excellent turning performance.

[0081]

[Table 4]

[0082]

According to the present invention, by using a compound represented by the general formula (I), (II) or (III) in a silver halide emulsion containing a transition metal coordination complex, the photosensitive property can be handled in a bright room. Natural fogging of the material and reduction of the maximum blackening density during underexposure could be prevented.

Claims (1)

(57) [Claims] 1. The method of claim 1, wherein at least one layer of photosensitive halo
Halogen having a hydrophilic colloid layer including a silver gemide emulsion layer
In silver halide photographic materials, each emulsion layer was equivalent to 1 mole of silver.
At least 1 × 10^-6Molar nitrosyl or thioni
Of the V-VIII group of the periodic table having a trosyl ligand
A silver halide containing a transition metal selected from the elements
Silver halide having a silver chloride content of 90 mol% or more
Wherein the hydrophilic colloid layer has the following general formula (I):
Less compound represented by [II] or [III]
Silver halide photographic sensitivity characterized by containing one or more
Light material. Embedded imageEmbedded imageWhere R¹~ R⁴May be the same or different from each other,
A hydroxy group, a hydroxylamino group, an amino group,
Alkylamino group, arylamino group, aralkylami
Group, alkoxy group, phenoxy group, alkyl group, ant
Group, alkylthio group, phenylthio group or hydrazine
A group represented by General formula [III] X₁-AX₂  Where X₁, X₂Is -OR₁Or -NR₂(R₃)
And (R₁Is hydrogen atom or water by hydrolysis
Represents a group which can be an element atom,₂, R₃Are hydrogen sources
, Alkyl group, aryl group, heterocyclic group, alkyls
Ruphonyl group, arylsulfonyl group, heterocyclic sulfoni
Group, alkylcarbonyl group, arylcarbonyl group,
Heterocyclic carbonyl group, sulfamoyl group or carbamo
Represents an yl group. ) A represents an arylene group, X₁, X
₂And at least one of A is included in the group
Hydrogen atoms are absorbed by silver halide grains
It may be substituted.