JPH0511382A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow handling in a bright room and to improve spread and chalk characteristics by using solid disperse dyes, superfine particle silver halide, and transition metal coordinate complex. CONSTITUTION:This photosensitive material has at least one layer of photosensitive silver halide emulsion layers on a base and has a nonphotosensitive hydrophilic colloidal layer contg. dyes subjected to solid dispersion to a fine particulate state on the outer side of the emulsion layers with respect to the base. The average particle size of the silver halide particles of the photosensitive emulsion layers is <=0.15mum. Transition metals selected from groups V to VIII of periodic table are incorporated at least at 1X10<-7>mol per 1mol silver into the silver halide particles. Tone reproducibility, tone variability, spread and chalk adaptability, and outline type adaptability are satisfied in this way. In addition, the density of the solid part at the time of under-exposing in the tone control of dot images is increased and further, the handling in bright room environment is possible.

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 called a bright room. .

[0002]

2. Description of the Related Art In the field of print reproduction, it is desired to improve the work efficiency of the photomechanical process in order to cope with the variety and complexity of printed matter. Especially in the work of plate collection and reversion process, it has been attempted to improve the work efficiency by performing the work in a brighter environment. Therefore, it is necessary to handle it in an environment that can be called a bright room. The development of silver halide photographic light-sensitive materials for plate making and the development of exposure printers have been promoted. The bright room silver halide photographic light-sensitive material described in this patent does not contain an ultraviolet light component.
A photographic light-sensitive material capable of using light having a wavelength of 00 nm or more as safelight light. Conventionally, in order to enhance the safety against the safelight light, a dye that absorbs visible light has been added to the hydrophilic colloid layer that is present on the side farther from the support than the photosensitive silver halide emulsion layer. When these dyes function as a filter layer, it is necessary that the layer be selectively colored so that the other layers are not substantially colored. This is because if the emulsion layer is substantially colored, not only the harmful photographic effect is exerted on the emulsion layer but also the effect as the filter layer is reduced. In particular, there are problems such as spread & choke suitability, tone changeability, and bag character suitability that are peculiar to the return field.

As a method for solving this problem, conventionally known is a method of localizing a so-called acidic dye having a sulfo group or a carboxyl group in a specific layer by using a mordant. Examples of such mordants include British Patent No. 685,4.
No. 75, ethylenically unsaturated compound polymers having a dialkylaminoalkyl ester residue, 85
Reaction products of polyvinyl alkyl ketones and aminoguanidines described in US Pat. No. 2,548,5.
No. 64, No. 2,484,430, No. 3,148,06
Nos. 1, 3,756,814 and vinyl pyridine polymers and vinyl pyridinium cation polymers are known, and in order to effectively mord the above-mentioned acid dye, secondary and A cationic mordant containing a tertiary amino group, a nitrogen-containing heterocyclic group and these quaternary cationic groups is used. In such a mordant, the acid dye described above was often found to diffuse to other layers, and it was considered to use a large amount of the mordant to eliminate the diffusion, but it is not possible to completely eliminate the diffusion. , The thickness of the layer to be contained was increased, and a new defect derived from that occurred.

Further, in the sensitizing material for printing plate making, a reduction operation using a reducing liquid is usually carried out for adjusting the density and gradation, but in this reducing liquid, a reducing agent is used. Since it contains a water-soluble iron complex, the cationic mordant described above has a drawback that it is electrostatically bound to the iron complex and causes yellow contamination by the iron complex.

Further, as another means for keeping a dye in a specific layer in a photographic light-sensitive material, JP-A-56-12639 and 55-55.
-155350, 55-155351, 52-
92716, 59-193447, 61-19
8148, 63-197943, 63-278.
38, 64-40827, European Patent 001
5601B1, 0276566A1 and WO88 / 04794, it is known to allow the dye to be present as a dispersed solid, but in combination with ultrafine silver halide has a high Dm and a reverted field. It is not known to satisfy the peculiar performance.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide the peculiar performance, tone reproducibility, required for the reversing sensitive material.
Silver halide photography that satisfies tone variability, spread & choke suitability, bag character suitability, high density of solid areas during underexposure in tone adjustment of halftone images, and can be handled in a bright room environment To provide a light-sensitive material.

[0007]

The above object of the present invention is to provide at least one photosensitive silver halide emulsion layer on a support, and to form a solid in the form of fine particles outside the emulsion layer with respect to the support. In a silver halide photographic light-sensitive material having a non-photosensitive hydrophilic colloid layer containing a dispersed dye, the average grain size of silver halide grains in the photosensitive emulsion layer is 0.15 μm or less, It was achieved by a silver halide photographic light-sensitive material characterized by containing at least 1 × 10 ⁻⁷ mol of a transition metal selected from the elements of Groups V to VIII of the Periodic Table per mol of silver.

In the present invention, dyes that can be solidly dispersed in a microcrystalline form are listed in Table I to WO88 / 04794 of International Patent WO88 / 04794.
Table X, (I) to (VII) shown below, and others are used.

[0009]

[Chemical 1]

[0010]

[Chemical 2]

[0011]

[Chemical 3]

(In the formula, A and A'may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, and X represents
And Y may be the same or different and each represents an electron-withdrawing group. R represents a hydrogen atom or an alkyl group, R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ may be linked to form a 5- or 6-membered ring. Good. R ₃ and R ₆ each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ each represent a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅ are linked. Represents a group of non-metal atoms required to form a 5- or 6-membered ring. L ₁ , L
₂ and L ₃ each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, and p is 0 or 1.
When p is 0, R ₃ represents a hydroxy group or a carboxyl group, and R ₄ and R ₅ represent a hydrogen atom.
B'represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group. Q represents a heterocyclic group. However, the compounds represented by the general formulas (I) to (VII) are dissociative compounds having a pKa in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 in one molecule. It has at least one group. The dyes used for the solid dispersion are specifically International Patent WO88 / 04794 and European Patents EP0274723A1 and 276,5.
66, 299,435, JP-A-52-92716.
No. 55-155350, No. 55-155351
No. 61-205934, No. 48-68623,
U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, and 41,304.
No. 29, No. 4040841, Japanese Patent Application No. 1-50874
Nos. 1-103751, 1-307363 and the like can be used. Dispersion method is also described in the above patent, but a method in which a dye is mechanically dispersed in water with a suitable dispersant by a ball mill, a sand mill, a colloid mill or the like, a dye in a dissociated state is applied in a salt form. After that, a method of obtaining dispersion fixation at the time of application by overcoating with acidic gelatin, making an alkaline aqueous solution by adjusting the pH at which the dye dissolves, and then decreasing the pH in the presence of protective colloid such as gelatin, followed by lowering the fine solid precipitate It is also possible to obtain a dispersed solid by dissolving the dye in a suitable solvent and then adding a poor solvent for the dye to cause precipitation. In the present invention, preferred dyes are 300-
It is a dye having an absorption maximum in the range of 500 nm. Specific examples of the dye are shown below. However, the present invention is not limited to the following compounds.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

[Chemical 14]

[0024]

[Chemical 15]

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18]

[0028]

[Chemical 19]

[0029]

[Chemical 20]

[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23]

[0033]

[Chemical formula 24]

[0034]

[Chemical 25]

The microcrystalline solid-dispersed dye in the present invention can be handled in a bright room where ultraviolet light is cut off, and outside the emulsion layer for the purpose of improving spreadability, chalk suitability and bag character suitability. To the non-photosensitive layer of. The coating amount of this dye is preferably 10 mg to 500 mg per square meter, and particularly preferably 50 to 300 mg. The dye used in the present invention is an international patent WO88 / 0.
4794, European Patent EP 0274723A1
No. 276, 566, 299, 435, JP-A Nos. 52-92716, 55-155350, 55.
-155351, 61-205934, 48-
68623, US Pat. Nos. 2,527,583, 348.
No. 6897, No. 37465939, No. 3933798
No. 4130429, No. 4040841, Japanese Patent Application No. 1-50874, No. 1-103751, No. 1-30.
It can be easily synthesized according to the method described in No. 7363 and the like.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention has an average grain size of 0.15.
It is preferably not more than μm, and particularly preferably 0.08 to 0.13 μm. Grains larger than 0.15 μm have a low covering power and are insufficient to obtain a high Dmax with a small amount of silver. Further, particles smaller than 0.08 μm are difficult to form particles having good monodispersity. In the present invention, the reaction temperature is 50 ° C. or lower, preferably 40 ° C. or lower as a mixing condition for preparing silver halide grains.
A silver potential of 70 mV or higher, preferably 300 mV to 500 mV, or 5,6-cyclopentane-4-hydroxy-1, under a condition of sufficiently high stirring speed for uniform mixing.
Good results can be obtained by adjusting at 80 mV to 120 mV in the presence of a stabilizer such as 3,3a, 7-tetrazaindene. The particle size distribution is basically not limited, but it is preferably monodisperse. The term "monodispersion" as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size, and more preferably within ± 20%. The silver halide grain of the present invention preferably has a regular crystal such as a cube and an octahedron, and a cube is particularly preferable.

The preferred transition metal used in the present invention is a transition metal coordination complex, which is a hexacoordination complex represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (In the formula, M is a transition metal selected from the elements of groups V to VIII of the periodic table. L is a bridging ligand. Y is oxygen or Sulfur, m = 0,1,2 and n = 0, -1,
-2 and -3. ) Preferred examples of L are halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyan. Nate ligands, acid ligands and aco ligands. When an aco 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.

Specific examples of the transition 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 ^-1 7. Re (NO) Cl ₅ ^-2 8. Os (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 -2 13. Os (NS) Cl (SCN) 4 - ² 14. ReCl ₆ ^-3 15. InCl ₆ ^-3 16. Re (NS) Cl ₄ (SeCN) ^-2

The above metal complex can be added to the silver halide during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10 ^-7 mol, preferably 10 ^{-6 to} 5 × 10 ^-4 mol, particularly 5 × 10 ^-6 to 1 mol per mol of silver halide. 2 x 10 ^-4
It is a mole. Moreover, you may use together the said transition metal. The distribution of the transition metal in the silver halide grain is not particularly limited, but it is preferable that the transition metal is more present outside the grain. The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is silver chlorobromide or silver chloroiodobromide containing 70 mol% or more of silver chloride. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific example is U.S. Patent No. 2,44
No. 8,060, British Patent 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins 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 or the like can be used.

A water-soluble dye may be used as a filter dye in the hydrophilic colloid layer or emulsion layer of the light-sensitive material produced by using the present invention, 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. Of these, 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, an active vinyl compound (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium Salts ((1-morpholino) carbonyl-3-
(Pyridinio) methanesulfonate, etc.), haloamidinium salts (1- (1-chloro-1-pyridinomethylene))
Pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. Among them, JP-A Nos. 53-41220, 53-57257, and 59-
The active vinyl compounds described in 162546 and 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferable.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (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 alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy salts, sulfo salts, phospho salts, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic primary surfactants. 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 can be used. Further, in order to prevent electrification, JP-A-60-80849 is used.
It is preferable to use the fluorine-containing surfactants described in No.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethylmethacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)
Acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or the like may be used alone or in combination, or a polymer having a combination of these with acrylic acid, methacrylic acid, or the like as a monomer component may be used. Gelatin is advantageously used as the condensing agent or protective colloid for 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 hydroxyethyl cellulose, carboxymethyl cellulose, 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 synthetic hydrophilic molecular substances such as a single or copolymer such as polyvinylpyrazole can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, potastyrene, polyethylene terephthalate paper, baryta coated paper,
Polyolefin coated paper or the like can be used.

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl are preferable. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. Examples of the dihydroxybenzene developing agent used in the present invention include 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 preferable. 1-phenyl-used in the present invention
As a developing agent for 3-pyrazolidone or its derivative, 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- There is pyrazolidone. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N
-(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 usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Also, dihydroxybenzenes and 1-phenyl-3-
When using a combination with pyrazolidones or p-amino-phenols, the former is 0.05 mol / l
It is preferable to use 0.5 mol / liter and the latter in an amount of 0.06 mol / liter 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 / sulfite
It is preferably at least liter, particularly at least 0.4 mol / liter. The upper limit is 2.5 mol / liter, especially 1.2.
It is preferable to be up to. Alkaline agents used to set the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate, and potassium silicate. Contains a buffer. As additives used in addition to the above components, boric acid, compounds such as borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol,
Organic solvents such as triethylene glycol, bimethylformamide, methyl cellosolve, bexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-
Mercapto compounds such as 5-sulfonic acid sodium salt,
Indazole-based compounds such as 5-nitroindazole, 5
-An antifoggant such as a benztriazole-based compound such as methylbenztriazole may be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, a water softener, a film hardener and the like may be contained. Particularly, JP-A-56-10624
The amino compounds described in No. 4 and the imidazole compounds described in JP-B-48-35493 are preferable from the viewpoint of promoting development or increasing sensitivity. In the developer used in the present invention, the compounds described in JP-A-56-24347 are used as the silver stain preventing agent, and the development unevenness preventing agent (JP-A-62-21).
2, 651), and the compounds described in JP-A-61-267759 can be used as dissolution aids. In the developing solution used in the present invention, boric acid described in JP-A-62-186259 and JP-A-60
-93433 sugars (eg saccharose), oximes (eg acetoxime), phenols 8
For example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like are used, and boric acid is preferably used.

The fixing solution is an aqueous solution containing a hardening agent (for example, water-soluble aluminum compound), acetic acid and dibasic acid (for example, tartaric acid, citric acid or salts thereof), if necessary, in addition to the fixing agent, and preferably , PH 3.8 or higher, 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 appropriately changed and is generally about 0.1.
Is about 5 mol / liter. 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 its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds are contained in an amount of 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like can be given. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. If desired, the fixer may contain preservatives (eg, sulfite, bisulfite),
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter. The fixing temperature and time are the same as in the case of development, and about 2
0 seconds to about 50 ° C and 10 seconds to 1 minute are preferred. In addition, anti-mold agents (for example, compounds described in "Bacterial and Antifungal Chemistry" by Horiguchi, compounds described in JP-A No. 62-115154), washing accelerators (sulfites, etc.), chelating agents, etc. may be used for washing water. May be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and the temperature is from about 20 ° C.
10 seconds to 3 minutes at about 50 ° C is preferred. About 40 ℃
It is carried out at about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes and 3 seconds. US Patent No. 302 for a roller-conveying type automatic processor
No. 5779, No. 3545971, and the like, and is referred to simply as a roller transport type processor in this specification. The roller transfer type processor has four steps of developing, fixing, washing and drying, and the method of the present invention also includes other steps (for example, stopping step).
However, it is most preferable to follow these four steps. Here, in the water washing step, water saving treatment can be performed by using a countercurrent water washing method of two or three stages. 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 developing solution used in the present invention is disclosed in JP-A-62-9193.
The replenishment system described in No. 9 can be preferably used. The silver halide photographic light-sensitive material of the present invention has a high Dma.
Since x is given, when the reduction processing is performed after the image formation, the high density is maintained even if the halftone dot area is reduced. There is no particular limitation on the reducing liquid used in the present invention, and for example, Mies, “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), etc., as well as JP-A Nos. 50-27543, 52-68429 and 55.
-17123, 55-79444, 57-10.
140, 57-142639, JP-A-61-61.
Those described in No. 155 and the like can be used. That is, as an oxidant, permanganate, persulfate, ferric salt, cupric salt, cerium salt, red blood salt, dichromate, etc. may be used alone or in combination, and further as 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 ethylenediaminetetraacetic acid salt, and a halogen such as thiosulfate, rhodan salt, thiourea or their derivatives. A reducing solution containing a silver halide solvent and, if necessary, an inorganic acid such as sulfuric acid is used. Typical examples of the reducer used in the present invention are so-called Farmer reducer, ethylenediaminetetraacetic acid ferric salt, potassium permanganate, ammonium persulfate reducer (Kodak R
-5), and a ceric salt reducing solution. The condition for the reduction treatment is generally 10 ° C to 40 ° C, particularly 15 ° C to 30 ° C.
It is preferable that the heating can be completed within a time of several seconds to several tens of minutes, particularly several minutes. By using the plate-making photosensitive material of the present invention, 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 through the non-photosensitive top layer containing the compound of the invention. Specifically, there are various methods. For example, the plate-making sensitizer is dipped in a reducing liquid to stir the liquid, or the reducing liquid is applied to the surface of the plate-making sensitizer with a brush or a roller. Methods are available.

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

[0048]

【Example】

Example 1 Preparation of Emulsion [Emulsion A] 5,6-Cyclopentane-4 kept at 40 ° C.
In a gelatin aqueous solution containing -hydroxy-1,3,3a, 7-tetrazaindene (5 x 10 ^-3 mol per mol of silver), an aqueous silver nitrate solution and 4 x 10 ^-5 mol per mol of silver were added.
An aqueous sodium chloride solution containing (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added simultaneously for 3 and a half minutes, and the potential during that period was controlled to 95 mV to prepare 0.08 μm of particles in the core. Then, 1.2 x 10 per 1 mol of silver and silver nitrate aqueous solution
^-Sodium chloride aqueous solution containing ⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added simultaneously for 7 minutes and the potential was controlled to 95 mV during that period to obtain an average particle size of 0.10 μm.
Of silver chloride cubic grains were prepared. [Emulsion B] Aqueous silver nitrate solution kept at 40 ° C. and 4 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per mol of silver
By simultaneously adding an aqueous solution of sodium chloride containing 4 minutes and controlling the potential during that time to 65 mV.
1.35 μm of core particles were prepared. Then, an aqueous solution of silver nitrate and 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh (H
_An aqueous sodium chloride solution containing ₂ O) Cl ₅ was added simultaneously for 8 minutes, and the potential was controlled to 65 mV during that period to prepare silver chloride cubic particles having an average particle size of 0.17 μm. [Emulsion C] In the same manner as in Emulsion A, cubic silver chloride particles having an average grain size of 0.10 μm and containing no transition metal were prepared.

Preparation of Coating Samples 5,6-Cyclopentane-4-hydroxy- was added to the above emulsion.
24 mg / m ^{2 of} 1,3,3a, 7-tetrazaindene, ethyl acrylate latex (average particle size 0.05 μm)
2-bis 770 mg / m ^2, the following compounds 3 mg / m ^2, as a hardening agent (vinylsulfonyl acetamide)

[0050]

[Chemical formula 26]

126 mg / m ^{2 of} ethane was added and coated on a polyester support so as to give silver of 3.0 g / m ² . The gelatin was 1.5 g / m ² . On top of this, as a lower layer of the protective layer, gelatin 0.8 g / m ² , lipoic acid 8 mg / m ² , C ₂ H ₅ SO ₂ SNa 6 mg / m ² , ethyl acrylate latex (average particle size 0.05 μm) 230 mg / m ² Further, 0.7 g / m ² of gelatin as the upper layer of the protective layer and the dyes shown in each table were coated on the above in a solid dispersion state. At this time, 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
m ² , 25 mg / m ^{2 of} sodium dodecylbenzenesulfonate as a coating aid, 20 mg of poly (degree of polymerization 5) oxyethylene nonylphenyl ether sulfate ester sodium salt
/ M ² , N-perfluorooctanesulfonyl-N-propylglycine potassium salt 3 mg / m ² were simultaneously applied to prepare a sample. The base used in this example has a back layer and a back protective layer having the following compositions. (The swelling rate on the back side is 110%.) (Back layer) Gelatin 170 mg / m ² Sodium dodecylbenzene sulfonate 32 mg / m ² Dihexyl-α-sulfosuccinate sodium 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 Dihexyl-α-sulfosuccinate sodium 20 mg / m ² sodium-dodecyl benzene sulfonate 67 mg / m ²

[0052]

[Chemical 27]

[0053]

[Chemical 28]

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 with a P-627FM printer (mercury) manufactured by Dainippon Screen Co., Ltd. through an optical wedge, and a developer LD-835 manufactured by Fuji Photo Film Co., Ltd. and an automatic processor FG8008RA were used. Was developed at 38 ° C. for 20 seconds, fixed, washed with water and dried. For these samples,
The following items were evaluated. 1) Sensitivity: The reciprocal of the exposure amount that gives a density of 0.1, and Sample No. 1 was set to 100, and the relative sensitivity of this sample was shown. 2) Dmax, Dmax (-1%); a film (halftone dot original document) on which a halftone image was formed was fixed on an adhesive base with an adhesive tape, and the protective layer of each film sample and the halftone original document were The maximum blackening densities when exposed so that 50% halftone dot areas are 50% and 49% halftone dot areas on the film sample are Dmax, respectively.
Dmax (-1%). 3) Gradation: (1.5-0.1) / {log (density 0.1)
Exposure amount) -log (exposure amount that gives a density of 1.5)} 4) Safelight property; Toshiba fading prevention fluorescent lamp (FLR4)
(0SW-DL-X NU / M) When irradiated with about 400 Lux and exposed, it is represented by the irradiation time of a fluorescent lamp in which the halftone dot, which is originally 50%, is thickened by 2%. 5) Spread & Choke: As shown in FIG. 1 of Japanese Patent Application No. 3-96072, the line width (μm) of a line image collapsed when an exposure amount returning to 1: 1 was given. As is clear from Table 1, the samples of the present invention have a hard toe gradation and a high Dmax,
It can be seen that this is a silver halide light-sensitive material that is suitable for spread and chalk and can be handled sufficiently in a bright room environment.

[0056]

[Table 1]

Example 2 Using the same sample as in Example 1, the developing solution was changed to the developing solution GR-D1 manufactured by Fuji Photo Film Co., Ltd., and the developing machine was changed to FG-710NH manufactured by Fuji Photo Film Co., Ltd. 38 It was developed at 20 ° C. for 20 seconds. The evaluation items are the same as in Example 1, and the results are shown in Table 2. As is clear from Table 2, even in the hybrid treatment, the sample of the present invention has a high toe gradation and a high Dma.
It can be seen that it is a silver halide light-sensitive material that is suitable for x, spread & chalk and can be handled sufficiently in a bright room environment.

[0058]

[Table 2]

Example 3 The sample used in Example 1 was used in the following prescription developing solution using an automatic developing machine FG-710NH manufactured by Fuji Photo Film Co., Ltd.
Development was performed at 8 ° C. for 15 seconds. The same evaluation as in Example 1 was performed, and the results are shown in Table 3. As is clear from Table 3, even in the rapid processing, the sample of the present invention has a hard toe gradation and a high Dm.
It can be seen that the silver halide light-sensitive material has ax, spread & choke suitability and can be sufficiently handled in a bright room environment.

[0060]

[Table 3]

Developer Formulation 1-Hydroxy-ethylidene-1,1-diphosphonic acid 2.0 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium carbonate 10.0 g Potassium sulfite 100.0 g Potassium bromide 10.0 g Diethylene glycol 20.0 g 5-methylbenzotriazole 0.2 g Hydroquinone 46.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g potassium hydroxide is added and water is added to make 1 liter. 1 liter pH is adjusted to 10.7. Example 4 Emulsions prepared at 35 ° C., 45 ° C. and 50 ° C. in the same manner as Emulsion A were designated as D, E and F, respectively. The average particle size is 0.
It was 08 μm, 0.14 μm and 0.18 μm. or,
_{(NH 4) 2 Rh (H} 2 O) Cl 5 and by changing the K ₂ Ru (NO) Cl ₅ Emulsion A,
Emulsions similar to D, E and F were prepared and designated as G, H, I and J. The same application and evaluation as in Example 1 were performed, and the results are shown in Table 4. As is clear from Table 4, the average particle size is 0.15
The sample of the present invention having a size of μm or less has a hard toe gradation and a high Dma.
It can be seen that it is a silver halide light-sensitive material that is suitable for x, spread & chalk and can be handled sufficiently in a bright room environment.

[0062]

[Table 4]

[0063]

INDUSTRIAL APPLICABILITY The present invention uses a solid disperse dye, ultrafine silver chloride and a transition metal coordination complex to impart spread and choke suitability of a light-sensitive material to be handled in a bright room, and also to Dmax and gradation. Could be raised.

Claims (2)

[Claims] 1. A non-photosensitive hydrophilic material having at least one light-sensitive silver halide emulsion layer on a support and containing a dye finely dispersed in solid form outside the emulsion layer with respect to the support. In a silver halide photographic light-sensitive material having a colloid layer, the average grain size of silver halide grains in the photosensitive emulsion layer is 0.15 μm or less, and at least 1 × 10 ⁻⁷ mol per mol of silver inside the silver halide grains. A silver halide photographic light-sensitive material containing a transition metal selected from the elements of Groups V to VIII of the periodic table. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide in the light-sensitive emulsion layer has a silver chloride content of 70 mol% or more.