JP2890274B2 - High-contrast silver halide photosensitive material for bright rooms - 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 used in the field of photolithography,
More specifically, the present invention relates to a returnable silver halide photographic light-sensitive material that can be handled in an environment that can be substantially called a bright room and can form a hard negative image.

[0002]

2. Description of the Related Art Among photoengraving processes in the field of print duplication, in particular, in the process of collecting and reversing plates, work is performed in a brighter environment to improve work efficiency and work environment. In addition, a silver halide photosensitive material for plate making that can be handled in an environment that can be substantially called a bright room is provided. As a method of producing a light-sensitive material that can be handled in a bright room by lowering the sensitivity to visible light, rhodium salts, iridium salts,
A method using an emulsion to which an inorganic or organic desensitizer such as pinacryptol yellow or phenosafranine is added is well known. 0.05 to 0.5 without chemical sensitization
A method in which a rhodium salt and / or an organic desensitizer is used in a μm fine grain silver chloride or fine grain silver chlorobromide emulsion is preferably used. Furthermore, in combination with these emulsions,
For the purpose of adjusting the sensitivity and imparting safelight safety, a method of incorporating a yellow dye or an ultraviolet absorbing dye into a photosensitive material is used.

On the other hand, the photosensitive material used in the plate-collecting and returning steps is required to improve the reproduction of line drawings and halftone images.
There is a need for an image part and a non-image part that have a high blackening density and have so-called ultra-high contrast photographic characteristics. In particular, a halftone dot image as a return document and a line image document are overlapped and exposed (so-called blank character image formation is performed).
In this case, there is a demand for a photosensitive material having good line drawing reproducibility (character quality without blank).

As a method of imparting ultra-high contrast photographic characteristics to a photosensitive material, a method of including a vitrazine derivative or a tetrazolium compound in the photosensitive material is known. The combination of the methods of causing the hydrazine derivative or the tetrazolium compound to contain in the material sometimes causes problems such as hindering the contrast enhancement effect of the hydrazine derivative or the tetrazolium compound or losing good line drawing reproduction performance.

[0005]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a reversible silver halide photographic material which can be handled under a bright safelight (substantially bright room) and has ultra-high contrast photographic characteristics. Is to provide. A second object of the present invention is to provide a photosensitive material that can be handled under a bright safelight (substantially a bright room) and has a good line drawing reproduction performance (character quality without blank).

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver chloride particle or silver chloride content of 80% adjusted in the presence of 1.times.10.sup.- ^{7 to} 5.times.10.sup.- ⁴ mole of rhodium salt per mole of silver. It has at least two silver halide emulsion layers comprising silver chlorobromide grains of not less than mol% and having different sensitivities, and the sensitivity of the underlying emulsion layer (located on the side closer to the support) is higher than that of the emulsion layer. Higher sensitivity than the emulsion layer located on the upper layer,
And at least one of the hydrophilic colloid layers other than the emulsion layer
This was accomplished by a silver halide photographic material containing a dye (preferably above the two silver halide emulsion layers) dispersed in fine particles in a layer. Further, when the hydrazine derivative or the tetrazolium compound is contained in the light-sensitive material to give super-high contrast photographic characteristics, the effect is remarkably exhibited when combined with the above-mentioned means.

The finely divided solid-dispersed dye used in the present invention is contained for the purpose of adjusting the sensitivity of the light-sensitive material in a bright room and imparting safelight safety.
(1) Do not diffuse from the added layer to other layers and adversely affect the photographic performance of the silver halide emulsion (for example, fog, gradation, latent image regression, etc.) (2) Photographic processing (3) No harmful coloring is left on the processed photographic material after processing, or it is eluted in the processing solution or washing water. (3) Excellent stability with time in solution or photographic material. It satisfies such performances as not fading. Since the solid disperse dye has insufficient solubility of the dye itself, it cannot exist in a molecular state in the added non-photosensitive colloid layer, and has a size that cannot be substantially diffused in the layer. It exists in the layer as a crystalline solid state.

[0008] These solid disperse dye compounds are listed in Tables I to X of International Patent Publication No. WO80 / 04,797 and the following general formulas (I), (II), (III), (IV) and (V). What is represented is used.

[0009]

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In the formula, A and A ′ may be the same or different, each represents an acidic nucleus, B represents a basic nucleus, and X and Y may be the same or different; 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,
Represents an acyl group or a sulfonyl group, and R ₁ and R ₂ may be linked to form a 5- or 6-membered ring; R ₃ and R ₆ each represent a hydrogen atom, an alkyl group, a hydroxy group, a carboxyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ are each a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅ are linked. Represents a group of non-metallic atoms necessary 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 are each 0,
Represents 1 or 2, p represents 0 or 1, and when p is 0, R ₃ represents a hydroxy group or a carboxyl group; and R ₄ and R ₅ represent a hydrogen atom. However, the general formula (I),
The compounds represented by (II), (III), (IV) and (V)
One molecule has at least one dissociable group having a pKa in the range of 4 to 11 in a mixed solution in which the volume ratio of water ethanol is 1: 1.

The solid disperse dye used in the present invention is 300
Those having an absorption maximum in the range of -500 nm are preferably used. Specific examples of the dye used in the present invention are shown below, but the present invention is not limited to these compounds.

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[0029]

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These dyes are described in International Patent WO 88/0.
4,794, European Patent EP 0274,723A
Nos. 1, 276,566 and 299,435, JP-A-52-92,716, and JP-A-55-155,350.
Nos. 55-155,351 and 61-205,934
No. 48-68,623, U.S. Pat. No. 2,527,5.
No. 83, No. 3,486,897, No. 3,746,53
Nos. 9, 3,933,798 and 4,130,429
No. 4,040,841 and the like and a method analogous thereto can be easily synthesized.

The preparation method is described in International Patent WO88 / 0
4,794, European Patent EP 0,276,566
No. A1, JP-A-63-197,945 and the like, a method of ball milling and stabilizing with a surfactant and gelatin, and dissolving a dye in an alkaline solution followed by p.
It is preferable to use a method of lowering H and precipitating. The solid disperse dye prepared by such a method can be added to a non-photosensitive hydrophilic colloid layer coating solution in a solid state.

The amount of the dye to be used in the present invention is preferably in the range of 10 to 500 mg / m ² , and more preferably 20 to 500 mg / m ^2.
A range of -300 mg is preferred.

The silver halide emulsion used in the present invention is:
A silver chloride emulsion or a silver chlorobromide emulsion having a silver chloride content of 80 mol% or more, and particularly preferably a silver chloride content of 90 mol%.
The above silver chlorobromide emulsion or pure silver chloride emulsion.

The silver halide emulsion of the present invention contains 1 × 10 ^-7 mol to 5 × 10 ^-4 mol, more preferably 1 × 10 ^-6 mol to 1 × 10 ^-4 mol of a water-soluble rhodium salt per mol of silver. Are used to form grains. Rhodium salts include rhodium trichloride and rhodium (III) hexachloride
And ammonium rhodium (III) hexachloride. If the added amount of rhodium salt is less than 10 ^-7 mol, safelight safety cannot be ensured, and
When added in an amount exceeding × 10 ⁻⁴ , the sensitivity becomes too low, and it is difficult to achieve high contrast with a hydrazine derivative or a tetrazolium compound.

The average grain size of the silver halide used in the present invention is preferably a fine grain of 0.5 μm, more preferably 0.3 μm or less. The particle size distribution is preferably as monodispersed as possible, and 90% or more of the total number of particles is preferably within ± 40% of the average particle diameter, more preferably ± 20%.
%. Silver halide grains preferably have regular crystals such as cubic and octahedral, but irregular (i.e.
It may have a crystalline form or a complex form of these crystalline forms.

The method of reacting the water-soluble silver salt (aqueous silver nitrate solution) with the water-soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. As one type of the double jet method, p in a liquid phase in which silver halide is formed is used.
A method of keeping Ag constant, that is, a control double jet method can also be used. Grains can also be formed using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. The control double jet method and the grain formation method using a silver halide solvent are effective means for producing a silver halide emulsion having a regular crystal form and a narrow grain size distribution.

As the silver halide emulsion of the present invention, an emulsion which has not been subjected to chemical sensitization is preferably used.

In the silver halide emulsion layer of the present invention, at least two types of silver halide emulsions having different sensitivities are used. The sensitivity of the lower emulsion layer is required to be higher than that of the upper emulsion layer in order to provide high contrast photographic characteristics. The difference in sensitivity between the lower emulsion layer and the upper emulsion layer is 0.05 to
It is 0.5 log E, more preferably 0.1 to 0.4 log E. For the sensitivity of each emulsion layer, coat each layer as a single layer,
It can be determined by developing. Silver halide emulsion layers with different sensitivities can be formed by changing the rhodium content, halogen composition, grain size, etc. of the silver halide emulsion grains used, or by additives adsorbing the silver halide grains to change the sensitivity. For example, a method of adding an antifoggant or the like is used.

In the present invention, a hydrazine derivative or a tetrazolium compound is preferably added to a light-sensitive material for the purpose of obtaining ultra-high contrast photographic characteristics.

As the hydrazine derivative used in the present invention, those represented by the following general formula (VI) are used. General formula (VI)

[0041]

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In the general formula (VI), the aliphatic group represented by A preferably has 1 to 30 carbon atoms, and is particularly straight-chain, branched or cyclic alkyl having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, the alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, and a sulfonamide group. For example, t-butyl group, n
-Octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group, tetrahydrofuryl group,
A morpholino group and the like can be given as examples.

In the general formula (VI), the aromatic group represented by A is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like. Among them, those containing a benzene ring are preferred.

Particularly preferred as A is an aryl group. The aryl group or unsaturated heterocyclic group of A may have a substituent. Representative substituents include linear,
A branched or cyclic alkyl group (preferably having 1 to 2 carbon atoms)
0), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably An amino group substituted by an alkyl group having 1 to 20 atoms), an acylamino group (preferably having 2 to 3 carbon atoms)
0), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms) and the like.

A may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. Can be. A may have a group incorporated therein for enhancing the adsorption on the surface of the silver halide grains. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups and the like, as described in U.S. Pat. Nos. 4,385,108 and 4,459,347.
JP-A-59-195,233 and JP-A-59-200,
No. 231, 59-201, 045, 59-20
Nos. 1,046, 59-201, 047, 59-2
Groups described in JP-A Nos. 01,048 and 59-201,049.

B is specifically a formyl group, an acyl group (acetyl group, propionyl group, trifluoroacetyl group,
Chloroacetyl group, benzoyl group, 4-chlorobenzoyl group, pyrvoyl group, methoxalyl group, methyloxamoyl group, etc., alkylsulfonyl group (methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.) ), An alkylsulfinyl group (such as a methanesulfinyl group), an arylsulfinyl group (such as a benzenesulfinyl group), a carbamoyl group (such as a methylcarbamoyl group and a phenylcarbamoyl group), a sulfamoyl group (such as a dimethylsulfamoyl group), and an alkoxycarbonyl group ( Methoxycarbonyl group, methoxyethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), sulfinamoyl group (methylsulfinamoyl group, etc.), alkoxysulfonyl group (methoxy, Shisuruhoniru group, ethoxysulfonyl group and the like), thioacyl group (methyl thio group, etc.), represents a thiocarbamoyl group (methyl thiocarbamoyl group) or a Hajime Tamaki (pyridine ring group). B
Is particularly preferably a formyl group or an acyl group.

R ₀ and R ₁ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a substituent such that the sum of the substituent constants of Hammett is -0.5 or more. Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more, or a linear or branched or A cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom,
Ether group, sulfonamide group, carbonamide group, hydroxyl group, carboxy group, sulfonic acid group)).
R ₀ and R ₁ are most preferably hydrogen atoms.

Specific examples of the compound represented by the general formula (IV) are shown below. However, the present invention is not limited to the following compounds.

[0049]

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[0050]

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[0051]

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[0052]

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The amount of the hydrazine derivative used in the present invention is preferably in the range of 5 × 10 ⁻⁷ mol to 5 × 10 ⁻² mol per mol of silver halide, and particularly preferably in the range of 1 × 10 ⁻⁶ mol to 1 × 10 ⁻ mol. A range of ² moles is preferred.

When the hydrazine derivative used in the present invention is contained in a photographic light-sensitive material, it is used as an aqueous solution when it is water-soluble, and when it is insoluble in water, it is an alcohol (for example, methanol or ethanol) or an ester (for example, ethyl acetate). And a solution of a water-miscible organic solvent such as ketones (for example, acetone) is added to the silver halide emulsion solution or the hydrophilic colloid solution. When it is added to a silver halide emulsion solution, the addition can be performed at any time from the start of chemical ripening of the emulsion to coating, but it is preferably performed after the completion of chemical ripening, and especially prepared for coating. It is preferably added to the prepared coating solution.

Examples of the tetrazolium compound used in the present invention include JP-A-52-18317 and JP-A-53-177.
Compounds described in Nos. 19 and 53-17720 and the like can be used, and typical compounds are those represented by the following general formula (VII)
And compounds represented by (VIII).

[0056]

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In the formula, R ₂ and R ₃ are each selected from a phenyl group (for example, phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group, etc.), thiazolyl group, benzothiazolyl group and triazyl group. R ₁₀ ,
R ₁₁ , R ₁₂ and R ₁₃ represent a phenyl group, and any of these may be a group that forms a metal chelate or a complex.

R ₄ is a phenyl group, a heterocyclic group (for example, a furyl group, a cyenyl group, a pyridoyl group, a quinolyl group, a benzoxazol group, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a mercaptomethyl group) ,
Mercaptoethyl group, etc.), hydroxyl group, carboxyl group or a salt thereof, carboxyalkyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), amino group (eg, amino group, ethylamino group, anilino group, etc.), mercapto group, nitro group represents a group selected from the group and a hydrogen atom, E is a radical selected from an alkylene group, an arylene group, aralkylene alkylene group, X ^- is n represents an anion represents 1 or 2. However, when the compound forms an inner salt, n is 1.

Next, specific examples of the tetrazolium compound used in the present invention will be shown, but the compounds that can be used in the present invention are not necessarily limited to these. (1) 2- (benzothiazol-2-yl) -3-phenyl-5-dodecyl-2H-tetrazolium-bromide (2) 2,3-diphenyl-5- (4-t-octyloxyphenyl) -2H- Tetrazolium chloride (3) 2,3,5-triphenyl-2H-tetrazolium (4) 2,3,5-tri (p-carboxyethylphenyl) -2H-tetrazolium (5) 2- (benzothiazole-2- Yl) -3-phenyl-5- (o-chlorophenyl) -2H-tetrazolium (6) 2,3-diphenyl-2H-tetrazolium (7) 2,3-diphenyl-5-methyl-2H-tetrazolium

(8) 3- (p-hydroxyphenyl) -5
-Methyl-2-phenyl-2H-tetrazolium (9) 2,3-diphenyl-5-ethyl-2H-tetrazolium (10) 2,3-diphenyl-5-n-hexyl-2H-tetrazolium (11) 5-cyano -2,3-diphenyl-2H-tetrazolium (12) 2- (benzothiazol-2-yl) -5-phenyl-3- (4-tolyl) -2H-tetrazolium (13) 2- (benzothiazole-2- Il) -5- (4-
Chlorophenyl) -3- (4-nitrophenyl) -2H
-Tetrazolium (14) 5-ethoxycarbonyl-2,3-di (3-nitrophenyl) -2H-tetrazolium (15) 5-acetyl-2,3-di (p-ethoxyphenyl) -2H-tetrazolium (16) 2,5-diphenyl-3- (p-tolyl) -2H-
Tetrazolium

(17) 2,5-diphenyl-3- (p-iodophenyl) -2H-tetrazolium (18) 2,3-diphenyl-5- (p-diphenyl) -2
H-tetrazolium (19) 5- (p-bromophenyl) -2-phenyl-3-
(2,4,6-trichlorophenyl) -2H-tetrazolium (20) 3- (p-hydroxyphenyl) -5- (p-nitrophenyl) -2-phenyl-2H-tetrazolium (21) 5- (3 4-dimethoxyphenyl) -3- (2-
Ethoxyphenyl) -2- (4-methoxyphenyl)-
2H-tetrazolium (22) 5- (4-dianophenyl) -2,3-diphenyl-2H-tetrazolium (23) 3- (p-acetamidophenyl) -2,5-diphenyl-2H-tetrazolium (24) 5-acetyl -2,3-diphenyl-2H-tetrazolium (25) 5- (flu-2-yl) -2,3-diphenyl-2
H-tetrazolium

(26) 5- (thien-2-yl) -2,3-
Diphenyl-2H-tetrazolium (27) 2,3-diphenyl-5- (pyrid-4-yl)-
2H-tetrazolium (28) 2,3-diphenyl-5- (quinol-2-yl)
-2H-tetrazolium (29) 2,3-diphenyl-5- (benzoxazole-
2-yl) -2H-tetrazolium (30) 2,3-diphenyl-5-nitro-2H-tetrazolium (31) 2,2 ', 3,3'-tetraphenyl-5,5'-
1,4-butylene-di-2H-tetrazolium (32) 2,2 ', 3,3'-tetraphenyl-5,5'-
p-phenylene-di- (2H-tetrazolium (33) 2- (4,5-dimethylthiazol-2-yl)-
3,5-diphenyl-2H-tetrazolium (34) 3,5-diphenyl-2- (triazin-2-yl) -2H-tetrazolium (35) 2- (benzothiazol-2-yl) -3- (4-
Methoxyphenyl) -5-phenyl-2H-tetrazolium

As described above, the tetrazolium compound used in the present invention can be either a diffusible tetrazolium compound or a non-diffusible tetrazolium compound when the silver halide of the present invention is used.
When a non-diffusible tetrazolium compound is used, a higher-contrast image can be obtained. Therefore, for example, when particularly excellent dot performance is required, it is relatively advantageous to use non-diffusible tetrazolium. The tetrazolium compound used in the present invention may be used alone or in combination. The tetrazolium compound used in the present invention is 1 × 10 ^{−3 to} 5 × 10 5 per mol of silver halide.
A range of ^-2 mol is preferably used.

With respect to other various additives and development processing methods used in the light-sensitive material of the present invention, for example, those described in the relevant portions of the following patents can be preferably used. 1 Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10; 2. Antifoggants Thiosulfinic acid compounds described in JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4, and JP-A 1-237538. 3 Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17. 4 Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to page 4, lower right Column, line 18. 5 Polymer latex, page 43, left column, line 43 to right column, line 11 of JP-B-2-28856. 6 Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1.

7. Binder JP-B-2-28856, page 17, left column, lines 25 to 42. 8 Matting agent, slip agent JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 9 Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10 Developing Solution and Developing JP-B-2-28856, page 18, left column, line 6 Method, page 19, left column, line 7.

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. Example 1 Preparation of Emulsions A and B An aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 7.times.10.sup.- ⁵ mol of ammonium hexachloride rhodium (III) per mol of silver were subjected to a double jet method at 40.degree. Gelatin concentration 1.5%,
(Containing 0.5 g / liter of sodium chloride) to produce monodispersed silver chloride grains having an average grain size of 0.15 μm k. After particle formation, after removing soluble salts by flocculation method well known in the art,
Gelatin was added, and 5 × 10 ⁻³ mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mol of silver was added as a stabilizer without chemical ripening. Emulsion A was prepared by adjusting the emulsion so that the gelatin contained in 1 kg of the emulsion was 50 g: silver 105 g. In the method for preparing Emulsion A, the addition amount of ammonium hexarhodate (III) was changed to 5 × 10 ⁻⁵ mol per mol of silver,
Otherwise, Emulsion B was prepared in the same manner as Emulsion A.

[Preparation of Coating Solution for Emulsion Layer and Protective Layer and Coating of the Coating Solution]
11 and VI-12, 2,2 as tetrazolium compounds
3,5-triphenyl-2H-tetrazolium (T in the table)
(Indicated as salt) in the amounts shown in Tables 1 to 3. Further, a dispersion of polyethyl acrylate was used as a polymer latex in an amount of 20 g per 1 mol of silver, and a hardening agent of 1,3-vinylfluonyl-2-propanol was added in an amount of 4 g / g of gelatin.
A 0 mg amount was added to prepare an emulsion layer coating solution, and a silver halide emulsion layer was coated on a polyethylene terephthalate film so as to have a coating amount of 3.6 g / m ² in one or two layers. Further, a gelatin solution to which a dye was added as shown in Tables 1 to 3 was coated as a protective layer on the emulsion layer. In this protective layer, gelatin was 1.0 g / m ² , polymethyl methacrylate having an average particle size of 2.5 μm was 50 mg / m ² , sodium dodecylbenzenesulfonate was used as a coating aid, and N-PAR was used as a charge control agent. Fluoroctanesulfonyl-N-propylbricine potassium salt was included.

[0068]

[Table 1]

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[Table 2]

[0070]

[Table 3]

[Sensitometric evaluation of samples] Each of the prepared samples was passed through an optical wedge to obtain a PNP manufactured by Dainippon Screen Co., Ltd.
After exposure with a -627FM type printer, the sample No.
For samples 1 to 30, the developer (a) was used for 38
The development was performed at 20 ° C. for 20 seconds, and the samples Nos. 31 to 40 were developed using the developer (b) for 28 ° for 30 seconds, followed by fixing, washing, and drying. The relative sensitivity was determined as the reciprocal of the exposure amount giving a density of 1.5,
The gradation was evaluated as an average gradation γ between 0.3 and 3.0 in the density of the characteristic curve.

[Formulation of developer (a)] Hydroquinone 45.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 5-Sulfosalicylic acid 45.0 g Boric acid 25.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium salt 1.0 g Potassium bromide 6.0 g 5-methylbenzotriazole 0.6 g n-butyl-diethanolamine 15.0 g Add water and add 1 liter (pH = 11.6)

[Developer (b) Formula] Hydroquinone 15.1 g Anhydrous potassium carbonate 60.4 g Potassium sulfite 51.7 g Ethylenediaminetetraacetic acid disodium salt 0.8 g Sodium bromide 2.2 g 5-methylbenzotriazole 0.13 g 1 -Phenyl-3-pyrazolidone 0.5 g 1-phenyl-5-mercaptotetrazole 0.02 g 5-nitro-indazole 0.1 g Diethylene glycol 98.0 g Water was added to add 1 liter (pH = 10.5)

[Evaluation of Safelight Safety of Samples] In order to evaluate the safelight safety of each sample, a test was performed for 2 minutes under 300 lux of a Toshiba anti-fading fluorescent lamp (FLR40SW-DL-X NU / M). After standing for 60 minutes, development processing was performed under the same conditions as the above-mentioned processing, and the limit irradiation time at which the fog value began to increase was determined.

[Evaluation of sample character image quality] In order to evaluate the sample character image quality, an original “transparent pasting base / line image positive image” having a configuration described in FIG. 1 of Japanese Patent Publication No. 2-28,856 was used. Film (line drawing manuscript) / transparent pasting base / film on which a halftone image is formed (halftone manuscript) in this order "is prepared, and the manuscript and the emulsion surface of each sample are prepared. , P-627FM
The image was exposed with a printer and developed. The exposure time of each sample was determined so that a halftone dot original portion having a halftone dot area ratio of 50% was image-formed on each sample as a halftone dot having a halftone dot area ratio of 50%. At this time, it was evaluated how many microns of blank characters were formed on each film sample as characters having a line width of 100 μm on the line drawing original. It can be said that the closer the line width of the blank character is to 100 μ, the better the quality of the blank character.

Tables 4 to 6 show the obtained results.

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[Table 4]

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[Table 5]

[0079]

[Table 6]

First, samples Nos. 1 to 10 containing no hydrazine derivative and tetrazolium compound were Nos. 3, 4, and 8 to which the water-soluble dye (a) was added.
No. 5, to which the solid disperse dye was added,
Samples 6, 9, and 10 have better safelight safety,
The width of the blank characters is also wide. Among them, especially the N according to the present invention
o. The sample No. 9 is excellent in both blank letters and safelight safety.

Next, the evaluation results of the samples of Nos. 11 to 40 containing the hydrazine derivative and the tetrazolium compound show that the γ value is large and the line width of the blank characters is wide. Compared to the sample to which (a) was added, the sample to which the solid disperse dye was added was
Good results were obtained for both the blank character and the safelight property. Among them, Sample Nos. 19, 27, and 2 according to the present invention
Nos. 9, 30, and 39 have safelight safety of 40 minutes or more and have a wide character line width.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification symbol FI G03C 1/83 G03C 1/83 (58) Investigated field (Int.Cl. ⁶ , DB name) G03C 1/825-1/83 G03C 1/035 G03C 1/06 G03C 1/36 G03C 1/46 G03C 1/83

Claims (2)

(57) [Claims] 1. The method according to claim 1, wherein 1 × 10 ^-7 per mol of silver is provided on the support.
At least two silver halide emulsion layers having different sensitivities each comprising silver chloride grains or silver chlorobromide grains having a silver chloride content of 80 mol% or more prepared in the presence of about 5 × 10 ^-4 mol of a rhodium salt; Silver halide photographic material having
The sensitivity of the lower emulsion layer (located closer to the support) is higher than the sensitivity of the upper emulsion layer, and the sensitivity of the hydrophilic colloid layer other than the emulsion layer is higher. A silver halide photographic light-sensitive material for a light room, characterized in that at least one layer contains a dye solid-dispersed in fine particles. 2. The light-sensitive silver halide photographic material of claim 1, wherein the silver halide emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative or a tetrazolium compound.