JP3296856B2 - Silver halide photographic materials - 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 light-sensitive material for an ultra-bright light room mainly used in the printing and plate-making industry.

[0002]

2. Description of the Related Art In recent years, in the printing field, due to the complexity of printed matter and the development of scanners, there has been a demand for an improvement in the efficiency of a turning operation process. For this reason, a photographic film with a low sensitivity of about 10 ^-4 to 10 ^-5 has been developed as compared with a return film that has been conventionally used, and a return film that can be handled in a bright room (under a white fluorescent lamp excluding ultraviolet rays). It is practically used as a film, that is, a light-sensitive material for a bright room. The performance required of such a light-room photosensitive material is that it can be handled for a long time in a bright room, has high sensitivity to a printer light source, and also has the conventional dark-room photosensitive material. The reason was to have a sufficient maximum density at a moderate or higher contrast. With respect to these performances, various techniques have been recently developed by those skilled in the art, and quite high levels have been achieved as in Japanese Patent Application No. 3-244910. Further, recently, in order to realize a more efficient plate making operation, it is required to shorten a vacuum contact step before exposure by a printer.

In order to improve the performance of shortening the vacuum contact step (hereinafter referred to as vacuum performance), it is effective to use a matting agent having a large particle size. However, thinning the silver halide emulsion layer locally or generating pinholes in order to reduce the amount of light during exposure increases the opaque time, which in turn reduces the efficiency of the plate making operation. Become. On the other hand, it is a fact known to those skilled in the art that when a hydrazine compound is added to a silver halide photographic light-sensitive material, a high-contrast image is obtained. The present inventors have confirmed that there is an effect of reducing this pinhole in the case of the above.

The addition of hydrazine compounds to silver halide photographic emulsions and developers is disclosed in US Pat. No. 3,730,7.
No. 27 (developing solution in which ascorbic acid and hydrazine are combined) and 3,227,552 (hydrazine is used as an auxiliary developing agent for directly obtaining a positive color image), and 3,386,831 (Containing β-monophenylhydrazide of an aliphatic carboxylic acid as a stabilizer for silver halide light-sensitive materials), 2,419,975, and Mees, "The Theory of Photographic process", 3rd ed. (1966), page 281 and the like.

[0005] Among them, in particular, US Patent No. 2,41
No. 9,975 discloses that a high contrast negative image is obtained by adding a hydrazine compound. That is, when a hydrazine compound is added to a silver chlorobromide emulsion and developed with a developer having a high pH such as 12.8, extremely hard photographic characteristics having a gamma (γ) exceeding 10 can be obtained.
Has been described. However, a strong alkaline developer having a pH close to 13 is easily oxidized by air, is unstable, and cannot withstand long-term storage or use.

In contrast, US Pat. No. 4,168,9
No. 77, No. 4,224,401, No. 4,243,73
No. 9, 4,269,929, 4,272,614
Nos. 4,323,643 and the like, disclose silver halide photographic light-sensitive materials which provide extremely hard negative photographic characteristics using a stable developing solution. It is known that nitrogen gas is generated during the development process, and this gas collects in the film to form bubbles, which may damage a photographic image.

Therefore, for the purpose of reducing the generation of air bubbles and at the same time lowering the cost of the production of photosensitive materials, hydrazine which is hard and has a sufficient maximum density even with a small amount of addition, and which is less likely to cause uneven development and sand fog. A silver halide photographic light-sensitive material containing a compound is disclosed in JP-A-62-178246 and JP-A-62-178246.
-180361, 62-275247, 63-63
253357.

The present inventors have found that when the above hydrazine compound is added to a silver halide photographic light-sensitive material, a high-contrast image can be obtained without impairing the image due to nitrogen gas, and even when a relatively large matting agent is used, pinholes can be obtained. Has been confirmed to be less likely to occur. However, in order to prevent deterioration of image quality due to irradiation, a dye which lowers the sensitivity of the photosensitive silver halide emulsion is contained in the photosensitive emulsion layer or other hydrophilic colloid layers, as in general light-sensitive materials for bright rooms. If you do, the light will not go around the shade of the large matting agent because irradiation is prevented,
It has been found that even if the hydrazine compound is contained, a non-developed portion remains and pinholes are frequently generated again. However, when no dye is contained, sharpness of an image may be impaired due to deterioration of image quality due to irradiation, and measures have been required. However, no means for sufficient improvement has been reported yet.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which is hard and has a sufficient maximum density and which can be handled for a long time in a bright room.

Another object of the present invention is to provide a silver halide photographic material having excellent vacuum performance.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having few pinholes and high image sharpness.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide at least 90 mol% of silver chloride on a support and 5 × 10 ^-7 to 2 × 10 ^-4 mol of aqueous solution per mol of silver halide. Having at least one photosensitive layer having silver halide grains containing a hydrophilic rhodium salt, and wherein the photosensitive layer or another hydrophilic colloid layer has a compound represented by the following chemical formula (3); A matting agent having an average particle size of less than 5.5 μm per square meter containing 5 to 50 mg of a matting agent in a layer above the photosensitive layer as viewed from the support. This is achieved by a silver halide photographic material characterized in that substantially no dye which lowers the sensitivity of the light-sensitive emulsion is contained in any layer on the side having the following.

The size of the matting agent used in the present invention has an average particle size of less than 5.5 microns. Preferably, it is 1 micron or more and less than 5.5 microns. There are no restrictions on the material such as silica-based and polymer-based materials, and the particle size distribution may be uniform or variable. Preferably not more than 10% of the particles. The particles may be either regular or irregular. In the case of non-circular particles, the particle size is represented by the diameter when the volume is converted into a spherical shape.

The addition amount of the matting agent is 5 per square meter.
５０50 mg may be used alone or in combination of several kinds. The method of adding these matting agents is not particularly limited, but it is preferable to uniformly disperse them in a suitable solvent, for example, water or methanol, and then add them to the coating solution. The matting agent of the present invention is added to a layer above the photosensitive layer as viewed from the support. It may be added in a plurality of layers. Most preferably, it is added to the outermost layer.

[0015]

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Wherein Ar represents an aryl group;
R represents a group represented by —OR ₁ , or —N (R ₂ )
Represents a group represented by (R ₃ ). R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ and R ₃ are
Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted pyridinium group. Further, R ₂ and R ₃ may be linked to each other to form a ring. ]

[0017]

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In the formula, R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or an alkylthio group. , R4 and R5 may together form a 5- or 6-membered ring. However, the total number of carbon atoms of R ₄ and R ₅ is 3 or more. R ₇ represents a hydroxy group or a mercapto group. ]

In the chemical formula 3, the aryl group represented by Ar is specifically a phenyl group or a naphthyl group which may have a substituent, and examples of the substituent include an alkyl group, Aryl group, hydroxyl group, halogen atom, alkoxy group, alkylthio group, aryloxy group, alkenyl group, amino group, acylamino group, sulfonamide group, alkylideneamino group, ureido group, thiourea group, thioamide group, heterocyclic group, or These combinations may be mentioned.

Further, Ar may have a ballast group incorporated therein which is practically used in immobile photographic additives such as color couplers. The ballast group is a group having eight or more carbon atoms and relatively inactive to photographic properties, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group and the like.

In Formula 3, R represents a group represented by —OR ₁ or a group represented by Formula 5.

[0022]

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R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group.

R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a pyridinium represented by the following formula: Represents a group. Also, R
₂ and R ₃ may be linked to each other to form a ring.

[0025]

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R ₈ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group. R ₉ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. X ^- represents an anion.

Specific examples of the compound represented by Chemical Formula 3 are shown below. However, the present invention is not limited to the following compounds.

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In the light-sensitive material of the present invention, the compound represented by Chemical formula 3 is preferably contained in a silver halide emulsion layer, but may be contained in another hydrophilic colloid layer. Since the content of the compound of formula 3 of the present invention in the layer depends on the characteristics of the silver halide emulsion to be used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range. A range of about 5 × 10 ^-6 to 8 × 10 ^-2 moles per mole of silver in the silver halide emulsion is practically useful, more preferably a range of 5 × 10 ^-5 to 1 × 10 ^-2 moles. Is good.

In the present invention, the tetrazaindene compound represented by the formula (4) is a 4-hydroxy or 4-mercapto-compound having a total of 3 or more carbon atoms in the substituents at the 5- and 6-positions.
1,3,3a, 7-tetrazaindene.

Specific examples of the compound represented by Chemical Formula 4 are shown below. However, the present invention is not limited to the following compounds.

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In the light-sensitive material of the present invention, the compound represented by Chemical formula 4 is preferably contained in a silver halide emulsion layer, but may be contained in another hydrophilic colloid layer. Since the content of the compound of formula 6 of the present invention in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content may vary over a wide range. A range of about 6 × 10 ^{-6 to} 6 × 10 ^-2 moles per mole of silver in the silver halide emulsion is practically useful, more preferably a range of 2 × 10 ^-4 to 4 × 10 ^-2 moles. Is good.

On the other hand, the addition of a tetrazaindene compound to a silver halide photographic light-sensitive material is called "photochemical".
(Photo Kogyo Publishing Co., Ltd.) and other techniques known to those skilled in the art. Further, the technique of adding a hydroxytetrazaindene compound to a silver halide photographic emulsion containing a hydrazine compound is disclosed in Showa 53-8471
4, No. 64-65541. However, all of the results are obtained when a hydrazine derivative different from that of the present invention is used, and further exhibit effects different from those of the present invention.

That is, the effect of the present invention is to provide a photographic light-sensitive material which does not substantially contain a dye which lowers the sensitivity of a light-sensitive emulsion in any layer having a light-sensitive layer with respect to the support. Is expressed only by a combination of a matting agent having a size of less than 5.5 microns, a hydrazine compound represented by the formula (3) and a specific tetrazaindene compound represented by the formula (4) in the present invention (4 commonly used in the photographic industry).
The effects of the present invention cannot be obtained with -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. ), Which is a completely new effect not expected from the prior art.

The silver halide used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention may be silver chloride, silver chlorobromide having at least 90 mol% of silver chloride, silver chlorobromoiodide,
Silver chloroiodide can be used. Preferably, silver chloride or silver chlorobromide of 5 mol% or less of silver bromide or
Silver chloroiodide of 1 mol% or less of silver iodide is preferred. The form, crystal habit, size distribution, etc. of the silver halide grains are not particularly limited,
It is preferable that the average particle diameter is 0.1 to 0.4 μm and 90% or more of all particles have a particle diameter in a range of ± 10% of the average particle diameter. The method for preparing the silver halide emulsion may be any of known methods such as forward mixing, reverse mixing, and simultaneous mixing.

As the water-soluble rhodium salt used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, conventionally known water-soluble salts are used. Typically, rhodium monochloride, rhodium dichloride, rhodium trichloride and the like are used. Chloride, rhodium ammonium chloride and the like are used.
In general, the water-soluble rhodium salt is preferably used at the time of silver halide precipitation or physical ripening, but may be at any time thereafter. The effective amount of the water-soluble rhodium salt is in the range of 5 × 10 ⁻⁷ to 2 × 10 ⁻⁴ mol per mol of silver halide, preferably 1 mol per mol of silver halide.
The range is preferably from × 10 ^-6 to 1 × 10 ^-4 mol.

In addition to the rhodium salt, a salt of a noble metal such as an iridium salt, or an iron compound such as an erythrocyte may be present at the time of physical ripening or nucleation of silver halide grains.

The emulsion after the physical ripening was desalted,
It is preferable that the coating is performed by adding a necessary additive, but the desalting treatment can be omitted.

As a binder or protective colloid which can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer, etc. of the light-sensitive material of the present invention, it is advantageous to use gelatin. Sex 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 Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, lime-processed gelatin, acid-processed gelatin, Bull. Soc. Sci. Phot. Japan, No. 16, P30 (19)
Enzyme-treated gelatin as described in 66) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing the photographic performance. . The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds,
Dioxane derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds, active halogen compounds (2,4
-Dichloro-6-hydroxy-S-triazine, etc.),
Etc. can be used alone or in combination.

In the photographic light-sensitive material used in the present invention, a dye known to those skilled in the art can be contained in the backing layer for the purpose of preventing image quality deterioration due to halation. In addition, on the emulsion layer side, as described in the claims,
Any layer is substantially free of dyes that reduce the sensitivity of the emulsion. As used herein, dye refers to any dye known to those skilled in the art for anti-irradiation. Substantially not containing means not containing to the extent that the effect of the present invention is impaired, and it can be contained in a trace amount to such an extent that the effect is not impaired. The degree is
It depends on the spectral absorption and molar extinction coefficient of the dye.
It can contain up to 10 mg per square meter.

Further, the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic properties (for example, Surfactants for various purposes such as development acceleration, high contrast, and sensitization. For example, nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surfactant containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfate group, a phosphate group, such as an alkyl carboxylate, an alkyl sulfate, an alkyl phosphate, etc. Agents; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates; heterocyclic quaternary ammonium salts such as aliphatic or aromatic quaternary ammonium salts, pyridinium and imidazolium What cationic surfactant can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefins, styrene and the like alone or in combination, or acrylic acid,
A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Any support known to those skilled in the art can be used for the photographic light-sensitive material used in the present invention. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (for example, polyethylene and polypropylene) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating by a known method as necessary.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or a pH 13 described in US Pat. No. 2,419,975 can be used.
It is not necessary to use a highly alkaline developer close to the above, and a stable developer can be used. That is, the silver halide photographic light-sensitive material of the present invention can use a developer sufficiently containing (especially, 0.15 mol / l or more) a sulfite ion as a preservative, and has a pH of 9.5 or more. Especially 10.5-1
With the developer of 2.3, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. Other developers include pH buffers such as sulfites, carbonates, borates, and phosphates of alkali metals, bromides, iodides, and organic antifoggants (particularly preferably
(Nitroindazoles or benzotriazoles), or a development inhibitor or an antifoggant. If necessary, a water softener, a dissolution aid, a color tone, a development accelerator, a surfactant, an antifoaming agent, a hardening agent, an antifouling agent for silver (eg, 2-mercaptobenzimidazoles) of a film, etc. May be included. Specific examples of these additives are described in Research Disclosure 176 No. 1
7643 and the like.

In the present invention, a method may be employed in which a developing agent is incorporated in a photosensitive material and the photosensitive material is processed with an alkaline activator solution. (JP-A-57-129436, 57-129433, 57-129434, and 5)
7-129435, U.S. Pat. No. 4,323,643). The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. It is preferable to use an automatic developing machine for photographic processing. In the present invention, the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is reduced to 60 seconds to 120 seconds.
Even if it is set to seconds, a photographic characteristic of a sufficiently high contrast negative gradation can be obtained.

[0146]

【Example】

Example 1 A gelatin silver chloride emulsion containing 6.4 × 10 ⁻⁶ mol / mol Ag of rhodium dichloride, which is composed of cubic crystals having an average particle size of 0.13 μm, was prepared by a double jet method, and the flocculation method was used. desalination, water washing, redissolved emulsion was divided, the present invention represented hydrazine compound of the invention 3 of shown in Table 1 and comparative compounds as of 107 2 × 10 ^-3 mol / mol Ag, with reduction 6 6 × 10 ⁻³ mol / mol Ag as a tetrazaindene compound and a comparative compound, and 4 × 10 ⁻³ mol / mol Ag for 1-phenyl-5-mercaptotetrazole, 2-hydroxy-4,6- after adding dichloro-1,3,5-triazine sodium salt, a surfactant of 109, backing (Hoechst oxonol yellow 200 mg / m ^2, hardeners, surfactants Sexual agent, with silver nitrate in the matting agent gelatin solution containing) already polyethylene terephthalate film 5
g / m ² and gelatin at 3 g / m ² .

[0147]

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[0148]

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[0149]

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As a protective layer, gelatin 1 g / m 2
² , a surfactant of the formula, 2-hydroxy-4,6-
In a solution containing dichloro-1,3,5-triazine sodium salt, as a matting agent, Siloid 3 manufactured by Fuji Devison Co., Ltd.
08 (average particle size of 3.5 microns) was applied so as to be 30 mg / m ² .

Further, as shown in Table 1, oxonol yellow of Hoechst Co., Ltd.
A sample to which g / m ^{2 was} added was also prepared as a comparative example.

These films were used as a light room printer (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.).
To perform solid black exposure at an exposure amount such that a 50% screen becomes 52%, and a developing solution having the following composition is developed at 38 ° C. for 20 seconds.
Fixing, washing and drying. In this processing, an automatic developing machine (LD-221QT, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. The obtained solid black image is placed on a light table for 10 minutes.
Observation was performed using a loupe, and the state of occurrence of pinholes was evaluated on a three-point scale with the best level being 3. (3: Good, 2: Slight occurrence, but no practical problem, 1: Pinholes frequently occur and cannot be used)

In order to evaluate the vacuum performance,
Under the condition of 80% relative humidity, the above-mentioned printer is exposed to the same exposure amount through the 50% flat screen original (after 8 seconds of evacuation), processed by the same method, and printed in the obtained halftone image. I checked for blur.

Further, in order to evaluate the sharpness of the image, a negative having a width of 20 μm with the same exposure amount and
And exposed through a positive line original, processed in the same manner, observed with a 100 × loupe, and evaluated as Δ ×.

<Developer> Hydroquinone 50.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.3 g Sodium hydroxide 18.0 g 5-Sulfosalicylic acid 55.0 g Potassium sulfite 110.0 g EDTA · 2Na 1 0.0 g potassium bromide 10.0 g 5-methylbenzotriazole 0.4 g 2-mercaptobenzoimidazole-5-sulfonic acid 0.2 g sodium 3- (5-mercaptotetrasole) benzenesulfonate 0.2 g sodium toluenesulfonate 8. Add 0 g water and adjust to pH 11.8 with 1 l potassium hydroxide.

Table 1 shows the results.

[0157]

[Table 1]

From the results shown in Table 1, the pinholes were less generated and the vacuum performance was inferior only in the samples claimed in the present invention, and there was no burning blur caused by the generation of gas during development. It can be seen that an image with good sharpness can be obtained. On the other hand, in the comparative example to which the hydrazine compound shown in Chemical formula 108 was added, the image was blurred, and when the tetrazaindene compound of Chemical formula 4 was not included or when Chemical compound 108 of Comparative example was added, the sharpness of the image became poor. ing. Further, when a dye which lowers the sensitivity of the photosensitive emulsion is added to the emulsion layer or the overlayer, pinholes are frequently generated.

Example 2 A gelatin silver chloride emulsion containing 6.4 × 10 ⁻⁶ mol / mol Ag of rhodium dichloride, consisting of cubic crystals having an average particle size of 0.13 μm, was prepared by the double jet method. The emulsion, which was desalted, washed with water, and re-dissolved, was divided by a filtration method, and the hydrazine compound of Formula 88 was separated into 2 × 1
0 ^-3 mol / mol Ag, of 100 tetrazaindene compound of 6 × 10 ^-3 mol / mol Ag, further 1-phenyl-5
4 × 10 ⁻³ mol / mol A of mercaptotetrazole
g, 2-hydroxy-4,6-dichloro-1,3,5-
Triazine sodium salt, a surfactant of Chemical formula 109 was added, and a back coat (Oxonol Yellow of Hoechst Co., Ltd.
A gelatin solution containing 00 mg / m ² , a hardener, a surfactant and a matting agent) was coated on silver terephthalate film with silver nitrate at 5 g / m ² and gelatin at 3 g / m ² .

On top of this, gelatin 1 g / m 2 was used as a protective layer.
² , a surfactant of the formula, 2-hydroxy-4,6-
In a liquid containing dichloro-1,3,5-triazine sodium salt, as a matting agent, A: Syloid 244 (average particle size: 1.8 μm) manufactured by Fuji Devison Co., B: Polystyrene beads (average particle size: manufactured by Nippon Synthetic Rubber Co., Ltd.) 3.2 μm), C: Syroid 308 (average particle diameter 3.5 μm) manufactured by Fuji Devison, D: Syloid 404 (average particle diameter 5.2 μm) manufactured by Fuji Devison, E: Syloid 162 manufactured by Fuji Davison (Average particle diameter of 5.5 microns) in the amount shown in Table 2 and applied.

These samples were evaluated in the same manner as in Example 1. Table 2 shows the results.

[0162]

[Table 2]

From the results shown in Table 2, it can be seen that pinholes are less generated only in the samples falling within the scope of claims of the present invention, and that there is no blurring due to poor vacuum performance. On the other hand, in the case of the matting agent having a particle size of 5.5 μm, pinholes are frequently generated and cannot be used with any amount of addition. Further, even with a matting agent having a particle size within the range of the present invention, if the amount is less than the amount specified in the present invention, the vacuum performance is poor, and if it is too large, pinholes occur frequently. Further, there is no difference between the material of the matting agent and that of the silica or polymer. As described above, from the results of Tables 1 and 2, it is understood that the combination of the present invention is unique and cannot be expected from the prior art.

[0164]

According to the present invention, a negative-working silver halide having a high contrast, a sufficient maximum density, a long-term use in a bright room, an excellent vacuum performance, a small number of pinholes, and a high image sharpness. A photographic light-sensitive material is obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-179928 (JP, A) JP-A-3-13934 (JP, A) JP-A-2-54249 (JP, A) 293657 (JP, A) JP-A-6-256044 (JP, A) JP-A-63-282731 (JP, A) JP-A-4-306643 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) G03C 1/06 501 G03C 1 / 32,1 / 34

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein at least 90 mol% of silver chloride is present on the support, and 5 × 10 ⁻⁷ to 2 × per mol of silver halide.
A compound having at least one photosensitive layer having silver halide grains containing 10 ^-4 mol of a water-soluble rhodium salt, and having the photosensitive layer or another hydrophilic colloid layer represented by the following chemical formula: And a layer above the photosensitive layer as viewed from the support, containing from 5 to 50 mg of a matting agent having an average particle size of less than 5.5 microns per square meter. A silver halide photographic light-sensitive material characterized in that any layer on the side having the light-sensitive layer does not substantially contain a dye which lowers the sensitivity of the light-sensitive emulsion. Embedded image [Wherein, Ar represents an aryl group, and R represents -OR
Represents a group represented by the group represented by ₁ or _{-N, (R 2) (R} 3). R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryl group. R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted pyridinium group. Further, R ₂ and R ₃ may be linked to each other to form a ring. ] In Chemical Formula 2, R _4, R _5, R _6, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an alkylthio group, R ₄ And R ₅ may together form a 5- or 6-membered ring. However, the total number of carbon atoms of R ₄ and R ₅ is 3 or more. R ₇ represents a hydroxy group or a mercapto group. ]