JP3126260B2 - 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 material, and more particularly to a light room photographic material mainly used in the printing and plate making industry.

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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 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. Furthermore, in order to enable long-term handling in a bright room, that is, to minimize the sensitivity to white fluorescent light excluding ultraviolet light, and to provide a high contrast and a sufficient maximum density, silver chloride in a silver halide emulsion is used. Increase the proportion (or 100% silver chloride)
The use of a fine grain emulsion is a technique often used by those skilled in the art. However, this method promotes the elution of silver halide into the developing solution, and causes silver staining of the developing tank, the developing rack, and the photosensitive material processed therein in the automatic developing machine. It is known in the art that other methods have a sufficient maximum density at a high contrast level equal to or higher than that of a conventional photosensitive material for a dark room as follows.

In the art, a special developing solution called a lith developing solution has been used to provide a high contrast and a sufficient maximum density. The squirrel developer contains only hydroquinone as a developing agent and uses a sulfite as a preservative in the form of an adduct with formaldehyde so as not to impair its infectious developability, and the concentration of free sulfite ions is extremely low. .
Therefore, the squirrel developer has a serious disadvantage that it is extremely susceptible to air oxidation and cannot withstand storage for more than three days.

On the other hand, in order to obtain a sufficient maximum density at a high contrast using a more stable developer, US Pat.
4,401, 4,168,977, 4,16
6,742, 4,311,781, 4,27
2,606, 4,221,857, 4,24
There is a method using a hydrazine derivative described in 3,739 or the like. According to this method, a high concentration of sulfite can be added to the developing solution, so that the stability of the developing solution against air oxidation is remarkably improved as compared with lith development.

[0005] However, a developer having a relatively high pH is required in order to sufficiently obtain the effect of the hydrazine derivative, and it is necessary to process at a high temperature in order to complete the process in a short time. Therefore, U.S. Pat.
By using an amine compound such as an alkylamine or an alkanolamine in a developer as described in JP-A-929, it becomes possible to perform low-temperature processing at a relatively low pH. However, compared to commonly used developing systems for rapid processing, it has a higher pH and a higher temperature, and the addition of an amine compound in the developer makes it possible to elute silver halide into the developer. The amount increases, which causes silver staining of the automatic developing machine and the photographic material processed there.

[0006] In addition, although a development inhibitor (particularly a heterocyclic compound having a mercapto group) also has an action of suppressing the elution of silver halide into a developing solution, in order to sufficiently obtain the effect of the hydrazine derivative, As with other photographic materials containing no hydrazine derivative, a large amount of a development inhibitor cannot be added to the photographic material. From this point, the amount of silver halide eluted into the developing solution is increased and the silver stain is reduced. Cause.

[0007]

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

The second object of the present invention is to provide a silver halide photographic light-sensitive material which can be processed with a stable developing solution, has little elution of silver halide into the developing solution, and has little silver stain. is there.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide at least a monodisperse silver halide grain having at least 90 mol% silver chloride and an average grain size of 0.2 micron or less on a support. A hydrophilic colloid layer outside the photosensitive layer as viewed from the support, which contains one photosensitive layer, contains a water-dispersible fine particle polymer, and has a surface opposite to the support opposite to the emulsion layer. A silver halide photographic light-sensitive material characterized by having a hydrophilic colloid layer containing a compound represented by the following formula:

[0010]

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In the formula, X represents a heterocyclic residue in which at least one hydrophilic group is directly or indirectly bonded. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium. ]

Hereinafter, Chemical formula 4 will be described in detail.

In the chemical formula 4, specifically, the heterocyclic residue represented by X is an oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring,
A pentazole ring, a pyrimidine ring, a thiadia ring, a triazine ring, a thiadiazine ring, or a ring bonded to another carbon ring or a hetero ring, such as a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a benzoselenazole ring, or a benzotriazole ring And a naphthoxazole ring.

In the chemical formula 4, specific examples of the hydrophilic group bonded to the heterocyclic residue include —SO ₃ M ₁ and —SO _{2
NHR 1, -NHCONHR 1, -NHSO 2} R 1, -
COONHR ₁ , -NHCOR ₁ , -PO ₃ M ₁ , -C
OOM ₁ , —OH and the like. Here, R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. M
₁ represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium.

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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The amount of the compound of formula 4 contained on the back surface of the photosensitive layer may vary depending on the size and halogen composition of the silver halide grains in the photosensitive layer, the type and amount of the binder and other conditions. Is preferably determined according to the amount of silver halide. 1 × per mole of silver halide in photosensitive layer
The range of 10 ^-5 to 1 × 10 ^-1 mol is practically useful, and the range of 1 × 10 ^{-4 to} 5 × 10 ^-2 mol is more preferable.

As the water-dispersible fine particle polymer used in the present invention, so-called synthetic polymer latex, a wide range of polymer latex can be used. Preferred are latexes comprising ethylenically unsaturated monomers, so-called vinyl polymer particles, and particularly preferred are copolymers of vinyl monomers.

Suitable vinyl monomers include acrylates (methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, etc.), α-substituted acrylate (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl hexyl methacrylate, etc.),
Acrylamide (butylacrylamide, hexylacrylamide, etc.), vinyl ester (vinyl acetate, etc.), vinyl halide (vinyl chloride, etc.), vinylidene halide (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene,
Examples thereof include ethylene, butadiene, and acrylonitrile.

Particularly preferred are alkyl acrylate and alkyl methacrylate. Particularly useful are alkyl acrylate or alkyl methacrylate copolymers containing acrylic acid, methacrylic acid, itaconic acid or vinyl monomers having sulfonic acid groups, preferably in a proportion of at most 30 mol%. Specific examples of these are described in JP-B-46-22506, JP-A-56-56227, and JP-A-51-21.
Reference can be made to the specification such as -59942. The synthetic polymer latex disclosed in the above-mentioned patent specification can be used particularly advantageously. For example, preferred synthetic polymer latices include (butyl acrylate-acrylic acid) copolymer, (methyl acrylate-acrylic acid) copolymer, (ethyl acrylate-acrylic acid) copolymer,
(Butyl acrylate-itaconic acid) copolymer, (ethyl acrylate-methacrylic acid) copolymer, (propyl acrylate-acrylic acid) copolymer, (butyl acrylate-styrene sulfonic acid) copolymer, (ethyl acrylate-styrene sulfonic acid) copolymer,
(Methyl acrylate-sulfopropyl acrylate)
Copolymer, (ethyl acrylate-acrylic acid-2-
(Acetoacetoxy-ethyl methacrylate) copolymer, (methyl methacrylate-acrylic acid) copolymer, (methyl methacrylate-itaconic acid) copolymer, and the like.

The synthetic polymer latex is used together with a binder constituting a photographic layer such as gelatin. In order to exhibit the effects of the present invention, the polymer latex is added to the hydrophilic colloid layer outside the photosensitive layer as viewed from the support. The content of the polymer latex in the hydrophilic colloid layer is more preferably 1 g or less per square meter in terms of solid content, and is 5% by weight or more of the amount of gelatin contained in the hydrophilic colloid layer. Incidentally, the content on the back side is not affected by these, and a necessary amount can be contained for the purpose of improving dimensional stability and the like.

In the present invention, a hydrazine derivative may be used.

The hydrazine derivative used in the present invention is a compound represented by the following formulas (28) and (29).

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Hereinafter, the chemical formula 28 will be described in detail.

In the chemical formula 28, the aryl group represented by Ar ₁ is specifically a phenyl group which may have a substituent or a naphthyl group. Examples of the substituent include an alkyl group , Aryl group, hydroxyl group, halogen atom,
Examples include an alkoxy group, an alkylthio group, an aryloxy group, an alkenyl group, an amino group, an acylamino group, a sulfonamide group, an alkylideneamino group, a ureido group, a thiourea group, a thioamide group, a heterocyclic group, and combinations thereof.

Further, Ar ₁ may have a ballast group incorporated therein, which is 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 28, R ₁ represents a group represented by —OR ₁₁ or a group represented by Formula 30.

[0054]

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R ₁₁ 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 ₁₂ and R ₁₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
Alternatively, it represents a pyridinium group represented by Chemical Formula 31. R ₁₂ and R ₁₃ may be linked to each other to form a ring.

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R ₁₄ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group. R ₁₅ 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.

Hereinafter, the chemical formula 29 will be described in detail.

In formula 29, the aryl group represented by Ar ₂ is the same as Ar ₁ in formula 28, wherein R ₂ is a hydrogen atom,
A substituted or unsubstituted alkyl group or aryl group is represented, wherein the alkyl group is a linear, branched or cyclic alkyl group (having 1 to 20 carbon atoms), and the aryl group is a phenyl group or a naphthyl group. As the substituents introduced into these alkyl groups and aryl groups, alkoxy groups (eg, methoxy group, ethoxy group, etc.), aryloxy groups (eg, phenoxy group, p-chlorophenoxy group, etc.), heterocyclic oxy groups ( For example, a pyridyloxy group), a hydroxy group, a mercapto group, a cyano group, an alkylthio group (eg, a methylthio group), an arylthio group (eg, a phenylthio group), a halogen atom (eg,
Chlorine, bromine), acyl group (eg, acetyl group, trifluoroacetyl group), alkylsulfomoyl group (eg, methylsulfamoyl group), acyloxy group (eg, acetyloxy, benzoyloxy group), alkylcarbamoyl group (For example, N-methylcarbamoyl group), alkoxycarbonyl group (for example, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), amino group, alkylamino group (for example, methylamino group, N, N-dimethyl group) Amino group) and the like. R ₂ is preferably a hydrogen atom.

Further, Ar ₁ , Ar ₂ , R ₁ , and R ₂ may have a group in which a group that enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, and the groups described in US Pat. No. 4,355,105.

Specific examples of the compounds represented by Chemical formulas 28 and 29 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 hydrazine derivative is preferably contained in a silver halide emulsion layer.
It may be contained in another hydrophilic colloid layer. Since the content of the hydrazine derivative 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 can vary over a wide range. A range of about 5 × 10 ^-6 to 8 × 10 ^-2 mole per mole of silver in the silver emulsion is practically useful, more preferably a range of 5 × 10 ^-5 to 1 × 10 ^-2 mole. .

A technique for incorporating a polymer latex into a silver halide photographic light-sensitive material containing a hydrazine derivative is as follows.
JP-A-2-41, JP-A-2-1834, JP-A-4-5114
2, No. 4-106542 (hereinafter referred to as Patent A, Patent B, Patent C, and Patent D, respectively). Among these, Patents A, B and D are examples in which a polymer latex is added as a means for preventing black spots peculiar to a photosensitive material containing a hydrazine derivative, and all of the polymer latex is added to the emulsion layer in the examples. From the above, it is apparent that it is better to add a polymer latex to the emulsion layer in order to maximize this effect. Patent C is an example in which the matting property is improved by combining a polymer latex and a matting agent. In this case, the polymer latex is also added to the emulsion layer in the examples. However, the present inventors have found that even if a polymer latex is added to an emulsion layer as shown in the above-mentioned patent, the effect of suppressing the elution of silver halide into a developer and reducing silver stains can be obtained. In addition, it is confirmed that the hydrazine derivative inhibits the high-contrast effect and loses the significance of adding the hydrazine derivative.

On the other hand, the present inventors, in the case of containing a hydrazine derivative, allow a silver halide photographic material to contain a polymer latex in a hydrophilic colloid layer outside the photosensitive layer as viewed from the support, and further support By providing a hydrophilic colloid layer containing the compound represented by Chemical Formula 4 on the surface opposite to the photosensitive layer with respect to the body, it is possible to use a hydrazine derivative in a developing solution without impairing high contrast and other effects. It has been found that silver halide is prevented from being eluted, and that the silver stain on the developing tank and the developing rack of the automatic developing machine and the photosensitive material processed therein is extremely reduced. In other words, the technology indicated by the claims of the present invention has completely different purposes and effects from the above-mentioned patents, differs in the actual state of the use of the polymer latex, and exhibits a remarkable effect in combination with the compound of formula 4 of the present invention. This is a completely new technology that is not expected from the conventional technology.

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 and the like of the silver halide grains are not particularly limited, but the silver halide grains that can be used in the present invention have an average grain size of 0.2
It is monodisperse at submicron. Here, the monodispersed emulsion means that 90% or more of the total number of grains is ± 10% of the average grain size.
%. The method for preparing the silver halide emulsion may be any of known methods such as forward mixing, reverse mixing, and simultaneous mixing.

In the present invention, a water-soluble rhodium salt such as rhodium monochloride, rhodium dichloride, rhodium trichloride and rhodium ammonium chloride can be contained in order to obtain a low-sensitivity emulsion which can be used for a long time in a bright room. 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 water-soluble rhodium salt is 5 × 10 ⁻⁷ per mol of silver halide.
The range of from 2 to ^10-4 mol is effective, and the range of from 1 x ^10-6 to 1 x ^10-4 mol per mol of silver halide is preferred.

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

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

In the light-sensitive material of the present invention, an intermediate layer, a backcoat layer, an undercoat layer and other hydrophilic colloid layers can be provided in addition to the photosensitive emulsion layer and the overcoat layer containing a polymer latex. And in those layers,
A matting agent can be included.

Gelatin is advantageously used 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. 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 light-sensitive material, or stabilizing 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.

The photographic emulsion used in the present invention may contain an emulsion layer, an overcoat layer, a backing layer, etc. for the purpose of enhancing image quality by irradiation, halation, etc., character extraction performance and other performances required in the printing plate making industry. Other hydrophilic colloid layers can contain filter dyes known to those skilled in the art.

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 characteristics (for example, Surfactants for various purposes such as development acceleration, high contrast, and sensitization. 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 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.

Any support known to those skilled in the art can be used for the photographic 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 plates 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 alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably
(Nitroindazoles or benzotriazoles), or a development inhibitor or an antifoggant. If necessary, a water softener, a solubilizing agent, a color tone agent, a development accelerator, a surfactant, an antifoaming agent, a hardening agent, a silver stain preventing agent for a film and the like may be contained. Specific examples of these additives are described in Research Disclosure 176, No. 17643, and the like.

Particularly, in order to obtain ultra-high contrast photographic characteristics, the developing solutions are described in JP-A-56-106244 and JP-A-61-26775.
Amine compounds described in JP-A Nos. 9,230-145, 62-21647, JP-A-2-50150 and 2-208652 can be added. The typical ones are listed below.

A-1) Nn-butyldiethanolamine A-2) 3-Diethylamino-1,2-propanediol A-3) 2-Diethylamino-1-ethanol A-4) 2-Diethylamino-1-butanol A -5) 3-Diethylamino-1,2-propanediol A-6) 3-Diethylamino-1-propanol A-7) 3-Diethylamino-1-propanol A-8) Triethanolamine A-9) 3-Dipropyl Amino-1,2-propanediol A-10) 2-Dioctylamino-1-ethanol A-11) 3-Amino-1,2-propanediol A-12) 1-Diethylamino-2-propanol A-13 ) N-Propyldiethanolamine A-14) 2-di-isopropylaminoethanol A-15) N, N-di- -Butylethanolamine A-16) 3-di-propylamino-1,2-propanediol A-17) 2-methylamino-1-ethanol A-18) 3-diethylamino-1,2-propanediol A-19 ) 4-Diethylamino-1-butanol A-20) 1-Diethylamino-2-butanol A-21) 1-Diethylamino-2-hexanol A-22) 5-Diethylamino-1-pentanol A-23) 6-Diethylamino- 1-hexanol A-24) 1-diethylamino-2-octanol A-25) 6-diethylamino-1,2-hexanediol

The amount of addition may be any amount that promotes high contrast,
Generally, an amount of 0.005 to 1.0 mol / l can be added.

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. (Japanese Unexamined Patent Publication Nos. 57-129436, 57-129433, 57-129434, and 5)
7-129435, U.S. Pat. No. 4,323,643). The treatment 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 to when it comes out is from 60 seconds to 120 seconds.
Even if it is set to seconds, a photographic characteristic of a negative tone of a super-high contrast can be sufficiently obtained.

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【Example】

Example 1 Oxonol Yellow from Hoechst was added to a gelatin solution.
00mg / m ^2, of 136 to 100 mg / m ^2, of 13
7 in an amount of 50 mg / m ² , a surfactant, polystyrene sulfonic acid, and a matting agent.
× 10 ^-4 mol / m ² , a hardening agent was added, and gelatin was applied on a polyethylene terephthalate film at 3 g / m ² to give a back coat.
A blank to which the compound of Chemical Formula 22 was not added was also applied as a blank.

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On the other hand, rhodium dichloride consisting of cubic crystals having an average particle size of 0.13 μm was added to 6.4 × 10 ^−6.
A gelatin silver chloride emulsion containing mol / mol Ag was prepared by a double jet method, and the hydrazine derivative of Chemical Formula 99 was added to the emulsion which was desalted, washed and re-dissolved by flocculation method at 2 × 10 ^-3 mol / mol Ag. 138
× 10 ⁻³ mol / mol Ag, 6 × 10 ⁻³ mol / mol Ag of the compound represented by Chemical Formula 139, and 4 × 10 ⁻³ mol / mol Ag of 1-phenyl-5-mercaptotetrazole.
-Hydroxy-4,6-dichloro-1,3,5-triazine sodium salt, polystyrenesulfonic acid,
Was added to the above-mentioned back-coated film so as to be 5 g / m ^{2 of} silver nitrate and 3 g / m ² of gelatin.

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[0191]

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On top of this, gelatin 1 g / m 2 was used as a protective layer.
2, surfactants, hardeners, matting agents, and the following A to
Samples shown in Table 1 were prepared by applying coating liquids containing 0.2 g / m ² of the seven types of polymer latexes G. As a comparative example, a sample containing no polymer latex was prepared at the same time. The blank in Table 1 is a sample in which neither the compound of formula 4 of the present invention nor the polymer latex in the protective layer is contained in the backing layer. A: (ethyl acrylate-acrylic acid) copolymer (5 mol% of acrylic acid) B: (butyl acrylate-acrylic acid) copolymer (10 mol% of acrylic acid) C: (ethyl acrylate-styrene sulfonic acid) copolymer (styrene sulfonic acid 4 D: (butyl acrylate-itaconic acid) copolymer (5 mol% of itaconic acid) E: (ethyl acrylate-methacrylic acid) copolymer (3 mol% of methacrylic acid) F: (methyl methacrylate-acrylic acid) copolymer (acrylic acid) G: (methyl methacrylate-butyl acrylate-acrylic acid) copolymer (acrylic acid 10 mol%)

After exposing these films through a sensitometry wedge with a printer for light room (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.), the film was developed at 38 ° C. for 20 seconds with a developer having the following composition. Fixing, washing,
Dried. In this processing, an automatic developing machine (LD-221QT, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. From this, the sensitivity and gamma were measured. The sensitivities are relatively expressed with the sensitivity of a blank sample as a comparative example as 100. Gamma is ta of a linear portion having an optical density of 1.0 to 2.5.
It was measured in nθ.

<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 N-n-butyldiethanolamine 12.0 g Sodium toluenesulfonate 8.0 g Water is added and the pH is adjusted to 11.8 with 1 l potassium hydroxide.

Further, these films were processed in the same automatic developing machine at a rate of 1.2 m ² per liter with the same developing solution as described above, and the amount of dissolved silver was measured by atomic absorption analysis. Also,
The developer was allowed to stand for 5 days to check for the presence of a precipitate and the level of adhesion of blackened silver to the vessel wall.

The results are shown in Table 1.

[0197]

[Table 1]

As shown in the present invention, the combination in which the polymer latex was contained in the overcoat layer and the compound represented by Chemical formula 4 was contained in the backcoat layer did not cause a decrease in sensitivity as compared with the comparative example. In addition, the silver halide stain is improved with less elution of silver halide into the developing solution even when processing a larger amount of photosensitive material than usual with a certain amount of processing solution without impairing the contrast enhancement by the hydrazine derivative. You can see that

Example 2 The same as Example 1 except that the compound of formula 4 and the comparative compound added to the backing layer were changed as shown in Table 2 and all A was added as the polymer latex in the protective layer. Thus, samples 10 to 15 shown in Table 2 were prepared and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0200]

[Table 2] * PMT = 1-phenyl-5-mercaptotetrazole MBI = 2-mercaptobenzimidazole

In Table 2, the blanks are the same as those in Table 1. Table 2 also shows that, when the protective layer contains a polymer latex as shown in the present invention and the backing layer contains a compound represented by Chemical Formula 4, there is no decrease in sensitivity as compared with Comparative Examples, In addition, the silver halide stain is improved with less elution of silver halide into the developing solution even when processing a larger amount of photosensitive material than usual with a certain amount of processing solution without impairing the contrast enhancement by the hydrazine derivative. You can see that This technology can be said to be a long-awaited technology that meets conventional demands. Moreover, the content of the present invention differs greatly from those of existing patents and the like, and it can be said that the present invention is a completely new technology which is not expected from the conventional technology.

[0202]

Industrial Applicability According to the present invention, a high contrast can be obtained with a sufficient maximum density, can be handled in a bright room for a long time, can be processed with a stable processing solution, and the elution of silver halide into a developing solution is small. Thus, a negative silver halide photographic light-sensitive material with little silver stain can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G03C 1/34 G03C 1/34 1/43 1/43 1/76 502 1/76 502 (56) References JP-A-3-3 91738 (JP, A) JP-A-2-289842 (JP, A) JP-A-4-43343 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/035 G03C 1 / 04 G03C 1/06 G03C 1/76

Claims (2)

(57) [Claims] 1. A support comprising at least one photosensitive layer having at least 90 mol% of silver chloride and monodispersed silver halide grains having an average grain size of not more than 0.2 μm on a support. The hydrophilic colloid layer outside the photosensitive layer from the viewpoint of the body contains a water-dispersible fine particle polymer, and further contains a compound represented by the formula 1 on the side opposite to the photosensitive layer with respect to the support. A silver halide photographic material having a hydrophilic colloid layer. Embedded image (In Chemical Formula 1, X represents a heterocyclic residue in which at least one hydrophilic group is directly or indirectly bonded. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium.) 2. The silver halide photographic light-sensitive material according to claim 1, wherein the light-sensitive layer or another hydrophilic colloid layer contains a compound represented by Chemical Formula 2 and / or Chemical Formula 3. Embedded image (In the chemical formula 2, Ar ₁ represents an aryl group, and R ₁ represents-
Represents a group represented by the group represented by OR ₁₁ or _{-N, (R 12) (R} 13). R ₁₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
Represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted aryl group. R ₁₂ and R ₁₃ 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. R ₁₂ and R ₁₃ may be linked to each other to form a ring. ) (In the chemical formula 3, Ar ₂ represents an aryl group, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group.)