JPH0766160B2 - Ultra-high contrast negative photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material and a superhigh contrast negative image forming method using the same, and particularly to a silver halide photographic used in a photomechanical process. The present invention relates to a photosensitive material and a super-high contrast negative image forming method using the same.

(Prior Art) In the field of graphic arts, image formation showing photographic characteristics of ultra-high contrast (especially gamma of 10 or more) in order to improve reproduction of continuous gradation images or halftone images by halftone dot images. System required.

Conventionally, a special developer called a lith developer has been used for this purpose. The lith developer contains only hydroquinone as a developing agent, and a sulfite as a preservative is used in the form of an adduct with formaldehyde so as not to impair the infectious developability thereof, and the concentration of free sulfite ion is extremely low (usually 0.1 Mol / below). Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method of obtaining a high-contrast photographic property using a stable developing solution, U.S. Patent Nos. 4,224,401 and 4,168,977.
No. 4,166,742, 4,311,781, 4,272,60
There is a method using a hydrazine derivative described in No. 6, No. 4,211,857, No. 4,243,739 and the like. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is not improved in the lith developer. Greatly improved compared to.

However, the above-mentioned image forming system causes an undesired phenomenon of black spots due to infectious development at the same time as a markedly high sensitivity and a serious problem in the photomechanical process. Black spots are, for example, black spots (also called black peppers) that occur in the areas that should be non-developed areas between halftone dots (also called black pepper), and increase with the passage of time of the sensitive material, especially under high temperature and high humidity. Due to the fatigue of the liquid over time, the phenomenon of sulfite ion, which is generally used as a preservative, and the increase in pH value cause frequent occurrence, and the commercial value as a photosensitizing material is significantly reduced. Therefore, great efforts have been made to improve this black spot, but the improvement of the black spot is often accompanied by a decrease in sensitivity and gamma (γ). It was strongly desired.

As described in Japanese Patent Application No. 60-68873, it has been found that it is effective to add an acidic substance to lower the film surface pH to 5.8 or less as a means for suppressing this black spot, but at the same time, some It became clear that it had harmful effects. That is, the progress of hardening of gelatin in the coating film is delayed, the mechanical strength of the coating film is lowered, and scratches are likely to occur during the developing, fixing and washing processes.

(Object of the invention) Accordingly, the object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic characteristic of γ exceeding 10 by using a stable developing solution, which has extremely high hardness and little black spots. is there.

More specifically, it is to provide a silver halide light-sensitive material having few black spots and a coating film having high mechanical strength.

(Means for Solving Problems) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and to contain a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer. A negative-type silver halide photographic light-sensitive material, characterized in that it comprises an amount of an acidic polymer having a film surface pH of 5.8 or less and a compound represented by the following general formula (I) or (II): It was achieved by using a high tone negative type silver halide light-sensitive material.

X ₁ is a halogen atom, an N-methylolamino group, a glycidoxy group, Y ₁ is H, a halogen atom, —OH, —OM (M is an alkali metal ion), an amino group, a substituted amino group (a phenyl group as a substituent, Sulfonated phenyl group, carboxylated phenyl group, alkyl group, sulfonated alkyl group,
Carboxylated alkyl group, hydroxyalkyl group),
Alkyl group or phenylpropyl ether group, an alkyl or phenylene thioether group, sulfonamide or alkyl sulfonamide group, Z ₁ is selected from the same group as Y _1, the same or different connexion may as Y _1.

Examples of the hydrazine derivative used in the present invention include a hydrazine derivative having a sulfinyl group described in US Pat. No. 4,478,928 and a compound represented by the following general formula (III). Formula (III) R ₀ -NHNH-CHO wherein R ₀ is an aliphatic group or an aromatic group.

In the general formula (III), the aliphatic group represented by R ₀ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group or the like.

Examples thereof include t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group, tetrahydrofuryl group and morpholino group.

The aromatic group represented by R ₀ in the general formula (III) 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 pyrrolazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, and among others, a ring containing a benzene ring is preferable.

Particularly preferred as R ₀ is an aryl group.

The aryl group or aromatic group of R ₀ may have a substituent.

Typical substituents include linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 1 to 3 carbon atoms in the alkyl moiety). ), An alkoxy group (preferably having 1 carbon atom)
~ 20), a substituted amino group (preferably having 1 to 20 carbon atoms)
, An amino group substituted with an alkyl group), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), an ureido group (preferably having 1 carbon atom). Those with ~ 30) and so on.

R _{0 in the} general formula (III) may be one in which a ballast group commonly used in a non-moving photographic additive such as a coupler is incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and includes, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can choose from.

R _{0 in the} general formula (III) may be one in which a group that enhances adsorption on the surface of the silver halide grain is incorporated. Examples of the adsorptive group include groups described in US Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

Methods for synthesizing these compounds are described in JP-A Nos. 53-20921 and 53-2.
No. 0922, No. 53-66732, No. 53-20318.

In the present invention, when the compound represented by the general formula (III) is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (for example, protective layer). Layer, intermediate layer, filter layer, anti-halation layer, etc.). Specifically, when the compound to be used is water-soluble, as a water solution, and when it is poorly water-soluble, as a solution of water-miscible organic solvent such as alcohols, esters, and ketones, a hydrophilic colloid solution. Can be added to. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. In particular, it is preferable to add it to the coating solution prepared for coating.

The content of the compound represented by the general formula (III) of the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer. It is desirable to select the optimum amount according to the kind of the antifoggant compound, etc., and the test method for the selection is well known to those skilled in the art. Usually, it is preferably used in the range of 10 ^-6 to 1 × 10 ^-1 mol, particularly 10 ^-5 to 4 × 10 ^-2 mol, per mol of silver halide.

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

Others described in U.S. Pat.No. 4,478,928 and so on.

The acidic polymer used in the present invention is a compound containing an acidic group having a pKa value of 9 or less, preferably a polymer having a carboxyl group, a sulfoxyl group, or an enediol group, which is disclosed in US Pat. No. 3,362,819. Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides; French Patent 2,
Copolymers of acrylic acid and acrylic esters as disclosed in US Pat. No. 290,699; US Pat. No. 4,139,383 and Research Disclosure No.
Mention may be made of a latex-type acidic polymer as disclosed in 16102 (1977).

Others, U.S. Pat.No. 4,088,493, JP-A-52-153,739,
53-1,023, 53-4,540, 53-4,541, 53
The acidic polymers disclosed in No. 4,542 and the like can also be mentioned.

More preferable specific examples of the acidic polymer can be represented by the following general formula (IV a) or (IV b).

General formula In the formula, X ₂ represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group.

Y ₂ is a hydrogen atom, a halogen atom or a cyano group, a substituted or unsubstituted alkyl group, (Here, R ¹ is a substituted or unsubstituted alkyl group having 2 or more carbon atoms, or a substituted or unsubstituted aryl group.), (Here, R ² is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.), (Here, R ³ and R ⁴ are both a hydrogen atom or a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ³ and R ⁴ may be the same or different. ), And a substituted or unsubstituted aryl group. A represents a repeating unit (monomer unit) derived from an ethylenically unsaturated monocarboxylic acid or monocarboxylic acid salt copolymerizable with an ethylenically unsaturated monomer. B is a polyfunctional crosslinking agent.

x, y, p, q and r are mole percentages of the monomer components in the copolymer and have the following relationships.

x + y = 100, 0 ≦ x <60, 40 ≦ y ≦ 100, p + q + r =
100, 0 ≦ p <60, 30 ≦ q <100, 0 <r ≦ 40 The substituent of the above-mentioned substituted alkyl group or substituted aryl group is a hydroxyl group, a halogen atom (preferably a chlorine atom), a cyano group, an alkyl group. , Aryl groups and the like.

Among the copolymers represented by the general formula (IV a) or (IV b), the following are more preferable. That is, in the formula, X ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms in the alkyl residue, and Y ₂ is (Here, R ¹ is a substituted or unsubstituted alkyl group having 2 to 12 carbon atoms in the alkyl residue), (Here, R ² is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.) Or (Here, R ³ and R ⁴ are both a hydrogen atom or a carbon number of 1 to 12
A substituted or unsubstituted alkyl group, R ³ and R ⁴ may be the same or different), and a styrene group.

Regarding the molar percentage of the monomer component, in the case of IVa, y is preferably 60 to 99, more preferably 70 to 90. In the case of IV b, r is preferably 5 to 35 and q is preferably 40 to 95, more preferably 10 to 30 and q is particularly preferably 50 to 80.

Among Y ₂ , particularly preferable ones are A group (wherein R ¹ is a substituted or unsubstituted alkyl group having 2 to 6 carbon atoms in the alkyl residue, more preferably 3 to 5 carbon atoms), or (Here, R ² is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms in the alkyl residue).

The monomer giving the component A is represented by the following general formula (V).

Formula _{(V) CH 2 = CH-} COOR 5 Specific examples of the monomer represented by the general formula (IV) in the form of the free acid are listed below.

Among the above monomers, the use of acrylic acid or methacrylic acid is particularly preferable.

Component B is a polyfunctional cross-linking agent and is substantially insoluble in water divinylbenzene, trivinylcyclohexane, trivinylbenzene, 2,3,5,6-tetrachloro-1,4-divinylbenzene, unsaturated. Esters of acids with unsaturated alcohols such as vinyl crotonate, allyl methacrylate,
Allyl crotonate, esters of unsaturated acids with polyfunctional alcohols such as trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate,
Butanediol dimethacrylate, 1,6-hexanediol-diacrylate, 1,5-pentanediol-diacrylate, pentaerythritol-triacrylate, tetraethylene glycol-diacrylate, triethylene glycol-diacrylate, unsaturated alcohols and Esters with functional acids such as diethyl phthalate, unsaturated polyethers such as triethylene glycol-divinyl ether, or water-soluble bisacrylamides such as methylene-bis-acrylamide,
Glyoxal-bis-acrylamide, N, N'-dihydroxyethylene-bis-acrylamide, N, N'-cystamine-bis-acrylamide, triacrylyl-diethylenetriamine, acrylic acid (or methacrylic acid) esters of polyethers such as polyethylene glycol-diacrylate (Or dimethacrylate), divinyl sulfone, etc.

Particularly preferred component B is divinylbenzene or diethylene glycol-dimethacrylate.

The copolymer represented by the general formula (IV a) or (IV b) includes other copolymerizable monomer components such as maleic acid, maleic anhydride, N-vinylpyrrolidone and N-.
Known monomers such as vinyl imidazole and the monomers described in US Pat. No. 4,438,278 may be included.

The acidic polymer represented by the general formula (IV a) is suitable for use by being dissolved in water or an organic solvent such as methanol, ethanol, acetone, methyl ethyl ketone, cellosolve, diacetone alcohol, and toluene, which are good solvents for these polymers. ing.

The acidic polymer represented by the general formula (IV b) is suitable for being manufactured and used as a latex dispersed in water in the form of fine particles by an emulsion polymerization method or a suspension polymerization method.

Specific examples of the copolymer represented by the general formula (IV a) or (IV b) are listed below (the copolymerization ratio in the compound examples represents a mole percentage).

Preferred as the acid polymer is one having acrylic acid as an acid group. As the monomer component copolymerized with acrylic acid, alkyl acrylate and alkyl methacrylate are preferable.

In particular, the preferred acid polymer is in the form of a water-dispersed latex, and when mixed with a water-soluble binder such as gelatin, polyacrylamide, or polyvinyl alcohol, it can be easily mixed without problems of aggregation and sedimentation.

The amount of acidic polymer used is 10 mg per square meter
It is preferably ˜1 g, especially 20 mg to 50 mg. In particular, it is preferable to add such an amount as described in Japanese Patent Application No. 60-68873 so that the film surface pH is 5.8 or less. In addition, the membrane surface pH is set to 60-68873.
It was measured by the method described in No. That is, 0.05 cc of distilled water was dropped on the surface of the silver halide light-sensitive material on the side of the emulsion layer of 1 cm ² , and after leaving it in the atmosphere of 90% RH for 10 minutes, the silver chloride electrode (AgCl / KC 1) was used as a reference. As an electrode, a flat glass electrode integrally formed (flat composite electrode, for example, flat composite electrode GS-165F manufactured by Toa Kogyo Co., Ltd.) is used for measurement.

Specific examples of the compound represented by formula (I) of the present invention are shown below.

Specific examples of the compound represented by formula (II) of the present invention are shown below.

Among the compounds represented by the general formula (I) or (II) of the present invention, particularly preferred are compounds in which X ₁ is a chlorine atom.

Although various kinds of Y ₁ can be selected, an alkylamino group or an arylamino group in which a water-soluble group such as -OM (M is an alkali metal ion), a sulfonic acid or a carboxyl group is substituted is preferable.

Particularly preferred compounds are I-1, I-2, I-4 and I-10.

The compound represented by the general formula (I) is 0.5 × 10 ^{−3 to} 100 × 10 ⁻³ mol, preferably 1.0 × 10 ³ per 100 g of gelatin.
^It is better to use ^-3 to 30 x 10 ^-3 mol.

When the compound of the general formula (I) or (II) of the present invention was used in the presence of an acid polymer, unexpectedly remarkable improvement in mechanical strength of the coating film was observed. It was also found that dural progression was specifically accelerated. However, the general formula (I)
Alternatively, when the compound (II) is added in an excessively large amount, there is a problem that the sensitivity of the light-sensitive material changes significantly.

In particular, it was revealed that the latent image is sensitized when the photosensitive material is exposed to light and developed for a long time before development.

As a result of further diligent studies, the present inventor unexpectedly obtained by using a compound having at least two vinyl sulfone groups in combination with the acidic polymer and the compound represented by the general formula (I) or (II), unexpectedly, Little change in sensitivity,
Moreover, they have found that the coating film has a high mechanical strength and the dura- tion proceeds rapidly.

The compound having at least two vinyl sulfone groups preferably used in the present invention is a compound represented by the following general formula (VI).

1) General formula _{(VI) CH 2 = CHSO 2} -R 11 -SO 2 CH = CH 2 R 11 represents a divalent linking group, the alkylene group or substituted alkylene group (the substituent, a halogen, a hydroxyl group, hydroxy Alkyl group, amino group) and may have an amide linking part, an ether linking part or a thioether linking part between them.

Specific examples of the compound represented by the general formula (VI) are shown below.

_{VI-1) CH 2 = CHSO} 2 CH 2 SO 2 CH = CH 2 VI-2) CH 2 = CHSO 2 (CH 2) 2 SO 2 CH = CH 2 VI-3) CH 2 = CHSO 2 (CH 2) ₄ SO ₂ CH = CH ₂ VI-4) CH ₂ = CHSO ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ VI-5) CH ₂ = CHSO ₂ (CH ₂ ) ₂ O (CH ₂ ) ₂ SO ₂ CH = CH ₂ Particularly preferred as the compound represented by the general formula (VI)
R ₁₁ is Or (Where s is an integer of 1 to 5).

Particularly preferred compounds are VI-4, VI-6, VI-7, VI-8.

These compounds are 1.0 × 10 ^-3 to 100 per 100 g of gelatin.
It is preferred to use x10 ^-3 mol, preferably 3.0 x 10 ^-3 to 30 x 10 ^-3 mol.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide, but 70 mol% or more, particularly 90 mol% or more is silver bromide. The silver halide consisting of The content of silver iodide is preferably 10 mol% or less, more preferably 0.1 to 5 mol%.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), and particularly preferably 0.5 μ or less. The particle size distribution is basically not limited, but it is preferably monodisperse. The monodispersion as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have a regular crystal such as a cube or octahedron,
Further, it may have irregular crystals such as spheres and plates, or may have a composite form of these crystal forms.

The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. are allowed to coexist in the process of formation or physical ripening of silver halide grains. Good.

The silver halide particularly suitable for use in the present invention is prepared in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol of silver, and the silver iodide content on the surface of the grain is the average grain size. The silver haloiodide has a higher silver iodide content.
When an emulsion containing such a silver haloiodide is used, higher sensitivity and high gamma photographic characteristics can be obtained.

In the above, it is desirable to add the above-mentioned amount of iridium salt before the physical ripening in the production process of the silver halide emulsion, particularly during grain formation.

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridium (III), potassium hexachloroiridium (IV), ammonium hexachloroiridium (III), etc. There is.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used.

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin.

As the reduction sensitizer, a primary tin salt, amines, formamidine sulfinic acid, a silane compound or the like can be used.

The sensitizing dyes described in JP-A-55-52050, pages 45 to 53 (for example, cyanine dyes and merocyanine dyes) can be added to the light-sensitive material used in the present invention. .

For example, when a cationic dye is used, a cyanine, hemicyanine or rhodacyanine dye is preferred, and the following dyes are particularly preferred.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Reserc
h Disclosure) Volume 176 17643 (December 1978) Page 23 IV
J section of.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes) ), Pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. are added. Rukoto can. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

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 (chromium deuterium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) Etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid etc.), epoxy compounds (tetramethylene glycol diglycidyl ether etc.) isocyanate compounds (hexamethylene diisocyanate etc.) etc. alone or in combination Rukoto can.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Non-ionic interfaces such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene A carboxy group, such as alkyl phosphates,
Anionic surfactants containing an acidic group such as a sulfo group, a phospho group, a sulfate ester group, and a phosphate ester group; amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, complex such as pyridinium and imidazolium Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. In particular, the surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. A fluorine-containing surfactant is preferably used as the antistatic agent. or,
A polymeric latex such as a polyalkyl acrylate may be included for dimensional stability.

To obtain super-high contrast and high sensitivity and photographic characteristics using the silver halide light-sensitive material of the present invention, the conventional infectious developer or US Patent No.
It is not necessary to use the highly alkaline developing solution close to pH 13 described in 2,419,975, and a stable developing solution can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ion as a preservative in an amount of 0.15 mol / or more and has a pH of 10.5 to
With a developer having a pH of 12.3, particularly pH 11.0 to 12.0, a sufficiently high-contrast negative image can be obtained.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-).
3-pyrazolidone), aminophenols (eg N-
(Methyl-p-aminophenol) and the like can be used alone or in combination.

In the silver halide light-sensitive material of the present invention, dihydroxybenzenes are particularly used as the main developing agent and 3-hydroxy compounds are used as the auxiliary developing agent.
It is suitable to be processed with a developing solution containing pyrazolidones or aminophenols. Preferably, the developer contains 0.05 to 0.5 mol of dihydroxybenzenes /
The 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / or less.

Also, as described in U.S. Pat.No. 4,269,929, by adding amines to a developing solution, the developing speed is increased,
It is also possible to shorten the development time.

Other developers include alkali metal sulfites, carbonates,
A development inhibitor such as a pH buffer such as borate and phosphate, bromide, iodide, and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant You can Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a film hardener, and a film silver stain preventive agent. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process of the invention is usually chosen between 18 ° C and 50 ° C.

Example 1 An aqueous solution of silver nitrate and an aqueous solution of potassium bromide and potassium iodide were prepared.
Monodisperse cubic silver iodobromide emulsion A (2 mol% of silver iodide, 98% of silver bromide) having an average grain size of 0.2 μm was mixed by mixing by the double jet method while keeping pAg at 7.9 in the presence of ammonia.
Mol%). Separately, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were mixed by the double jet method in the presence of ammonia while keeping the pAg at 7.9, and the average particle size was 0.
A 35 micron monodisperse cubic silver bromide emulsion B was prepared. Emulsion A was sulfur sensitized with sodium thiosulfate.

Further, in each of the emulsions A and B, the sensitizing dye "5,5'-dichloro-3,3'-di (3-sulfopropyl) -9-ethyl-
Oxacarbocyanine sodium salt "was added to emulsions A and B at 6 × 10 ^-4 mol and 4.5 mol per mol of silver, respectively.
Spectral sensitization was performed by adding × 10 ^-4 mol.

Furthermore, 4-hydroxy-6-methyl-1,3, as a stabilizer,
3a, 7-Tetrazaindene was added.

Emulsions A and B were mixed at a silver halide weight ratio of 6 to 4, and then compound IV-11 was added at 0.40 g / m ²
Was added.

Further, as shown in Table-1, the compounds of Comparative Examples and the present invention were added.

Further, a hydrazine derivative represented by the following formula was added at 4 × 10 ⁻³ mol per mol of silver.

Further, as a surfactant, alkylbenzene sulfonate was added to adjust the pH of the emulsion to 5.8, and then each emulsion prepared above was coated on a polyethylene terephthalate support having a thickness of 100 μm and the coating silver amount was 3.0 g. / m ² and so as to be applied, and further coated to a gelatin 1 g / m ² as a protective layer to the upper layer, each sample in Table 1 (1) -
Created (16).

Each of these samples was stored at 40 ° C and 65% RH for 16 hours, then exposed to 3200 ° K tungsten light for 5 seconds through an optical wedge for sensitometry, and then developed at 38 ° C for 30 seconds with a developing solution having the following composition. Then, it was fixed, washed with water and dried. (For development processing, Fuji Photo Film Co., Ltd. automatic processor FG-660F
Was used. ) The density of the obtained sample was measured with a Macbeth densitometer, and the photographic characteristics were examined.

Developer Basic Formula Hydroquinone 35.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Potassium triphosphate 74.0g Potassium sulfite 90.0g Ethylenediaminetetraacetic acid tetrasodium salt 1.0g Potassium bromide 4.0 g 5-Methylbenzotriazole 0.6g 3-Diethylamino-1,2-propanediol 15.0g Add water 1 (pH = 11.5) As the relative sensitivity, the relative value of the exposure logE value giving a density of 1.5 was shown with reference to the comparative sample e. The gradation (γ) is the slope of the straight line connecting the density 0.3 and the density 3.0 of the characteristic curve. The swelling thickness was determined by immersing the coating film in water and measuring the swelling thickness, and expressed as (swelling thickness / dry film thickness) × 100.

The wet film strength is 38% higher than that of the developer with the composition shown above.
It is the strength when the surface is scratched by various loads with a stainless needle having a diameter of 0.5 mm after being dipped at ℃ for 30 seconds and kept wet. The value shows the load at which scratches started to occur, and the larger the value, the stronger the film strength.

From the results in Table 1, it is understood that the samples of the present invention have a stronger wet film strength.

Example 2 Instead of the compound IV-11 of Example 1, IV-10 and IV-12
Was used.

Similar to Example 1, the sample of the present invention had a strong wet film strength.

Example 3 The procedure of Example 1 was repeated, except that the compounds of Table 2 were used instead of the compounds represented by the general formulas I, II, and VI of Example-1.

1) The latent image regression shown in Table 2 is indicated by the difference in sensitivity between the case where the developing treatment was carried out immediately after the exposure and the case where the developing treatment was carried out after the exposure was carried out at 20 ° C.-80% RH for 24 hours. . Negative values represent desensitization.

2) In addition, the speed of hardening of the coating film after coating and drying is 20
The samples were stored at 55% RH and evaluated by measuring the degree of swelling 7 and 21 days after application.

From the results in Table 2, it can be seen that the samples of the present invention have a higher wet film strength and a faster diffusivity than the comparative sample g.

In addition, a large amount of the compound of general formula (I) (9.6 × 10 ^{−3 to} 19 × 1)
When used at 0 ^-3 mol / 100 g of gelatin, the latent image progress becomes large, so it is preferable to use it at 9.6 × 10 ^-3 mol or less. At this time, when the compound of the general formula (VI) is used in combination, the latent image progress is increased. It was found that the strength was slightly improved and the strength of the wet film was increased.

The result is unpredictable.

Claims (1)

[Claims] 1. A negative type silver halide light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the emulsion layer or other hydrophilic colloid layer, the pH of the film surface being A super-high contrast negative-working silver halide light-sensitive material comprising an acidic polymer in an amount of 5.8 or less and a compound represented by the following general formula (I) or (II). X ₁ is a halogen atom, an N-methylolamino group, a glycidoxy group, Y ₁ is H, a halogen atom, —OH, —OM (M is an alkali metal ion), an amino group, a substituted amino group (a phenyl group as a substituent, Sulfonated phenyl group, carboxylated phenyl group, alkyl group, sulfonated alkyl group,
Carboxylated alkyl group, hydroxyalkyl group),
Alkyl group or a phenyl ether group, an alkyl or a phenyl thioether group, sulfonamide or alkyl sulfonamide group, Z ₁ is selected from the same group as Y _1, may be the same or different from Y _1.