JPH0618000B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material having an improved inter-image effect and improved sharpness and graininess.

(Prior Art) By color-developing a silver halide color photographic material, an oxidized aromatic primary amine color developing agent and a coupler react to react with indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is known that similar dyes are formed and color images are formed. In this method, a subtractive color method is usually used for color reproduction, and a yellow, magenta, and cyan color image forming agents that have a complementary color relationship with a silver halide emulsion that is selectively exposed to blue, green, and red, respectively. Is used. To form a yellow color image, for example, an acylacetanilide or a dibenzoylmethane-based coupler is used, and for forming a magenta color image, mainly pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano are used. Acetophenone or indazolone type couplers are used, and mainly phenol type or naphthol type is used for forming a cyan image.

By the way, the dyes produced from these couplers are not ideal spectral absorption spectra, and particularly magenta and cyan dyes have broad absorption spectra or have sub-absorption in the short wavelength region, which makes them suitable for color photographic materials. Not desirable for color reproduction.

In particular, the secondary absorption in the short wavelength region tends to cause a decrease in saturation. As a means for improving this, it can be improved to some extent by expressing an inter-image effect.

The inter-image effect is described, for example, in Hanson et al., “Journal of the Optical Society of America”.
ical Society of America ", Vol. 42, pp. 663-669, and by A. Thiels,
"Zeitschrift frWissenschaftliche Photographie, P
hotophysique und Photo-chemie), Volume 47, Volume 10
6-118 and 246-255.

U.S. Pat. No. 3,536,486 discloses the incorporation of diffusible 4-thiazoline-2-thiones into exposed color reversal photographic elements and also U.S. Pat. No. 3,536,4.
No. 87 describes the introduction of diffusible 4-thiazoline-2-thiones into unexposed color reversal photographic elements to obtain the desired interimage effect.

Further, in Japanese Patent Publication No. 48-34169, when a color photographic light-sensitive material is developed to reduce silver halide to silver, the presence of an N-substituted 4-thiazoline-2-thione compound causes a remarkable interimage effect. It is described that appears.

Providing a colloidal silver-containing layer between the cyan and magenta layers of a color reversal photographic element to obtain a preferred interimage effect is described in Research Disclosure, No. 131, page 13116 (1975). Year).

Further, U.S. Pat. No. 4,082,553 discloses a color reversal light-sensitive material having a layer arrangement capable of moving iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains. , Another layer with latent image forming silver halide grains,
A method for obtaining a good inter-image effect is described by including silver halide grains whose surfaces are fogged so that they can be developed independently of image exposure.

However, in the above method, the inter-image effect is insufficient, the use of a colloidal silver-containing layer, the introduction of fogged silver halide grains, etc. leads to a reduction in the color density of the color reversal light-sensitive material. It has a major drawback.

In addition to the above, for example, in the color development processing step, a coupler (DIR coupler) capable of releasing a development-inhibiting substance such as a benzotriazole derivative or a mercapto compound during a coupling reaction with an oxidized product of a color developing agent is used. It is also known that by using or by using a hydroquinone compound capable of releasing a development inhibitory substance such as an iodine ion or a mercapto compound at the time of development, an interimage effect can be produced, but these compounds are used. However, their use has been limited because of marked desensitization and a decrease in color density.

(Object of the Invention) An object of the present invention is, firstly, to provide a multilayer color photographic light-sensitive material having a large inter-image effect without impairing other photographic characteristics.

The second object of the present invention is to provide a silver halide photographic light-sensitive material excellent in sharpness.

The third object of the present invention is to provide a black-and-white silver halide light-sensitive material having high sharpness and good graininess.

(Constitution of Invention) The object of the present invention has been achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula [I] or [II].

General formula [I] General formula (II) In the formula, R represents a linear or branched alkylene group, an alkenylene group, an aralkylene group, or an arylene group, and Z or Z ′ represents a polar substituent.

R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents an aryl group, an alkenyl group, or an aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a precursor. n represents 0 or 1. More specifically, R is a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-
Methylethylene group, etc.), linear or branched alkenylene group (for example, vinylene group, 1-methylvinylene group,
Etc.), a linear or branched aralkylene group (eg, benzylidene group, etc.), and an arylene group (eg, phenylene, naphthylene, etc.).

Z or Z ′ is a quaternary ammoniumyl group (eg, trimethylammonium milkyl chloride group, dimethylbenzylammonium milkolide group, etc.), an alkoxy group (eg,
Methoxy group, ethoxy group, 2-hydroxyethoxy group,
Etc.), an alkylthio group (for example, a methylthio group, a butylthio group, etc.), an arylthio group (for example, a phenylthio group, etc.), a heterocyclic oxy group (for example, a 2-pyridyloxy group, a 2-imidazolyloxy group, etc.), Carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.) Sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.) , An ureido group (for example, an unsubstituted ureido group,
Methylureido group, ethylureido group, etc.) thioureido group (eg, unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, p-toluenesulfonyloxy group, etc.) .

Z'is a substituted or unsubstituted amino group (including a salt form, for example, amino group, amino group hydrochloride, methylamino group, dimethylamino group, dimethylamino group hydrochloride,
Diethylamino group, hydrochloride of diethylamino group, dibutylamino group, dipropylamino group, N-dimethylaminoethyl-N-methylamino group, etc.), aryloxy group (eg, phenoxy group, etc.), heterocyclic group (eg, 1 −
Morpholino group, 1-piperidino group, 2-pyridyl group, 4
-Pyridyl group, 2-thienyl group, 1-pyrazolyl group, 2
-Imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group, etc.) and cyano group.

R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, etc.), or a substituted or unsubstituted aryl group (eg, phenyl group, 2- A methylphenyl group,
Etc.), a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

X represents a hydrogen atom, an alkali metal atom (for example, sodium atom, potassium atom, etc.), an ammoniumyl group (for example, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), or a precursor (under alkaline conditions). , X = H, or a group that can be an alkali metal, and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, or the like.

In the general formula [I] or [II], preferably, R is an alkylene group and n = 1 in the general formula [I].

Even in a black-and-white photographic light-sensitive material having two or more silver halide emulsion layers, an effect similar to the interimage effect in a color photographic light-sensitive material can be seen between the silver halide emulsion layers.

For example, in a black-and-white photographic light-sensitive material, the silver halide emulsion layer is composed of two layers, a high-sensitivity layer in which the grain size of the silver halide emulsion is generally large and a low-sensitivity layer in which the grain size of the silver halide emulsion is generally small. In the high exposure amount region where the low-sensitivity layer is developed, the high-sensitivity layer is also developed. At this time, the compound represented by the general formula (I) or (II) of the present invention is contained in either the high-sensitivity silver halide emulsion layer or the low-sensitivity silver halide emulsion layer, or both of them, so that the high exposure amount can be increased. In the region, development suppression works from a low-sensitivity silver halide emulsion to a high-sensitivity silver halide emulsion. As a result, the amount of developed silver in a high-sensitivity silver halide emulsion, which generally has a large grain size, is reduced, so that the graininess in a high exposure amount region is improved.

According to the present invention, the sharpness is improved in the color photographic light-sensitive material and the black-and-white photographic light-sensitive material comprising at least one silver halide emulsion layer.

At the same time as the inter-image effect that occurs between different silver halide emulsion layers, the development inhibiting effect occurs within the layers.

This development inhibiting effect is exhibited at the edges of the high-exposed portion and the low-exposed portion of each silver halide emulsion layer (edge effect).

By incorporating at least one compound represented by the general formula (I) or [II] of the present invention in the silver halide emulsion layer, the high-exposed portion and the low-exposed portion are changed from the high-exposed portion to the low-exposed portion at the edges. Development suppression works.

By suppressing the development of the edge portion, the edge becomes clearer and the sharpness is improved.

Specific examples of the compound represented by the general formula [I] or [II] are shown below, but the compound of the present invention is not limited thereto.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) The compound represented by the general formula [I] used in the present invention is
"Advances in Heterocyclic Chemistry", 9th
Volume 165 to 209 (1968) for reference.

A typical synthesis example is shown below.

Synthesis Example 1 Synthesis method of compound (2) 15 g of 2,5-dimercapto-1,3,4-thiadiazole was added to 300 ml of acetone, and then 22 ml of sodium methoxide 28% solution and 12 g of β-chloropropionamide were added. added. Further, 15 g of sodium iodide was added to this reaction liquid, and the mixture was heated under reflux for 20 hours. After cooling, the obtained crystals were collected by filtration and washed with water. The crystals were recrystallized from a mixed solvent of dimethylformamide-methanol to give the compound
I got (2).

Yield 12.0 g Melting point 175 to 177 ° C. Synthesis example 2 Synthesis method of compound (4) 2,5-dimercapto-1,3,4-thiadiazole 1
5.0 g and 20 ml of 28% sodium methoxide solution were added to 100 ml of ethyl alcohol, dissolved by heating, and 13.5 g of 2-chloroethylurea was added dropwise. After the dropping, the mixture was heated under reflux for 4 hours. After the reaction, the reaction solution was poured into 700 ml of ice water, and the precipitated crystals were taken and recrystallized from methanol.

Yield 16.4 g Melting point 174-176 ° C. Synthesis example 3 Method for synthesizing compound (3) 17.6 g of 1- (3-dimethylaminopropyl) thiosemicarbazide was added to 150 ml of ethyl alcohol, and then potassium hydroxide 7.9 g. Was added and dissolved. Subsequently, 34.3 g of carbon disulfide was added dropwise at room temperature, and the mixture was heated under reflux for 5 hours. The crystals obtained after cooling were taken and recrystallized from methyl alcohol and concentrated hydrochloric acid to obtain the target product (3).

Yield 11.3 g Melting point 204-205 ° C. Synthesis example 4 Synthesis method of compound (5) 30.0 g of 2,5-dimercapto-1,3,4-thiadiazole and sodium methoxide 28% solution 40 ml were added to ethyl alcohol 200 ml and heated. After dissolution, 20.8 g of methoxyethyl chloride was added dropwise. After the dropping, the mixture was heated under reflux for 2 hours. After the reaction, the reaction solution was passed, the solution was evaporated to dryness under reduced pressure, and then recrystallized from ethyl acetate and n-hexane to obtain the desired product.
I got (5).

Yield 29.8 g Melting point 59-60 ° C. Synthesis example 5 Synthesis method of compound (7) 10.5 g of 2,5-dimercapto-1,3,4-thiadiazole and sodium methoxide 28% solution 14 ml were added to ethyl alcohol 100 ml and heated. After dissolution, 8.5 g of methylthioethyl chloride was added dropwise. After the dropping, the mixture was heated under reflux for 3 hours. After the reaction, the reaction solution was poured into ice water 1 and the precipitated crystals were collected and recrystallized from ethyl acetate and n-hexane to obtain the desired product (7).

Yield 8.6 g Melting point 75 to 76 ° C. Synthesis example 6 Synthesis method of compound (29) 15.0 g of 2,5-dimercapto-1,3,4-thiadiazole, 2-chloroethyltrimethylammonium chloride 17.4 g and n-butyl alcohol 100 ml was added and dissolved by heating, and 7.8 ml of pyridine was added dropwise. After the dropping, the mixture was heated under reflux for 3 hours. After the reaction, the reaction solution is cooled and the precipitated crystals are collected and recrystallized from methyl alcohol to obtain the desired product (2
Got 9).

Yield 18.1 g Melting point 222-225 ° C. When the compound represented by formula (I) or (II) of the present invention is used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer or a yellow layer adjacent to the emulsion layer is used. It is contained in at least one layer such as a filter layer, an antihalation layer, an intermediate layer, or a protective layer, but it is most preferably contained in a silver halide emulsion layer.

Further, when the present invention is applied to a black-and-white photographic light-sensitive material,
The compound represented by the general formula [I] or [II] is contained in the silver halide emulsion layer and / or the protective layer.

The compound of the present invention represented by the general formula [I] or [II] is used for the properties and purposes of the silver halide photographic light-sensitive material to be applied.
Alternatively, depending on the development method, it is generally 10 with respect to 1 mol of silver halide present in the same layer or an adjacent layer.
⁻¹ to 10 ⁻⁵ mol, preferably 3 × 10 ⁻²
Is about 3 × 10 ⁻⁴ mol.

To introduce the compound represented by the general formula [I] or [II] of the present invention into a light-sensitive material, it is dissolved in a solvent such as water, methanol, ethanol, propanol or fluorinated alcohol which is usually used in a light-sensitive material. After that, it is added to the hydrophilic colloid.

Photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer), color papers, color positive films, color reversal papers,
Color photographic light-sensitive materials such as color diffusion transfer process, die transfer process, and black and white negative film,
Any black-and-white photographic light-sensitive material such as black-and-white photographic paper, X-ray film and lith film can be used.

In the present invention, a coupler can be incorporated into a silver halide emulsion layer by a known method, for example, US Pat. No. 2,322,027.
The method described in No. 1 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), quench Acid ester (eg, tributyl acetylcitrate), benzoic acid ester (eg, octyl benzoate), alkylamide (eg, diethyllaurylamide), fatty acid ester (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid ester ( Or a solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol. Methyl isobutyl ketone, beta chromatography ethoxyethyl acetate, then dissolved in methyl cellosolve acetate, etc., are dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853 and JP-A No. 51-5994.
The dispersion method using a polymer described in No. 3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in Arthur Weuice, The Macromonocular Chemistry of Gelatin, (Academic Press, 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. In particular, good results are obtained when at least one photographic emulsion layer contains 0.5 to 15 mol% iodine-containing silver chloroiodobromide, silver iodobromide, and silver chloroiodide.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter in the case of spherical grains or grains close to spheres, the edge length in the case of cubic grains, and the average based on the projected area) is used. Although not particularly limited, it is preferably 3 μm or less.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octagons, and spherical,
Those having an irregular crystal body such as a plate shape, or a composite form of these crystal forms may be used. It may consist of a mixture of particles of various crystal forms.

Further, an emulsion may be used in which ultra-thin tabular silver halide grains having a grain diameter of 5 times the thickness or more account for 50% or more of the total projected area.

The silver halide grains may have different phases in the inside and the surface layer. Further, the particles may be such that the latent image is mainly formed on the surface, or the particles are mainly formed inside the particles.

The photographic emulsion used in the present invention is described in "Chimie et Phisique Photographiqu" by P. Glafkides.
e) ”, published by Paul Montel (196)
7), G. F. GF Duffin, "Photographic Emulsion Chemistry (Photog
raphic Emulsion Chemistry ”, published by Focal Press (1966), VL Zelikman, et al.,“ Making and Coating Photographic Emulsion ”(Maki).
ng and Coating Photographic Emulsion) ”published by Focal Press, Inc. (1964) and the like, that is, any of acid method, neutral method, ammonia method, etc., and soluble silver. As the method of reacting the salt with the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.

As one form of the simultaneous mixing method, a method of keeping PAg in a liquid phase in which silver halide is produced constant, that is, a so-called controlled double jet method can be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt and the like may coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Frieser edited by “Die Grundlagender Photographischen Prozesse mit
Silber-halogeniden ”(Akademische Verlagsgesellschaft, 1968) 675
~ The method described on page 734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt, Reduction sensitization of amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds; precious metal compounds (eg, gold complex salts, Pt, I)
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as r and Pd) can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; for example, oxadrine Thioketo compounds such as thione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; benzenethiosulfone Many compounds known as antifoggants or stabilizers such as acids, benzenesulfinic acid, benzenesulphonic acid amides and the like can be added.

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.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary compound. Ammonium salt compound, urethane derivative,
It may contain a urea derivative, an imidazole derivative, 3-pyrazolidones and the like.

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

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine nuclei, indole nuclei, benzoxadol nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

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.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Amino still compounds substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,635,7).
21), an aromatic organic acid formaldehyde condensate (for example, those described in US Pat. No. 3,743,510), a cadmium salt, an azaindene compound and the like.

The invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material produced by using the present invention, another dye-forming coupler, that is, an aromatic primary amine developing agent (for example, phenylene) in a color developing process is used. A compound capable of forming a color by oxidative coupling with a diamine derivative or an aminophenol derivative) may be used. For example, as a magenta coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, a pyrazoloimidazole coupler, a pyrazolopyrazole coupler, a pyrazolotriazole coupler, a pyrazolotetrazole coupler, a cyanoacetylcoumarone coupler, an open chain acylacetonitrile. There are couplers and the like, yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), and the like, and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule or polymerized ones. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having a color correcting effect, or a coupler (so-called DIR coupler) which releases a development inhibitor upon development.

In addition to the DIR coupler, a non-colored DIR in which the product of the coupling reaction is colorless and releases a development inhibitor.
A coupling compound may be included. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development.

With respect to the couplers and the above-mentioned couplers which can be used in the photographic light-sensitive material of the present invention, two or more kinds can be used in the same layer in combination in order to satisfy the characteristics required for the light-sensitive material, and the same compound can be used in different compounds. Of course, it may be added in more layers.

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 alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), An active vinyl compound (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, mucophenoxycycloric acid, etc.) and the like can be used alone or in combination.

In the light-sensitive material produced by using the present invention, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber,
They may be mordanted with cationic polymers and the like.

The light-sensitive material produced by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color antifoggant.

The light-sensitive material produced by using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in US Pat. No. 3,533,794) and 4-thiazolidone compounds (for example, US Pat. Nos. 3,314,794 and 3,352,681) Those described), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
Nos. 05,805 and 3,707,375), butadiene compounds (for example, US Pat. No. 4,045,
229) or a benzooxide compound (for example, those described in US Pat. No. 3,700,455). An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used.
These UV absorbers may be mordanted in a specific layer.

The light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

Photographic processing of layers of photographic emulsions made using the present invention include, for example, Research Disclosure 176, No. 2,
Any of known methods and known processing solutions as described on pages 8 to 30 can be applied. The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

When the silver halide photographic light-sensitive material of the present invention is a black-and-white light-sensitive material, the black-and-white development / fixing step is carried out, in the case of a color light-sensitive material, color development and bleaching / fixing steps are carried out, and in the case of a color reversal light-sensitive material, black-and-white development is carried out.・ Reversal, color development, bleaching, and fixing steps are performed.

Known developing agents can be used in the first developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-).
Aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and U.S. Pat. No. 4,067,872.
A heterocyclic compound in which the 1,2,3,4-tetrahydroquinoline ring and the indrene ring described in No.
They can be used alone or in combination.

In the black-and-white developer used in the present invention, if necessary, a preservative (for example, sulfite, bisulfite, etc.), a buffer (for example, carbonate, boric acid, borate, alkanolamine),
Alkaline agents (eg hydroxides, carbonates), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium) Salt), a development accelerator, a surfactant, a color tone agent, a defoaming agent, a film hardener, a viscosity imparting agent and the like.

The first developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and the zincate added as a preservative usually plays the role. As the sulfite and silver halide solvent capable of other uses, specifically _{KSCN, NaSCN, K 2 SO 3} , Na 2 SO 3, K 2 S 2 O 5, Na 2 S 2 O 5, K 2 S ₂ O
₃ , Na ₂ S ₂ O _{3 and the} like can be mentioned.

Further, a development accelerator is used for imparting a development accelerating action. Particularly, a compound represented by the following formula (A) described in JP-A-57-63580 is used alone or in combination of two or more kinds, May be used in combination with the above silver halide solvent.

General formula [A] If the amount of these silver halide solvents used is too small, the progress of development is slowed, and if the amount is too large, fogging occurs in the silver halide emulsion, and therefore, there is a preferable amount used by itself. Can be easily done by those skilled in the art.

For example, SCN ⁻ is 0.005 to 0.0 per developer.
It is preferably 2 mol, particularly 0.01 to 0.015 mol, and SO ₃ ²⁻ is 0.05 to 1 mol, particularly 0.1
It is preferably ˜0.5 mol.

When the compound of the general formula [A] is used by adding it to a black and white developing solution, the addition amount is preferably 5 × 10 ⁻⁶ mol to 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁶ mol per developing solution. ^-4 mol to 2 × 10 ^-1 mol.

The pH value of the developer thus adjusted is selected to an extent sufficient to give the desired density and contrast, but is preferably in the range of about 8.5 to about 11.5.

To perform a sensitization process using such a first developing solution,
The time may be extended up to about 3 times the standard processing.
At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The fogging bath used in the inversion step may contain a known fogging agent. That is, stannous ion-organic phosphate vinegar (US Pat. No. 3,617,282),
Stannous Ion Organic Phosphonocarboxylic Acid Acetate (Japanese Patent Publication Sho 5
6-32616), stannous ion-aminopolycarboxylic acid complex salts (British Patent No. 1,209,050), and other stannous ion complex salt borohydride compounds (US Pat. No. 2,984,567). Compounds), boron compounds such as heterocyclic amine borane compounds (British Patent No. 1,011,000), and the like. The fogging bath (inversion bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to 1.
The range is 0, particularly preferably 3 to 9.

The color developer used in the present invention has a composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are the following p-phenylenediamine derivatives. N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-
N-laurylamino) toluene, 4- [N-ethyl-N
-(Β-Hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, N-ethyl-N- (β-methanesulfoamidoethyl) -3 -Methyl-4-aminoaniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-
Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline and 4-amino-3-methyl-N-ethyl-described in U.S. Pat. Nos. 3,656,950 and 3,698,525. N-β-ethoxyethylaniline and 4-amino-3-methyl-
N-ethyl-N-β-butoxyethylaniline and salts thereof (for example, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.) are preferred representative examples.

The color developer may contain other known developer component compounds. For example, caustic soda, caustic potash, sodium carbonate, potash carbonate, and the like can be used as the alkaline agent and the buffer.
Tertiary sodium phosphate or potassium, potassium metaphoric acid, borax, etc. may be used alone or in combination.

A sulfite salt (for example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine which is usually used as a preservative can be added to the color developer.

If necessary, any development accelerator can be added to the color developing solution. For example, various pyridinium compounds represented by U.S. Pat. No. 2,648,604, Japanese Patent Publication No. 44-9503, and U.S. Pat. No. 3,671,247, other cationic compounds, cationic dyes such as phenosafranine, thallium nitrate and potassium nitrate. Neutral salts such as JP-B-44-9504, US Pat. No. 2,533,990, US Pat. No. 2531832, US Pat.
No. 970, No. 2577127, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, JP-B-44-9509, Belgian Patent No. 682862, organic amines, ethanolamines, Ethylenediamine, diethanolamine, etc. F. A. Mason, "Photographic Processing Chemistry"
Chemistry) ", pages 40-43 (Focal Press, 1966).

Further, the color developer may contain an aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid as a water softener. .

Competing couplers and compensating developers can also be added to the color developer.

Citrazinic acid, J acid, H acid and the like are useful as competitive couplers.

As the compensating developer, p-aminophenol, N-benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone, etc. can be used.

The pH of the color developing solution is preferably in the range of about 8-13. The temperature of the color developing solution is selected in the range of 20 ° C to 70 ° C, preferably 30 ° C to 60 ° C.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (VI) and copper (II), peracids, quinones and nitrone compounds are used. For example, ferricyanide, dichromate, iron (II
Organic complex salts of I) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, malic acid Persulfates, permanganese acetyls, nitrosphenols and the like can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetate (III) acetate and ammonium ethylenediaminetetraacetate (III) ammonium salt are particularly useful. Aminopolycarboxylic acid iron (III)
The complex salts are useful in either a stand-alone bleaching solution or a one-bath bleach-fixing solution.

As the bleaching or bleach-fixing solution, U.S. Pat. Nos. 3,042,520 and 3,241,966, JP-B-45-85.
06, Japanese Patent Publication No. 45-8836, US Pat. No. 3,893,858, West German Patent Nos. 1,290,812.
No. 2,059,988, JP-A-53-32736.
No. 53, No. 53-57831, No. 53-37418, No. 53-95630, No. 53-95631, and No. 53-.
In addition to the bleaching accelerators described in No. 72623, No. 53-65732, Research Disclosure No. 17129 (July 1978), various additives can be added.

In the fixing bath of the present invention, as a fixing agent, ammonium salts, sodium salts and potassium salts of thiosulfate are 30 g /
It is used in an amount of up to about 200 g / s. In addition, stabilizers such as sulfites and isomeric bisulfites, hardeners such as potassium alum, acetates, borates, phosphates, carbonates, etc.
A pH buffer or the like can be included. The pH of the fixer is 3-10
And more preferably 5 to 9.

After bleach-fixing treatment or fixing treatment, washing treatment and stabilizing treatment are usually carried out. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, bactericides and antibacterial agents that prevent the formation of various bacteria, algae, and molds. An agent, a metal salt typified by a magnesium salt or an aluminum salt bismuth salt, a surfactant for preventing drying load or unevenness, and various hardeners can be added as necessary. Or by West Photographic Science and Engineering magazine `` LE West, Phot.
Sci. Eng., Volume 6, pages 344-359 (1965).
You may add the compound as described in the above. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the water washing step, JP-A-57 / 57
You may implement the multistage countercurrent stabilization treatment process as described in -8543. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example membrane pH
Buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, etc.) for adjusting (for example, pH 3 to 9)
Representative examples include aldehydes such as monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids used in combination) and formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, and other additives may be used, and two or more of the same or different target compounds may be used. You may use together above.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). At this time, if the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, though it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat. No. 3,34
Indoaniline compounds described in No. 2,597, No. 3,
342, 599, Research Disclosure 14
Schiff base type compounds described in 850 and 15159, aldol compounds described in 13924, metal salt complexes described in US Pat. No. 3,719,492, JP-A-53
Including urethane compounds described in JP-A-135628, JP-A-56-6235 and JP-A-56-16133,
56-59232, 56-67842, 56
No. 83734, No. 56-83735, No. 56-83
No. 736, No. 56-89735, No. 56-81837.
No. 56-54430, No. 56-106241,
Various salt type precursors described in JP-A-56-107236, JP-A-57-97531, JP-A-57-83565 and the like can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-144547.
No. 57-211147, No. 58-50532,
No. 58-50536, No. 58-50533, No. 58
-50534, 58-50535 and 58-
No. 115438.

Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C. to 38 ° C. is standard, but it is possible to increase the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

When the light-sensitive material of the present invention is a color paper, it can be generally bleach-fixed if necessary and when it is a color photographic material for photographing.

(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1. As a sample, a multi-layer color light-sensitive material 1 comprising each layer having the composition shown below on a cellulose triacetate film support.
01 was produced.

First layer: antihalation layer Black colloidal silver: gelatin layer containing 0.18 g / m ² Second layer: intermediate layer 2,5-di-t-pentadecylhydroquinone: 0.18 g / m ² coupler C- 3 ...... 0.11 g / m ² gelatin layer a third layer comprising; first red-sensitive emulsion layer silver iodobromide emulsion (silver iodide 4 mol%, average particle size 0.4 micron) ...... silver laydown (hereinafter 0.72 g / m ² Sensitizing dye A: 9.0 × 10 ⁻⁵ mol for 1 mol of silver Sensitizing dye B: 3.0 × 10 ⁻⁵ mol for 1 mol of silver Dye C: 4.2 × 10 ⁻⁴ mol per 1 mol of silver Sensitizing dye D: 3.0 × 10 ⁻⁵ mol per 1 mol of silver Coupler C-4: 0.093 g / m ² gelatin layer a fourth layer including a coupler C-5 ...... 0.31g / m ² coupler ^{C-6 ...... 0.01g / m 2} ; the second red-sensitive emulsion layer iodo Halide emulsion ...... 1.2g / m ² (silver iodide 10 mol%, average particle size 1.0 micron) Sensitizing dye A ...... 1 mol of silver relative to 7.8 × ^{10 -5} mol sensitizing dye B ... to 1 mol of silver 2.2 x 10 ^-5 mol Sensitizing dye C ... to 3.0 mol of silver 1 mol 3.0 x 10 ^-4 mol Sensitizing dye D ... to 1 mol of silver 2. gelatin layer fifth layer containing 2 × ^{10 -5} mol coupler C-4 ...... 0.1g / m ² coupler C-5 ...... 0.061g / m ² coupler ^{C-6 ...... 0.046g / m 2} ; Third red-sensitive emulsion layer Silver iodobromide emulsion: 1.5 g / m ² (silver iodide 10 mol%, average grain size 1.5 μ) Sensitizing dye A: 8.0 × with respect to 1 mol of silver 10 ⁻⁵ mol Sensitizing dye B: 1 mol of silver 2.4 × 10 ⁻⁵ mol Sensitizing dye C: 1 mol of silver 3.3 × 10 ⁻⁵ mol Sensitizing dye D: 1 mole silver Gelatin layer Sixth layer containing 2.4 × ^{10 -5} mol Coupler C-7 ...... 0.32g / m ² Coupler C-5 ...... 0.001g / m ² for; intermediate layer Gelatin layer seventh layer; First green-sensitive emulsion layer Silver iodobromide emulsion: 0.55 g / m ² (silver iodide 5 mol%, average grain size 0.5 μ) Sensitizing dye G: 3.8 × with respect to 1 mol of silver 10 ⁻⁴ mol Sensitizing dye E ······· 1 mol of silver 1.5 × 10 ⁻⁴ mol Coupler C-8 ·· 0.29 g / m ² coupler C-3 ··· 0.04 g / m ² coupler C -10 ...... 0.055g / m ² coupler C-11 ...... 0.058g / m gelatin layer eighth layer comprising a ^2: second green-sensitive emulsion layer silver iodobromide emulsion ...... 1.0g / m ² ( silver iodide 6 mol%, the spherical particles having an average particle size 1.2 microns) sensitizing dye G ...... 1 mol of silver relative to 2.7 × ^{10 -4} mol sensitizing dye E ...... silver 1.1 × ¹⁰ moles ^-4 mol Coupler C-8 ...... 0.25g / m ² Coupler C-3 ...... 0.013g / m ² Coupler C-10 ...... 0.009g / m ² Coupler C -11 ... Gelatin layer containing 0.011 g / m ² 9th layer; third green-sensitive emulsion layer Silver iodobromide emulsion 2.0 g / m ² (silver iodide 8 mol%, average grain size 1. Spherical particles of 8 μ) Sensitizing dye G: 3.0 × 10 ⁻⁴ mol for 1 mol of silver Sensitizing dye E: 1.2 × 10 ⁻⁴ mol for 1 mol of silver Coupler C-3. ... 0.008 g / m ² coupler C-12 ...... 0.05g / m ² coupler C-18 gelatin layer tenth layer containing ...... 0.001g / m ^2; the yellow filter layer yellow colloidal silver ...... 0.04g / M ² 2,5-di-t-pentadecylhydroquinone ... Gelatin layer containing 0.031 g / m ² Eleventh layer: First blue-sensitive emulsion layer Silver iodobromide emulsion: 0.32 g / m ² (5 mol% of silver iodide, average grain size 0.4 μ) Coupler C-13: 0.68 g / m ² Coupler C-14: 0.03 g / m ² Coupler C-19: gelatin layer containing 0.015 g / m ² 12th layer: second blue-sensitive emulsion layer Silver iodobromide emulsion: 0.29 g / m 2 ² (Silver iodide 10 mol%, average grain size 1.0 μ) Sensitizing dye F: Gelatin layer containing 2.2 × 10 ⁻⁴ coupler C-13: 0.22 g / ² with respect to 1 mol of silver. Thirteenth layer; Fine grain emulsion layer Silver iodobromide emulsion ... Gelatin layer containing 0.4 g / m ² (silver iodide 2 mol%, average grain size 0.15 μ) Fourteenth layer: Third blue-sensitive emulsion layer Iodine silver bromide emulsion ...... 0.79g / m ² (silver iodide 14 mol%, average grain size 2.3Myu) against the sensitizing dye F ...... 1 mol of silver 2 3 × ^{10 -4} mol Coupler C-13 ...... 0.19g / m ² Coupler C-15 ...... 0.001g / m gelatin layer 15th layer comprising ^2; first protective layer UV absorber C-1 ...... 0.14 g / m ² UV absorber C-2: gelatin layer containing 0.22 g / m ² 16th layer; second protective layer Polymethylmethacrylate particles (diameter 1.5 μm) 0.05 g / m ² In addition to the above composition, a gelatin hardening agent C-16 and a surfactant were added to each layer. The sample manufactured as described above was designated as Sample 101.

The compounds used to prepare the samples are shown below.

C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-10 C-11 C-12 C-13 C-14 C-15 C-16 C-17 C-18 C-19 Sensitizing dye A Sensitizing dye B Sensitizing dye C Sensitizing dye D Sensitizing dye E Sensitizing dye F Sensitizing dye G Preparation of Samples 102 to 115 Samples other than the compounds shown in Table 1 were added to the fourth and fifth layers of Sample 101 so that 0.5 × 10 ⁻⁵ mol / m ^{2 was} applied per layer. Sample 102 ...
115 was produced.

Part of each of these samples 101 to 115 was subjected to red wedge exposure, and the other part was subjected to white wedge exposure (red + green + blue light). The amount of red exposure during white exposure,
The amount of exposure during red exposure was the same.

These exposed samples were color developed.

The development processing in this case was performed at 38 ° C. as described below.

By comparing the cyan of red light exposure and the cyan of white light exposure, it can be said that the inter-image effect is larger as the exposure amount difference ΔogE at the density of 0.6 is larger.

The sharpness was determined by the MTF value.

1. Color development: 3 minutes 15 seconds 2. Bleaching: 6 minutes and 30 seconds 3. Washing with water ... 3 minutes 15 seconds 4. Fixation: 6 minutes and 30 seconds 5. Washing with water …… 3 minutes 15 seconds 6. Stable ... 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate: 1.0 g Sodium sulfite: 4.0 g Sodium carbonate: 30.0 g Potassium bromide: 1.4 g Hydroxylamine sulfate: 2.4 g 4- (N-ethyl-) N-β-hydroxyethylamino) -2-methylaniline sulphate ...... 4.5g Add water ...... 1.0 Bleaching solution Ammonium bromide ...... 160.0
g Ammonia water (28%) ...... 25.0CC Ethylenediamine-sodium tetraacetate iron salt ...... 130.0
g Glacial acetic acid …… 14.0CC Add water …… 1.0 Fixer Sodium tetrapolyphosphate …… 2.0g Sodium sulfite …… 4.0g Ammonium thiosulfate (70%) …… 175.0
CC Sodium bisulfite …… 4.6g Add water …… 1.0 Stabilizer Formalin …… 8.0CC Add water …… 1.0 Example 2 Next, the first to twelfth layers were coated on the triacetate film base in the following order to prepare a sample 201.

First layer: antihalation layer (gelatin layer containing black colloidal silver).

Second layer: gelatin intermediate layer.

2,5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate,
10 kg together with 1 kg of a fine grain emulsion (grain size 0.06 μ, 1 mol% silver iodobromide emulsion) not chemically sensitized with 2 kg of an emulsion obtained by stirring at high speed with 1 kg of an aqueous solution of 10% gelatin.
% Gelatin 1.5 Kg and coated so that the dry film thickness would be 2 μm (silver amount 0.4 g / m ² ).

Third layer: low-sensitivity red-sensitive emulsion layer 100 g of 2- (heptafluorobutylamide) -5- {2 '-(2 ", 4" -di-t-aminophenoxy) butylamide} -phenol, which is a cyan coupler, was added to a tri coupler. Cresyl phosphate 100CC and ethyl acetate 100CC
500 g of an emulsion obtained by dissolving in a 1% aqueous solution of 10% gelatin and stirring at high speed to obtain 1 kg of a red-sensitive silver iodobromide emulsion.
(Containing 70 g of silver and 60 g of gelatin, the iodine content was 4 mol%), and coated so that the dry film thickness was 1 μm.
(Silver amount: 0.5 g / m ² ) Fourth layer: High-sensitivity red-sensitive emulsion layer 2- (heptafluorobutyramide) -5- {2 ′-(2 ″, 4 ″ -di-t-, which is a cyan coupler. Aminophenoxy) butyramide} -phenol (100 g) was added to tricresyl phosphate (100 CC) and ethyl acetate (100 CC).
1000 g of an emulsion obtained by dissolving in a 1% aqueous solution of 10% gelatin and stirring at high speed to obtain 1 kg of a red-sensitive silver iodobromide emulsion.
(It contains 70 g of silver and 60 g of gelatin, and the iodine content is 2.
5 mol%) and coated so that the dry film thickness would be 2.5 μm. (Silver amount: 0.7 g / m ² ) Fifth layer; Intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate,
1 kg of an emulsion obtained by stirring 1% of an aqueous solution with 10% of gelatin at high speed was mixed with 1 kg of 10% of gelatin to obtain a dry film thickness of 1
It was applied so as to have a thickness of μ.

Sixth layer: low-green emulsion layer Magenta coupler instead of cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3-
300 g of an emulsion obtained in the same manner as the emulsion of the third layer except that (2,4-di-t-amylphenoxyacetamide) benzamide} -5-pyrazolone was used, was mixed with a green-smelling iodine odor. A silver halide emulsion (1 kg) (containing 70 g of silver and 60 g of gelatin and having an iodine content of 3 mol%) was mixed and coated so as to have a dry film thickness of 1.3 µ. (Silver amount: 0.7 g / m ² ) 7th layer: Highly sensitive green emulsion layer A magenta coupler instead of a cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3-
1000 g of an emulsion obtained in the same manner as the emulsion for the third layer except that (2,4-di-t-amylphenoxyacetamide) benzamide} -5-pyrazolone was used, was mixed with a green-smelling iodine odor. Silver Kg emulsion 1kg (including 70g silver, 60g gelatin,
Iodine content is 2.5 mol%), dry film thickness 3.5
It was applied so as to have a thickness of μ. (Amount of silver: 0.8 g / m ² ) Eighth layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated so as to have a dry film thickness of 1 μm.

Ninth layer: low-sensitivity blue-sensitive emulsion layer α-which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, and 1 kg of a blue-sensitive silver iodobromide emulsion (70 g of silver). , Containing 60 g of gelatin,
Iodine content is 2.5 mol%), dry film thickness 1.5
It was applied so as to have a thickness of μ. (Silver amount: 0.6 g / m ² ) 10th layer: high-sensitivity blue-sensitive emulsion layer α- which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
3-Hydantoynyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, except that 1000 g of an emulsion obtained in the same manner as the emulsion of the third layer was used and 1 kg of silver iodobromide emulsion (70 g of silver, 60 g of gelatin was added). It was mixed with iodine content of 2.5 mol%) and coated so as to have a dry film thickness of 3 μm. (Silver amount 1.1 g / m ² ) Eleventh layer; Second protective layer 1 kg of the emulsion of the ultraviolet absorber C-1 used in Example 1
It was mixed with 1 kg of 10% gelatin and applied so as to give a dry film thickness of 2 μm.

Twelfth layer: first protective layer A 10% gelatin aqueous solution containing polymethylmethacrylate particles (diameter: 1.5 μm) was applied so as to have a dry film thickness of 0.8 μm.

A gelatin hardening agent C-16 and a surfactant were added to each layer.

Preparation of Samples 202 to 216 Sample 201 to Sample 201 was completely different from Sample 201 except that the compounds shown in Table ² were added so that each layer was coated with 1 × 10 ⁻⁵ mol / m ^{2 of} each compound. Sample 201
~ 216 were produced.

Each of these samples 201 to 216 was exposed to red wedge exposure, green wedge exposure, and blue wedge exposure at different locations, and white wedge exposure (red + green + blue light) was applied to the other portion. . The exposure amounts of red light, green light, and blue light during white exposure were the same as those of red exposure, green light exposure, and blue light exposure, respectively.

The exposed samples were subjected to the following development processing.

Treatment process Temperature Time First development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Fixing 4 minutes 〃 Water washing 4 minutes 〃 Stable 1 minute Room temperature Drying composition Uses the following:

First developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 3 g Sodium sulfite 20 g Hydroquinone monosulphonate 30 g Sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-methyl Hydroxymethyl-3 pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water added 1000 ml Reversal solution water 700 ml Nitro NNN Trimethylenephosphone Acid ・ 5 sodium salt 3 g Stannous chloride (2 water 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water added 1000 ml Color developer water 700 ml Nitrilo ・ N ・ N ・ N-trimethylene phosphone Acid ・ 5 sodium salt 3g Sodium sulfite 7g 3rd sodium phosphate Umium (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazine acid 1.5 g N.ethyl-N- (β-methanesulfonamidoethyl) -3.methyl-4 -Aminoaniline / sulfate 11g Ethylenediamine 3g Add water 1000ml Adjusted water 700ml Sodium sulfite 12g Ethylenediamine sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml Bleach water 800g Ethylenediamine Sodium tetraacetate (dihydrate) 2 g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120 g Potassium bromide 100 g Water added 1000 ml Fixer water 800 ml Formalin (37% by weight) 5.0 ml Fuji Drywell (Fuji Film (Surfactant manufactured by Co., Ltd.) 5.0 ml of water was added and 1000 ml of cyan at the time of exposure to red light and cyan at the time of exposure to white light were compared, and an exposure amount difference ΔogE at a density of 1.0 was measured.

Also, in the case of green light exposure and blue light exposure, Δo
gE was measured.

These are shown in Table 2.

From these results, it can be said that the present invention has a very large inter-image effect as compared with the comparative example.

Example 3 Preparation of Emulsion A Potassium bromide and potassium iodide and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to prepare a silver iodobromide emulsion (AgI = 3 mol%) having an average particle size of 0.6 μ, After desalting, silver iodobromide emulsion A was prepared by optimally sensitizing gold and sulfur with chloroauric acid and sodium thiosulfate.

Emulsion B (average particle size 1.2 μAgI = 3 mol%) was prepared in the same manner.

As a sample, a black-and-white photographic light-sensitive material having the following composition was prepared on a cellulose triacetate film support.

First layer: low-sensitivity silver halide emulsion layer Emulsion A (coating silver amount 1 g / m ² ) Second layer: high-sensitivity silver halide emulsion layer Emulsion B (coating silver amount 2.5 g / m ² ) Third layer: Protective layer Gelatin (1.3 g / m ² ) Polymethylmethacrylate particles (diameter 1.5 μ)
In addition to the above composition, a gelatin hardening agent C-16, a surfactant and a thickening agent sodium polystyrene sulfonate were added to each layer of 05 g / m ² . The sample manufactured as described above was designated as sample 301.

Preparation of Sample 302 During the formation of silver halide grains in the emulsion A of the first layer and the emulsion B of the second layer of Sample 301, the compound A was added in an amount of 0.3 × 10 5 each.
Sample 3 except that the coating amount was ^-5 mol / m ^2.
Sample 302 was prepared in exactly the same manner as 01.

Preparation of Samples 303 to 312 Samples 303 to 312 were prepared in exactly the same manner as Sample 302, except that the compounds shown in Table 3 were added in the amounts shown in Table 3 instead of the compound A of Sample 302.

Preparation of Samples 313 and 314 During the formation of silver halide grains in the emulsion B of the second layer of Sample 301, the compounds shown in Table 3 were each applied so that the coating amount was 0.3 × 10 ⁻⁵ mol / m ² . Samples 313 and 31 were added in exactly the same manner as Sample 301 except that the compounds shown in Table 3 were added at the time of preparing the coating liquid for the third layer.
4 was produced.

These samples were exposed through a pattern for measuring graininess or a pattern for measuring sharpness, and then subjected to the development processing described below.

Developer Metol 2 g Sodium sulfite 100 g Hydroquinone 5 g Borax.5H ₂ O 1.53 g Water was added 1 Fixer Ammonium thiosulfate 200.0 g Sodium sulfite 20.0 g Boric acid 8.0 g Ethylenediaminetetraacetate disodium 0.1 g Aluminum sulfate 15. 0 g Sulfuric acid 2.0 g Glacial acetic acid 22.0 g Water was added to 1.0 (pH is adjusted to 4.2) Black-and-white development was carried out at 20 ° C. for 7 minutes with the above developing solution.

Granularity (RMS granularity) is 1000 of the standard deviation of the density fluctuation that occurs when scanning with a microdensitometer.
The value is doubled.

The sharpness was measured by the MTF value.

The results are shown in Table 3.

As shown in Table 3, it is understood that the present invention improves the graininess and sharpness as compared with the comparative example.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeki Nakamura 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. Examiner Toshiyasu Kimura (56) Reference JP-A-59-74557 (JP, A) JP-A-57-164734 (JP, A) JP-A-53-147529 (JP, A) JP-A-60-6940 (JP, A) JP-B-49-8334 (JP, B2)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [I] or [II]. General formula [I] General formula (II) In the formula, R represents a linear or branched alkylene group, an alkenylene group, an aralkylene group or an arylene group,
Z or Z ′ is a quaternary ammoniumyl group, an alkoxy group,
Alkylthio group, arylthio group, heterocyclic oxy group,
Carbamoyl group, sulfamoyl group, acyloxy group,
It represents an ureido group, a thioureido group, or a sulfonyloxy group. Further, Z'represents a substituted or unsubstituted amino group, aryloxy group, heterocyclic group or cyano group. R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents an aryl group, an alkenyl group, or an aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a precursor. n represents 0 or 1.