JPS62168139A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high gamma and superior graininess by using a singly dispersed silver halide emulsion to form an emulsion layer and by incorporating a precursor of a photographically useful reagent into the emulsion layer and/or other photographic constituent layer. CONSTITUTION:A singly dispered silver halide emulsion in used to form an emulsion layer and a precursor of a photographically useful reagent in incorporated into the emulsion layer and/or other photographic constituent layer. The precursor is a compound which is stably present under storage conditions and releases a photographic reagent by the separation of a blocking group at the necessary time during processing. The precursor used may be selected among compounds represented by formulae I-V (where A is a hetero atom substituted known photographic reagent and X is a bivalent timing group bonding to methyl through O, cleaves as X-A during processing, are releases A quickly). The preferred amount of the precursor added is 1X10<-8>-1X10<-1>mol per 1mol silver according to the kind of the reagent. Thus, a sensitive material having improved graininess especially in a low density region as well as high sensitivity and high gamma can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high gamma and excellent graininess.

[Prior art]

In recent years, the sensitivity of colorne 7y film has increased and small 7y film has become more sensitive.
With the advancement of photosensitive materials, there is an increasing demand for higher image quality of silver halide photographic materials. In particular, many studies have been conducted regarding graininess, which is contradictory to the demand for higher sensitivity.

Conventionally, in color photography, there is a known technique for improving graininess by incorporating a compound or coupler (hereinafter referred to as a DIR compound) that reacts with the oxidation product of a developing agent to release a development inhibitor during development. .

[Problem that the invention seeks to solve]

However, with this technology, it is necessary to add a large amount of old R compound to improve graininess, and sensitivity and gradation (
It had the disadvantage of requiring a large amount of sacrifice.

In particular, the highly sensitive halogenated 11? When using a silver halide emulsion with a high silver iodide content, which is essential for obtaining an L agent, there was a disadvantage that a practical silver halide photographic emulsion could not be obtained due to a noticeable decrease in the silver halide emulsion. .

The technical problem of the present invention is to provide a silver halide photographic photosensitive material that has high sensitivity and high gamma, but also has improved graininess, particularly in the low grain density region. do.

[Means for solving problems]

As a result of extensive studies, the present inventors have found that in a silver halide photographic light-sensitive material having at least an IM silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is monodisperse. containing a certain silver halide emulsion,
We have also found that the above object can be achieved by a silver halide photographic material whose VF image contains a photographically useful reagent precursor in the silver halide emulsion layer and/or other photographic constituent layers, DISCLOSURE OF THE INVENTION The present invention will be explained in detail below.

The photographically useful reagent precursor used in the present invention refers to a compound that exists stably under storage conditions and whose blocking group is released at the required timing during processing to release a photographic reagent. Compounds represented by formulas (1) to (IX) can be mentioned.

General formula (IV) General formula (Vl) General formula (■) General formula (■) 1(' General formula (IX) Here, in general formulas (1) to (IM), A is substituted with a heteroatom. Known photographic reagents, specifically flucaptotetrazoles, mercaptoti7noazoles,
Anti-fogging agents represented by benzotriazoles or ingusols, developers (auxiliary developers) represented by pyrazolidones, hydroquinones or P-phenylene noamizos, hydranones, hydranodes, quaternary salts, or Caprase agents or nucleating agents such as acetylenes, thioethers, silver halide solvents such as hypo or rhodanine M, azo dyes, photographic reagents having a redox function in which the above photographic reagents are released as a function of development, e.g. It also contains a coloring material for color diffusion transfer sensitive materials.

X in general formulas (1) to (Vl) represents a divalent timing group, which is bonded to the methyl group via an oxygen atom,
Represents a group that quickly releases A after converting X-A to "Ctill !A" during processing. Such a linking group includes:
A product that releases A by an intramolecular ring-opening reaction described in JP-A-54-145135, British Patent No. 2072363,
JP-A-57-154234, etc., which releases A by intramolecular electron transfer; JP-A-57-17984;
Examples include those which release A with the elimination of carbon dioxide gas, as described in No. 2, etc., and the linking group for formalin elimination described in Japanese Patent Application No. 57-20344. Regarding the representative X mentioned above, their structural formulas are as follows: It represents an integer, and n represents 0 or 1. Q represents 100- or -502-, and Z represents an atomic group forming 5 to 7 shells.

W in general formula (II) is -CR5R'-1-0-1
-S-1-NR represents Fu and forms a 5-shell or 7-shell ring with Y,! forms a 4-shell ring of O.

R5, R6, R? are hydrogen atom, chlorine atom, bromine atom, alkyl group having 1 to 20 carbon atoms, and 6 to 2 carbon atoms, respectively.
represents a 7-aryl group of 6, an alkoxy group having 1 to 16 carbon atoms, and a 7-aryloxy group having 6 to 26 carbon atoms, and may have a substituent.

Y represents a group of nonmetallic atoms forming a five-shell ring together with W,
Examples of the 5-shell ring formed include conolylic acid imide, maleimide, oxazolidinone, thiohyguntoin, hydantoin, urazole, parabanic acid, and the like. Examples of the 6-ring include glutaric imide, 3-oxygluculimide, barbylic acid, uracil, and penzoxazinone.

In the general formula (Vl), each Yl is a hydrogen atom,
Rodene atom, furkyl group, alkenyl group, aryl group,
Alkoxy group, aryloxy group, acyloxy group, carbonate ester group, ami7 group, galbonamide group, ureido group, carboxyl group, oxycarbonyl group, carbamoyl group, acyl group, sulfo group, sulfonyl group, sulfamoyl group, cyano group, nitro group Represents a group, etc.

In the general formula (■), x' represents a carbon atom or a sulfur atom, D represents an electrophilic group (for example, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, a 7lyl group, a benol group, etc.), L represents a linking group bonded to R-C- through a carbon atom, and R represents a substituent bonded to a hydrogen atom or a carbon atom. till and Ill each represent 1-3, preferably 1-2.

l' in general formulas (1), (ill ) (■) and [7 (V) represents a substituent on the phenyl nucleus.

R2 in general formulas (III) and (V) represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 26 carbon atoms, and the alkyl group and aryl group may have a substituent. good.

In general formulas (IV) and (V), R' and R4 are respectively an alkyl group having 1 to 16 carbon atoms, a 7-aryl group having 6 to 26 carbon atoms, an alicyclic group having 5 to 10 carbon atoms, and an alicyclic group having 1 to 10 carbon atoms. 1
0 heterocyclic residues, each of which may have a substituent.

R in general formula (■)? , R8, and R9 each represent a substituent, and at least one of R7, R8, and R9 is an electron-withdrawing group that may be generated during development and is bonded to the amide nitrogen atom via a π bond. ,R? , R8
, R9 is substituted with a photographically useful reagent at a position that can be cleaved by intramolecular nucleophilic reaction of the amide nitrogen atom or intramolecular electron transfer from the amide nitrogen atom, and +12 is O or It represents an integer of 1 to 4, and m2 represents an integer of 1 to 3.

In the general formula (■), 81°, R eyes and R12 each represent a substituent, the mark represents Oll or 2, and 13 represents 0
or 1, and the sum of gloss and n is 1 to 3.

Next, specific examples of photographically useful reagent precursors used in the present invention will be shown, but the invention is not limited thereto.

[Exemplary compounds]

0bU2N112 Nl+ ■ P-15 H2 P-21 P-22 0Jlh υ These photographically useful reagent precursors are described in, for example, JP-A-Sho 2.
No. 7-135949, No. 59-3434, No. 59-9
No. 3442, No. 59-137945, Ii 59-1
No. 40445, No. 59-201057, No. 59-21
No. 8439, No. 59-219741, No. 60-410
It is synthesized by a known method as described in No. 34, etc.

The photographically useful reagent precursor according to the present invention includes a silver halide emulsion layer, an undercoat n layer, a protective layer,
It may be added to any layer including an intermediate layer, a filter layer, an antihalethane layer, and other auxiliary layers.

In order to add the photographically useful reagent precursor used in the present invention to these layers, the photographically useful reagent precursor may be added to the coating solution for forming the layer as is, or it must not have an adverse effect on the photographic light-sensitive material. It can be added after being dissolved in a solvent such as water, alcohol, etc. to an appropriate concentration. It is also possible to weld the photographically useful reagent precursor to a high-boiling point organic solvent and/or a low-boiling point organic solvent, and then add the precursor by emulsifying and dispersing it in an aqueous solution.

As a high-boiling solvent, it does not react with the oxidized form of the developing agent 7=
Organic solvents having a boiling point of 150° C. or higher, such as 7-alyl derivatives, 7-tar acid alkyl esters, phosphoric acid esters, citric acid esters, benzo-hexate esters, alkylamides, fatty acid esters, and trimesic acid esters, are used.

As the high boiling point organic solvent that can be used in the present invention,
U.S. Patent No. 2,322,027, U.S. Patent No. 2,533.514
No. 2,835.579, No. 3,287,134, No. 2,353,262, No. 2, 852, 383
No. 3,554,755, No. 3,676.137, No. 3,678,142, No. 3,700,454,
No. 3,748.141, No. 3,779,765, No. 3,837,863, British Patent No. 958.441, No. 1,222,753, 0LS2,538,889, JP-A No. 1983- No. 1031, No. 49-90523, No. 50
-2382: II No. 51-26037, No. 51-
No. 27921, No. 51-27922, No. 51-260
No. 35, No. 51-26036, No. 50-62632, No. 53-1520, No. 53-1521, No. 53-
No. 15127, No. 54-119921, No. 54-11
No. 9922, No. 55-25057, No. 55-3686
No. 9, No. 56-19049, No. 56-81836,
Examples include those described in Japanese Patent Publication No. 48-29080.

Low-boiling or water-soluble organic solvents that can be used with or in place of high-boiling solvents are disclosed in U.S. Pat. No. 2,801,171;
Examples include those described in No. 2,949,380. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and examples of water-soluble organic solvents include 7setone. , methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, 7-cetonitrile, dioxane, trimethylformamide, trimethylsulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, etc. Can be mentioned.

The photographically useful reagent precursor of the present invention may be added at any time during the manufacturing process, but it is generally preferable to add it immediately before coating.

The preferable addition amount of the photographically useful reagent precursor of the present invention varies depending on the type of photographically useful reagent, but is preferably 1×10'' to 1X10-' mol per 1 mol of silver, preferably 1X10-' to 1X10-' for the mekabuto-based antifoggant. lXl0-'mol, azole antifoggants such as benzotriazole are 1xio
-s~lXl0-' moles.

The monodisperse silver halide emulsion used in the present invention is preferably a silver iodobromide emulsion having a silver iodide content of 5 mol% or more, more preferably a silver iodide content of 6 to 20 mol%,
Particularly preferred is a silver iodobromide emulsion containing 7 to 15 mol%.

The monodisperse silver halide emulsion according to the present invention may contain silver chloride to the extent that the effects of the present invention are not impaired.

In the present invention, monodisperse silver halide grains are those in which the weight of silver halide contained within a grain size range of ±20% around the average grain size T is 60% or more of the weight of all silver halide grains. It is preferably 70% or more, more preferably 80% or more.

Here, the average particle size γ is the frequency n of particles having particle size ri
Define the grain size ri when the product niX ri of i and ri3 is maximum.

(3 significant digits, minimum 4 to 5 decimal places.) The grain size referred to here means, in the case of spherical /"10 silver denide grains,
In the case of particles having a shape other than spherical, the diameter is the diameter when the projected image is converted into a circular image with the same area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on a print. (
The number of defined particles is assumed to be 1000 or more indiscriminately.

) Particularly preferred highly monodispersed emulsions of the present invention have a broad distribution defined by! The content is preferably 20% or less, more preferably 15% or less.

Here, the average particle diameter and standard deviation are r i h · as defined above.
shall be requested.

To obtain a monodisperse emulsion, a water-soluble silver salt solution and a water-soluble halide solution are added to a gelatin solution containing seed particles at ρ
It can be obtained by adding by double jet method under control of g and pH.

In determining the addition rate, refer to JP-A-54-48521.
No. 58-49938 can be referred to.

As a method for obtaining a more advanced monodisperse emulsion,
The growth method in the presence of tetrazaindene disclosed in Japanese Patent No. 122935 can be applied.

In the silver halide emulsion of the present invention, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride, etc. are used as silver halide in ordinary silver halide emulsions. Any one that can be used can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. Seed particle (
The method of growing and the method of growing may be the same or different.

In the silver halide of the present invention, the halogen composition of the grains may be changed using the Compernoyon method at any step of the formation.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of the silver halide grains of the present invention.

The silver halide grains of the present invention can be formed using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including fa salts) during the process of grain formation and/or grain growth. By adding metal ions using at least one selected from iron salts and iron salts (including complex salts), these metal elements can be contained inside the particles and/or on the particle surface, and in an appropriate reducing atmosphere. By leaving the particles in place, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. When removing the salts, use Research Disclosure (Research Disclosure).
Disclosure (hereinafter abbreviated as RD) 17643
It can be carried out based on the method described in item (■).

The silver halide grains of the present invention may be grains in which a latent image is mainly formed on the surface, or may be grains in which a latent image is mainly formed inside the grain.

The halogenated kite particles of the present invention may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as spherical or twin crystals. . In these particles, any ratio of 11001 planes to 11111 planes can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The size of silver halide grains is 0.05 to 30μ, preferably 0.1 to 30μ.
20μ can be used.

The silver halide emulsion of the present invention may be a mixture of separately formed silver halide emulsions of 2M1 or more.

The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, an f# gold metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
A combination of two or more types may be used. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

The most useful pigments are cyanine pigments, merocyanine pigments,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or to maintain stable photographic performance, during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating the silver halide emulsion. , compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as the bangu (or protective colloid) in the silver halide emulsion of the present invention, but
Synthetic hydrophilic polymers such as gelatin derivatives, graft polymers of gelatin and polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers
Hydrophilic colloids of I″!P can also be used.

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention and other hydrophilic colloids contain one or more hardeners that crosslink the baingu (or protective colloid) molecules and increase the film strength. It can be used to harden the membrane. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methylolnomethylhyguntoin, etc.), nooxane-derived 4F derivatives (2,3-dihydroxydinoxane, etc.), activated vinyl Compound (1,3,5-
triacryloyl-hexahydro-5-)ryanone, 1
, 3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-fuchloro-6-hydroxy-S-trianone, etc.), mucohalogen acids (mucochloric acid, mufufenoxychloroic acid, etc.), etc. alone. Or they can be used in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, Section 2, A.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycytyl acrylates, (meth)acrylic 7mides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with these. Polymers containing a combination of acrylic acid, methacrylic acid, α,β-unsaturated nocarboxylic acid, hydroxyalkyl (meth)7 acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used.

In the emulsion layer of a photosensitive material, a dye is formed by a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative) during color development processing. Dye-forming couplers are used. The dye-forming couplers are usually selected for each emulsion layer so that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion/l A magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful 7-ragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called Dllt couplers. Instead of the DIR coupler, a DIR compound may be used which undergoes a camping reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose.

A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylaceto-7nilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3,265.506, No. 3,4
No. 08,194, No. f53,551,155, No. 3
．． No. 51112,322, No. 3,725.072,
No. 3.891.445, West German Patent No. 1,547.8 [
No. 38, West German Application Publication No. 2,219,917, No. 2,2
No. 61,361, No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-73147,
No. 50-6341, No. 50-87650, No. 50-
No. 123342, No. 50-130442, No. 51-2
No. 1827, No. 51-102636, No. 52-824
No. 24, No. 52-115219, No. 58-95346
This is what is written in the number etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, single-chain acylacetonitrile couplers, ingzolone couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
No. 8, - No. 3,062,653, No. 3.127,
No. 269, No. 3,311,476, No. 3,419
, No. 391, No. 3,519,429, m 3.5
No. 58,319, No. 3,582.322, No. 3.
No. 615,506, No. 3,834.908, No. 3
, No. 891.445, West German Patent No. 1,810.464,
West German Patent Application (OLS) No. 2.408,885, 2.
No. 417,945, No. 2,418.959, No. 2,4
No. 24,467, Japanese Patent Publication No. 40-60: (No. 1, Japanese Patent Publication No. 49-74027, No. 49-74028, No. 49-
No. 129538, No. 50-80233, No. 50-15
No. 9336, No. 51-20826, No. 51-2654
No. 1, No. 52-42121, No. 52-58922,
Examples include those described in Japanese Patent Application No. 53-55122 and Japanese Patent Application No. 55-110943.

As cyan dye-forming couplers, phenolic or cabtol couplers are generally used. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
No. 3,730, f52,474.29:3, No. 2
．． No. 801,171, No. 2,895.826, No. 3.478,563, No. 3,737,326, No. 3.758,308, No. 3.893.044 Japanese Patent Publication No. 47-37425, No. 50-10135
No. 50-25228, No. 50-112038,
Couplers described in JP-A-50-117422, JP-A-50-130441, etc., and couplers described in JP-A-58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. The oil-in-water type emulsion dispersion method uses a conventionally known method for dispersing hydrophobic additives such as couplers, and usually has a boiling point of 150
A high boiling point organic solvent of C or above is dissolved in combination with a low boiling point organic solvent and/or a water soluble organic solvent depending on the deafness, and a surfactant is used in a hydrophilic binder such as a gelatin aqueous solution. After emulsification and dispersion using a dispersing means such as a homonizer, colloid mill, 70-knot mixer, or ultrasonic device, it may be added to the desired hydrophilic colloid liquid.

Same as dispersion or dispersion, ? A step of removing the low boiling point organic solvent may also be added.

High-boiling, α-solvents such as phenol I conductors, 7-tar acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trinosic acid esters, etc., which do not react with the oxidized form of the developing agent, have a boiling point of 150. An organic solvent having a temperature of ℃ or higher is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butyl, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, Dll compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be treated as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color anticapri agent can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in Section 2 J of R017643.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD176.
The compound is a compound described in No. 43, Section XXI, Section B-1), and the development retardant is a compound described in Section XXI, Section E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, etc. (1.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds that can be preferably used as optical brighteners are described in Section V of No. 11017643.

The photosensitive material can be provided with auxiliary layers such as a single filter layer, a halide prevention layer, an irradiation prevention layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Examples of such dyes include oxonol dyes, hemioxol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl (fatty), polycarbonate, etc. and styrene polymers and copolymers thereof.The particle size of the matting agent is 0.05μ to 10μ.
Preferably. The amount to be added is 1 to 300 tag
/ta 2 is preferred.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used to prevent static electricity on the side of the support that has not been subjected to 7L scraping, and may also be used to prevent static electricity on the side on which the 7L scraping and/or emulsion layer has been laminated to the support. The antistatic agent may be used in a protective colloid layer other than the protective colloid layer.Preferably used antistatic agents are the compounds described in the former) No. 17643 XI [[].

The photographic emulsion and/or hydrophilic (hydrophilic) a-side layer of the light-sensitive material has properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (accelerating development, hardening, sensitization, etc.) ) Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. films, flexible supports with reflective features on these films, glass, metal,
Includes pottery etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be coated via one or more subbing layers to improve antihalation properties, friction 1, v properties, and V/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which have quick reactivity and will cause delta before coating if added to the coating solution in advance, should be mixed immediately after coating using a static mixer or the like. is preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, 7-ion surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkylamines, quaternary ammonium salts, pyridine, and others. heterocycles, cationic surfactants such as phosphonitums or sulfonits, carboxylic acids, sulfonic acids,
An acidic group such as phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc.
Anionic surfactants such as amino acids, amino sulfonic acids, and amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a more bath using a one-bath development, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. It is also possible to perform a processing step.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and development is performed with a 7 activator solution, or a 7 activator solution may be used for the monobath treatment. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process / Activator process - Bleach-fix process - 7 Activator process - Bleach process Constant fixation process / Morebath process Processing temperature is usually 10°C It is selected in the range of ~65℃,
The temperature may exceed 65°C. Preferably 25℃
Processed at ~45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes amino 7 ether/- and p-7 nylenone amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, and for example, salts of salts, sulfates, PL luenesulfonates, sulfites, sulfur a, W, benzenesulfonates, etc. can be used. can.

These compounds are generally about 0.0% in color developer 11.
A concentration of 1 to 30 g, more preferably about 1 to 15 g per color developer 11 is used. Sufficient color density cannot be obtained with addition amounts smaller than O and Xfl.

Examples of the above-mentioned ami77er-based developers include 10-amino7er, p-7er, 5-amino7er, and 5-amino7er.
Included are 2-oxy-toluene, 2-amino-3-oquine-toluene, 2-oxy-3-amino-1,4-tmethylbenzene, and the like.

Particularly popular primary aromatic amine color developers are N, Nl
-Dialkyl-p-phenylenenoamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted.

Among them, examples of particularly useful compounds include N-N-tmethyl-1)-phenylenenoamine hydrochloride, N-methyl-p
-Phenynnoamine hydrochloride, N,N-dimethyl-p-
722 diamine hydrochloride, 2-7 minnow 5-(N-x
Tyl-N-F7'zylami/)-)luene, N-ethyl-N-β-methanesulfone 7midoethylruthyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino- 3-methyl-N,
N-nonitylaniline, 4-ami/-N-(2-
/)xyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, use alkaline silver halide color photographic material instead of color developing solution! It is also possible to process with an alkali solution (activator solution), and after the alkali solution treatment, the bleach-fixing process is carried out immediately. , potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax, etc., and may further contain various additives such as benzyl alcohol, halides, etc. It may contain an alkali metal such as potassium bromide or potassium chloride, a development regulator such as citradinic acid, and a preservative such as hydroxylamine or sulfite. Furthermore, various antifoaming agents and surfactants, as well as growth solvents such as methanol, dimethylformamide, and trimethylsulfoxide, can be appropriately contained.

1) 11 of the color developing solution used in the present invention is usually 7 or more, preferably about 9 to 13.

In addition, the color developing solution used in the present invention may optionally contain antioxidants such as noethylhydrooxy7mine, tetronic acid, tetronimide, 2-anilinoethanol, nohydroxyacetone, aromatic secondary alcohol, and hydroxamic acid. , pentoses or hexoses, beer rolls 1.
It may also contain 3-methyl ether or the like.

In the color developing solution used in the present invention, various chelate wastes can be used in combination as a metal ion sequestering agent. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriami7pentaacetic acid, etc.
- Hydroquinethylidene-Natured phosphonic acids such as 1,1°-diphosphonic acid, 7mi/polyphosphonic acids such as ami/tri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2 Examples include phospho/carboxylic acids such as -phosphonobutane 1,2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As the bleaching agent, a metal complex salt of an organic acid is used, such as polycarboxylic acid, polycarboxylic acid, oxalic acid, citric acid, etc. An acid coordinated with metal ions such as iron, cobalt, copper, etc. is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and amide/polycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, noethylenetriaminebentaacetic acid, and ethylenediamine-N-(β-oxyethyl).
-N, N'.

N'-) diacetic acid, propylenenoamine thitraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, imi7noacetic acid, nohyroxyethylglycine citric acid (or tartaric acid), ethyl ethernoamine thitraacetic acid, glyfur ethernoamine tetraacetic acid Examples include acetic acid, ethylenediaminetetrapropionic acid, phenylenenoaminetitraacetic acid, and the like. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches are used in amounts of 5 to 450 g/l, more preferably 20 to 250 g/l.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenenoaminetitraacetate iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleaching solution has a pt+ of 2.0 or higher, but is generally 4.0 to 9.5, preferably 4.5 to 8.0.
and most preferably 5.0 to 7.0.

A fixer having a commonly used composition can be used. Examples of fixing agents include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, and thiosulfates such as ammonium thiosulfate, which are used in conventional fixing processes. Typical examples thereof include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in amounts of 5 g/l or more within the range of dissolution, but are generally used in amounts of 70 to 250 g/l. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or constant
1t! The c-shock agent may be contained alone or in combination of two or more. Furthermore, various optical brighteners, t'+'J foaming agents, or surfactants can be contained. Also, hydroxylamine, hydranone,
Preservatives such as bisulfite adducts of aldehyde compounds, amino/
Organic chelating agents such as polycarboxylic acids, stabilizers such as nitro alcohols and nitrates, hardeners such as water-soluble aluminum salts, growth solvents such as methanol, trimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained. .

The pH of the constant ff1l is used at 3.0 or higher, generally from 4.5 to 10, preferably from 5 to 9.5, and most preferably from 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, a sulfite as a preservative. (■) A bleaching constant consisting of a complex salt bleach and a small amount of a halide such as ammonium bromide in addition to the above silver halide fixing agent; 4 parts, or conversely, a large amount of a halide such as ammonium bromide. A bleach-fix solution consisting of the added composition, furthermore, iron ethylenedi7minetetraacetate (
III) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, heptammonium iodide, etc. may also be used. I can do it.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the additives for the pH buffer shavings that can be included in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The bleach-fix solution has a pl+ of 4.0 or more, but is generally used in the range of 5.0 to 9.5, preferably 6.0 to 8.
．． 5, most preferably 6.5 to 8.5.

The photosensitive emulsion layer containing the photographically useful reagent precursor-containing layer of the present invention and the monodisperse silver halide emulsion of the present invention comprises:
It can be applied to any of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer in a multilayer color light-sensitive material.
If the color-sensitive layer is composed of two or more layers with different sensitivities, it can be applied to any of the highest sensitivity layer, medium sensitivity layer, and lowest sensitivity layer, but it is especially applicable to medium and high sensitivity layers. Preferably, it is applied in layers.

When the present invention is applied to a multilayer color photosensitive material, blue sensitivity,
The silver iodobromide emulsion of the present invention and the photographically useful reagent precursor of the present invention may be contained in at least one of the green-sensitive and red-sensitive light-sensitive emulsion layers, but preferably, a plurality of light-sensitive emulsion layers or more. Preferably, all the photosensitive emulsion layers contain the photosensitive emulsion layer of the present invention.

The photographically useful reagent precursor of the present invention is preferably added in the same layer as the monodisperse silver halide emulsion of the present invention.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to examples, which will explain how the present invention can be carried out. 2! There are no restrictions on who you are.

Silver iodobromide emulsions Em-1 to E+o-4 (
Table 1) was divided into silver halide contents equivalent to 0.35 mol, and chemical sensitization was applied to each portion using ammonium thiocyanate, sodium thiosulfate, and chloroauric acid.
Furthermore, as a green-sensitive sensitizing dye, anhydro-5,5゛-dichloro-9-ethyl-3゜3゛-no(3-sulfopropyl)oxacarpocyanine hydroquine;
5,5゛-no7uni-9-ethyl-3,31-c(
3-Sulfopropyl)oxacarbocyanine; Add 1 g each of 18II of anhydro-9-ethyl-3,3'-no(3-sulfopropyl)-5, G, 5°, 6'-dibenzoxacarbocyanine hydroxide, Furthermore, 4-hydroxy-6-methyl-1,3,3a,? −
Tetrazaindene and 5-phenyl-1-mercaptotetrazole were added. Next, a dispersion (M-1) with the following composition
120ω11 saponin and 1,2-bisvinylsulfonylethane were added and coated on a cellulose triacetate base support so that the silver amount was 15+ag/dm2,
A sample with a dry and stable coating was obtained.

These samples were designated as samples N001-21.

Dispersion (M-1) 1-(2,4,6-)lichlorophenyl)-3-13-(2,4-diterL-7mil72/xyacetamide)-benzamidej-5 as magenta coupler - Using 8X 10-2 mol of pyrazolone per mol of silver halide, 2-(1-722-5
-Tetrazolylthio)-4-octatecylsuccinimide-1-indanone (1)-1) was added at 0.28X 10-2 mol per mol of silver halide, and the compounds of the present invention shown in Table 2 were used. . This is used as a high boiling point organic solvent to coupler ff! 1 times the amount of trifrenol phosphate was used and mixed with this, and ethyl acetate was added to the mixture and heated to 60° C. to completely dissolve it. Add this solution to 50 ml of a 10% aqueous solution of Alkanol B (registered trademark, alkylnaphthalene sulfonate manufactured by DuPont).
and 10% gelatin aqueous solution 700I11 and dispersed using a colloid mill.

These samples N011 to 21 were KS- based on the JIS method.
After exposure to white light using a type 1 sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), the following color development treatment was performed.

[Processing process] (37.8℃) Processing time 1, color development 3 minutes 15 seconds 2, bleaching
6 minutes 30 seconds 3, wash with water
3 minutes 15 seconds 4, established 6 minutes 30
Second 5, Washing with water 3 minutes 15 seconds 6, Stabilization 1 minute 30 seconds 7, Drying Color developing solution composition: Bleaching solution composition Fixing solution composition: Stabilizing solution composition: Sensitometry was performed on each sample obtained. The results are shown in Table 2 below. In the same table, the sensitivity is +0
．． It is expressed as a relative value of the reciprocal of the exposure amount that gives 1.

Granularity is the variation in density value (= 1000 times the sieve difference showed that.

Table 1 As is clear from the results in Table 2, the photosensitive material containing the monodisperse silver halide emulsion of the present invention and the blecaser of the present invention is different from the conventional photosensitive material containing a DIR compound or the precursor of the present invention. Compared to a light-sensitive material containing a silver halide emulsion with low monodispersity, it has excellent sensitivity and graininess in a low density region, and has a high gamma.

In addition, the conventional relationship in which the higher the silver iodide content or the addition of a DIR compound, the higher the sensitivity and the lower the mma, has been improved; It can be seen that the ratio is better.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Hand stamped ITJE document (method) % formula % 2. Name of the invention Silver halide photographic light-sensitive material 3. Relationship with the hli positive fraud case Patent applicant address Shinjuku, Tokyo Konishiroku Photo Industry Co., Ltd., 1-26-2, Nishi-Shinjuku, 1-chome, Nishi-Shinjuku, 1-26-2, Sakura-cho, Hino-shi, Tokyo 191 Japan (0425-83-1521)
Patent No. 11-5, Specification subject to amendment 6, Contents of amendment

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a monodisperse silver halide emulsion, and the halogen A silver halide photographic light-sensitive material characterized in that a silver halide emulsion layer and/or other photographic constituent layers contain a photographically useful reagent precursor.