JPS6057839A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity, graininess, and storage stability of a magenta dye by incorporating a specified magenta coupler in a silver halide emulsion layer. CONSTITUTION:Color developing density can be raised and image sharpness and graininess can be enhanced by incorporating in a silver halide emulsion layer a magenta coupler represented by the shown formula in which R1 is alkyl, aryl, or heterocyclic; R2, R3 are each alkyl; and Ar is aryl. Said silver halide photosensitive material is formed by coating a support good in surface property and small in dimensional change during manufacture and processing. As said support, plastic film, plastic laminated paper, baryta paper, synthetic paper, besides, a hard material, such as glass plate, metal, and earthenware, are usable. Said emulsion is prepared by mixing a soln. of water-soluble silver salt with a soln. of water-soluble halide in the presence of a soln. of a water-soluble polymer, such as gelatin.

Description

DETAILED DESCRIPTION OF THE INVENTION 16. BACKGROUND OF THE INVENTION Technical Field The present invention relates to a silver halide photographic material containing a novel magenta dye-forming coupler.

Prior art and its problems As is well known, in subtractive color photography, an aromatic primary amine color developing agent produces oxidation products of the color developing agent by reducing exposed silver halide grains. Dye images are formed by oxidative coupling of couplers that form yellow, cyan, and magenta dyes in silver halide emulsions. In these cases, as the yellow coupler for forming the yellow dye, a compound having an open chain active methylene group is generally used, and as the magenta coupler for forming the magenta dye, pyrazolone type, pyrazolinobenzimidazole type, Compounds such as the indacylon series are used, and as cyan couplers to form cyan dyes, 7-No I17-7-? fI+-1
--yk-1++ Pakushi death〉” 7 or right hand 11 rem ones are used.

Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or in combination with an auxiliary solvent as necessary,
It is added to a silver halide emulsion, or dissolved in an alkaline aqueous solution and added to a silver halide emulsion. The former uses an oil droplet dispersion method, and the latter uses an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, color sharpness, etc. .

The basic properties required of each coupler are not only to form a dye, but also to have high solubility in high-boiling organic solvents or alkalis, as well as dispersibility and stability in silver halide photographic emulsions. The good thing is that the dye formed by it has fastness to light, heat, moisture, etc., has good spectral absorption characteristics, good transparency, and high color density. It is desired that the images produced have various characteristics such as excellent sharpness and graininess.

However, to the best of the knowledge of the present inventors, no conventional magenta coupler has yet been found that satisfies all of the above-mentioned required properties.

Various pyrazolone derivatives are known as magenta couplers, but these couplers have low coloring efficiency, and in so-called mouth equivalent couplers in which the coupling active site is unsubstituted, the proportion of coupler used for dye formation is about half. , the rest is not useful for pigment formation.

As a method for improving this coloring efficiency, a so-called two-pixel magenta coupler is known in which a substituent (leaving group) capable of splitting off during color development is introduced into the active position of a pyrazolone derivative. As these two-pixel magenta couplers, for example, turnip 2 having an acyloxy group as a leaving group
- is in U.S. Pat. No. 3,311,476, and a coupler having an aryloxy group is in U.S. Pat. No. 3,419,391.
No. 3, U.S. Pat.
214.437 and 3,253,924, 2-
A coupler having a triazolyl group is disclosed in U.S. Patent No. 3.61.
No. 7,291 and couplers having acylthio or thioacylthio groups are described in U.S. Pat. No. 4,032,346, respectively. However, when these two-equivalent magenta koglars are used, significant color capri occurs, coupling activity is low,
The couplers are chemically unstable and change over time into substances that cannot develop color, and furthermore, there are many difficulties in synthesis.

In addition, as previously disclosed in U.S. Pat. compounds were also known.

However, many of these known thio-substituted pyrazolone compounds are so-called development inhibitor-releasing couplers (DIR couplers), and the mercaptan produced as a result of the coupling reaction interacts with silver halide to delay development. It was something.

A thio-substituted pyrazolone coupler having a mercaptan compound having a diffusible group as a leaving group was published in Japanese Patent Publication No. 53-340.
No. 44, JP-A-54-80744 and JP-A-57-
However, these couplers do not have sufficient coupling activity and there are problems with the storage stability of the magenta dye produced, making it difficult to apply them to general color photographic materials.

Furthermore, JP-A-55-62454 describes a magenta coupler in which the 4-position of a pyrazolone derivative is substituted with R'-8- (R' represents a straight or branched alkyl or aralkyl). In these couplers, the mercaptan compound that is released after coupling has virtually no development inhibitory effect, but the coupling activity of the puller is low, and the image storage stability, especially the light resistance, is poor. It has drawbacks such as:

Furthermore, in JP-A No. 55-29805, the 4-position of the pyrazolone derivative is -8-CH2-Dou, : (-N, ,; is)
Magenta couplers substituted with (representing a molecule) have been described, but these couplers do not have sufficient coupling activity and have problems in multi-image storage stability.

In addition, JP-A No. 57-4044 describes a bis-form magenta coupler with active point substitution components, but such magenta couplers have poor solubility in organic solvents, so they disperse and separate, resulting in poor color development. is also inferior.

Furthermore, JP-A-57-17950 describes a magenta coupler in which the 3-position of 5-pyrazolone is substituted with a tertiary alkylamide group and the 4-position is substituted with a thioether group. The improvement effect is small,
Usage is limited.

■ Purpose of the Invention The present invention has been made in view of the above circumstances, and its first object is to have sufficient reaction activity and a high yield without producing unnecessary capri and sting. An object of the present invention is to provide a silver halide photographic material containing a novel two-equivalent magenta coupler that forms a dye.

A second object of the present invention is to provide a silver halide photographic light-sensitive material in which the amount of silver halide in the photographic emulsion layer containing the new two-equivalent i-genta coupler and the amount of coupler used are reduced by using the new two-equivalent i-genta coupler. It is about providing.

A third object of the present invention is to provide a silver halogenide photographic material with excellent graininess using a new two-equivalent magenta coupler.

A fourth object of the present invention is to provide a silver halide photographic material that uses a new two-equivalent magenta coupler and has a fast dye image with excellent light resistance, heat resistance, and moisture resistance.

A fifth object of the present invention is to provide a silver halide photographic material in which the active site substitution component of the coupler does not desorb during color development and react with silver halide to cause adverse effects.

A sixth object of the present invention is to provide a silver halide photographic material with excellent storage stability that does not develop abnormal color during development even if it is left in a place where formalin exists before development. .

■Specific structure of the invention As a result of research on various Magenta Cubes 2-, the present inventors have found that in a silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, the halogen It has been discovered that the above object can be achieved by using a silver halide photographic material characterized by containing at least 1 m of a magenta coupler represented by the following general formula CI) in the silver emulsion layer, and in completing the present invention. It's arrived.

General formula CI) Ar (wherein R1 represents an alkyl group, a ring group, or a heterocyclic group, R2 and R3 each represent an alkyl group, and Ar represents an aryl group) In the present invention, The alkyl group represented by R1 in the general formula CI) is a linear or branched alkyl group, preferably an alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group). group, amyl group, octyl group,
decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), and when these alkyl groups have a substituent, the substituent includes a hydroxyl group, hydroxycarbonyl group, cyano group, aryl group (e.g. phenyl group). , tolyl group, etc.), alkyloxycarbonyl group (e.g., ethoxycarbonyl group, hexadecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylsulfonamide group Acylamino groups (e.g. acetamido groups, benzamide groups, etc.), alkoxy groups (e.g. methoxy groups, pendyl group, etc.), aryloxy groups (e.g. phenoxy groups, etc.), sulfonyl groups ( For example, methanesulfonyl group, etc.).

The aryl group represented by R1 is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. When the aryl group has a substituent, the substituent is
For example, halogen atoms (e.g. chlorine atoms, bromine atoms, etc.),
Hydroxyl group, nitro group, cyano group, hydroxycarbonyl group, alkyl group (straight chain or branched alkyl group, such as methyl group, ethyl group, propyl group, butyl group, agyl group, octyl group, decyl group) group, dodecyl group,
hexadecyl group, octadecyl group, etc.), alkoxy group (
For example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc.), alkylcarbonylamino group (for example, undecylcarbonylamino group, dodecylcarbonylamino group, etc.), R-carbonylamino group (e.g., tolylamino group, tolylamino group,
benzoylamino group), alkylsulfonamide group (
(e.g., dodecylsulfonamide group, etc.), arylsulfonamide group (e.g., benzenesulfonamide group, etc.), alkylaminosulfonamide group (e.g., dimethylaminosulfonamide group, etc.), arylaminosulfonamide group (e.g., Ayu 1.1 sulfonamide group, etc.), alkylcarbamoyl group (e.g., hexadecylcarbamoyl group, etc.), arylcarbamoyl group (e.g., side-lit phenylcarbamoyl group, etc.), sulfonyl group (e.g., methylsulfonyl group, n-dodecylsulfonyl group, etc.), alkyloxycarbonyl group groups (such as dodecyloxycarbonyl groups),
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), alkylsulfamoyl group (sidelight Ff, N
-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), arylsulfamoyl group (eg, phenylsulfamoyl group, etc.), and the like.

The heterocyclic group represented by R3 is preferably a 5-membered or 6-membered heterocyclic group, and examples of the 5-membered cyclic group include a chenyl group, a pyrrolyl group, a furyl group, a thiazolyl group, an imidazolyl group, a pyrazolyl group, and a succinimide group. , triazolyl group, tetrazolyl group, etc., and examples of the six-membered ring group include pyridyl group, pyrimidinyl group, triazinyl group, thiadiazinyl group, dithiazinyl group, etc.

These heterocyclic groups may further form a condensed ring with a benzene ring, such as purinyl group, imidazolyl group, benzoxasilyl group, benzimidazolyl group, quinolyl group,
Examples include indolyl group and phthalimide group.

When these heterocyclic groups have a substituent, examples of this substituent include the above-mentioned substituents when R□ is an alkyl group,
Or the same substituents as the above-mentioned substituents when R1 is an aryl group are mentioned. When it has, the effect of the present invention is particularly remarkable.

is a straight-chain or branched alkyl group, such as a methi group,
These include ethyl group, propyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, hexadecyl group, etc. These alkyl groups can have a substituent, and as a substituent, R1 is an alkyl group. The same substituents mentioned in the case of a group can be mentioned.

The sum of the carbon numbers of R2 and 83 is preferably 8 or less,
Particularly preferably, it is 3 or less. R2 and R3 may be the same or different. Particularly, when R2 and R1+ are both methyl groups, the effects of the present invention are particularly apparent.

In the present invention, the aryl group represented by Ar in general formula CI) is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group. When the aryl group has a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyl group, a nitro group, a cyano group, an alkyl group (for example, a methyl group,
Trifluoromethyl (certain 8-cyatunotyl) -triyl group (e.g. phenyl group, tolyl group, naphthyl group, etc.), alkyloxy group (e.g. methoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, etc.), hydroxycarbonyl group, alkyloxycarbonyl group (e.g., ethoxy group A/ yy = L group, etc.)
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), alkylsulfonyl group (sidelight id' methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, dodecylsulfonyl Me), arylsulfonyl group (sidelight phenylsulfonyl, l), Alkylacyloxy group (e.g. acetyloxy group, cyclohexylcarbonyloxa group, etc.), arylacyloxy group (e.g. benzoyloxy group, etc.), alkylamino group (e.g. ethylamino group, dimethylamino group, jetanolamino group, etc.), arylamino group (e.g. anilino group, etc.),
Alkylcarbamoyl group (e.g. ethylcarbamoyl group, etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group etc.), alkanamide group (e.g. acetamido group etc.), arylacylamino group (e.g. benzamido group etc.)
"groups, etc.), alkylsulfonamide groups (e.g. methylsulfonamide groups, ethylsulfonamide groups, etc.), arylsulfonamide groups (e.g. benzenesulfonamide)"
), alkylsulfamoyl groups (e.g., N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), arylsulfamoyl groups (e.g., phenylsulfamoyl group, etc.), etc. It will be done.

When the aryl group represented by Ar has a substituent,
This substituent may have one or more, preferably one or two, and these substituents may be the same or different.

Typical specific examples of the magenta coupler of the present invention represented by the general formula [■] are shown below, but the present invention is not limited thereto.

Below is the margin [Example magenta coupler] L (2) (4) (5) (6) (7) (9) (10) (12) (13) (14) (15) (16) (17) t (18 ) (Eng. 9) (21) (22) (,23) (25) (26) (27) (28) (29) (30) (33) (35) (36) (37) (39) (4 (42) (43) (44) (45) The magenta coupler of the present invention represented by the general formula [■] can be synthesized by applying a conventionally known method.

In particular, the following synthetic methods are available for introducing a thio group as a leaving group into the 4-position of pyrazolone. That is, sulfenyl chloride was synthesized according to the method for synthesizing a DIR magenta coupler having an arylthio group or a heterocyclic thio group as a leaving group described in U.S. Pat. A method for reacting an equivalent pyrazolone coupler with an active methylene group, JP-A-4
As described in No. 9-62464, the 4-position of a pyrazolone coupler is dibrominated and reacted with about 3 times the mole of mercaptan, Research Disclosure? -(Research Disclosure)
Chem, Pharm, Bul.
1, 20.1862-1868 (1972), in which an orally equivalent pyrazolone coupler is reacted with an S-alkylthioisothiourea.

Typical synthesis examples of the magenta coupler represented by the general formula CI) of the present invention will be described below, but the present invention is not limited thereto.

Synthesis Example 11 Synthesis of Exemplary Coupler (12) 1-(3,4-
dichlorophenyl)-3-isobutanamido-5-pyrazolone 3]1 and P-dodecyloxyphenylmercaptan 29.59% in dimethylformamide (DMF) 500%
-, and bromine 162 was added dropwise thereto. After dripping, 8
It was heated to 0°C and reacted for 2 hours. The reaction solution was poured into ice water 2, and NacL was added to precipitate a solid. After filtering the solid and washing it with water, the solid was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain exemplified coupler (12).
I got 51. The F and D mass spectra of this coupler are M't = 605 (M"), and the melting point is 134~
The temperature was 137°C.

Synthesis Example 21 Synthesis of Exemplified Coupler 18) 1-(2゜3-
Dichlorophenyl)'-3-inbutanamide 5-pyrazolone 314 and P-dodecyloxyphenylmercaptan 29.5f were dissolved in dimethylformamide 500, and bromine IGt was added dropwise thereto. After dropping, the mixture was heated to -80°C and reacted for 2 hours. When the reaction solution was added to 2 tons of ice water, a solid precipitated. The solid was filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain the target product a7r. The FD mass spectrum of this target product was Δi/e = 605 (
The melting point was 131-137°C.

In order to produce a silver halide photographic light-sensitive material, the couplers of the present invention may be used alone or in combination of two or more. The coupler of the present invention can be used in both internal and external systems, but particularly good results can be obtained when it is incorporated into a silver halide emulsion.

When these couplers of the present invention are used as internal photographic materials, solutions or dispersions of these couplers are mixed with silver halide emulsions.

The timing of its addition is arbitrary, but usually after the second ripening,
Preferably, it is added to the emulsion.

At least one type of coupler of the present invention is contained in the silver halide emulsion. Its content is usually equivalent to 1 mole of silver halide! 00.07 to 0.7 mol, preferably 0.07 to 0.7 mol.
It is 1 to 0.4 mol. The coupler of the invention can also be contained in a layer adjacent to the silver halide emulsion layer.

The couplers of the present invention include dibutyl 7-talate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl 7-ether), N5N
- High-boiling water-immiscible organic solvents such as diethylcaprylamide, N,N-diethyllaurylamide, N,N-dibutyllauramide, or low-boiling organic solvents such as ethyl acetate, butyl acetate, or methanol, ethanol, acetone. photographic emulsions advantageously by dissolving them in either water-soluble organic solvents such as dioxane, tetra and dolofuran, or in high-boiling water-immiscible organic solvents and/or low-boiling organic solvents and/or water-soluble organic solvents. added to.

It is advantageous to use surfactants to help finely disperse the solution or dispersion of coupler i in the hydrophilic colloid used in the photographic emulsion.

After the coupler is dissolved in a suitable organic solvent, it is mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed in a high-speed rotary mixer or colloid mill, and then added directly into the silver halide emulsion, or After setting the dispersion liquid, it may be chopped, and after removing the low boiling point organic solvent by washing with water or the like, it may be added to the silver halide emulsion. The magenta coupler of the present invention can also be added by the Fischer dispersion method.

The silver halide photographic light-sensitive material using the magenta coupler according to the present invention may contain other known magenta couplers as necessary, specifically, pyrazolone type, pyrazolotriazole type, pyrazolinopenzimidazole type, indacylon. Couplers of the same type may be used in combination.

Among such magenta couplers, as the colored magenta turn 2-, a compound in which the active site of a colorless magenta coupler is substituted with arylazo or heteroarylazo is used.

The silver halide photographic light-sensitive material applied to the present invention can contain other color couplers together with the magenta coupler of the present invention in order to form a multicolor image, but yellow couplers that can be used in combination include: A combination of a benzoylacetanilide type yellow coupler, a pivaloylacetanilide type yellow coupler, and a 2-equivalent yellow coupler in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction may be used.

Cyan couplers include phenol or naphthol derivatives, and colored cyan couplers include arylazo-substituted phenoxy groups substituted directly or via an alkoxy group at the coupling position of the 2-less cyan coupler. Examples of such compounds include:

Furthermore, for the purpose of improving the sharpness, graininess, etc. of color images, so-called combining couplers, development inhibitor-releasing couplers (so-called DIR couplers), or those that do not form a dye by reaction with an oxidized form of a developing agent are used. It is also possible to use development inhibitor releasing materials. These may be used alone or in combination of two or more.

Moreover, the magenta coupler of the present invention is disclosed in Japanese Patent Publication No. 49-265
No. 85, U.S. Patent No. 3,486,890, Research Disc.
Closure) 12044, 12840, and the like. That is, by incorporating both the magenta coupler and the aromatic primary amine developing agent into a light-sensitive material and, after imagewise exposure, processing with an alkaline bath, black and white developer, or heat treatment, It is possible to perform color development and obtain a dye image with uniform gradation.

The silver halide photographic material applied to the present invention basically consists of a support and a light-sensitive emulsion layer, but depending on the type of silver halide photographic material, it may include a subbing layer, an intermediate layer,
Filter layer, anti-nolation layer, anti-curl layer,
Generally, auxiliary layers such as a back layer and a protective layer are appropriately combined and overlaid. In addition, the photosensitive layer itself is composed of a layer containing silver halide with relatively high sensitivity and a layer containing silver halide with relatively low sensitivity, which are spectrally sensitized to the same wavelength range or different wavelength ranges. may be configured.

The emulsion layer containing the coupler of the invention, other emulsion layers, or other auxiliary layers may contain reducing agents or antioxidants, such as sulfites (sodium sulfite, potassium sulfite, etc.), bisulfites (bisulfite), IJum, potassium bisulfite, etc.)
, hydroxylamines (hydroxylamine, N-methylhydroxylamine, N-phenylhydroxylamine, etc.), sulfinic acids (sodium phenylsulfinate, etc.), hydrazines (MSN'-dimethylhydrazine, etc.), reductones (ascorbic acid, etc.) , aromatic hydrocarbons having one or more hydroxyl groups (p-aminophenol, gallic acid, catechol, hyrogallol,
It is preferable to use resorcinol, 2,3-dihydroyacinaphthalene, etc.) in order to fully exhibit the effects of the present invention.

In order to further increase the stability of the dye image formed,
Alkyl-substituted hydroxynes and their alkoxy derivatives, bishydroxynes, polymeric hydroquinones, etc. may be contained alone or in an amount of 2 fiJi or more in the emulsion layer containing the coupler of the present invention or in a layer adjacent thereto. Furthermore, p-alkoxyphenols, 6-chromanol, 6,6'-dihydroxy-2,2'-spirochroman and their alkoxy or acyloxy derivatives can also be used.

The silver halide photographic light-sensitive material according to the present invention contains benzotriazoles, triazines, or It may contain a benzophenone compound or an acrylonitrile compound.

To form a photosensitive material, silver halide is dispersed in a suitable protective colloid to constitute a photosensitive layer, and the photosensitive layer and other auxiliary layers such as an intermediate layer, a protective layer, a filter layer, etc. The protective colloid used in the composition is generally alkali-treated gelatin, and other types include acid-treated gelatin, derivative gelatin, colloidal albumin, cellulose derivatives, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, which can be used alone or Used in combination.

The silver halide photographic material according to the present invention is produced by coating on a support that has good flatness and exhibits little dimensional change during the production process or processing. In this case, the support may be a plastic film, glass laminated paper, baryta paper, synthetic paper, or even a hard material such as a glass plate, metal, or ceramic.

These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion with the photographic emulsion layer, such as saponification treatment, corona discharge treatment, subbing treatment, setting treatment, etc. processing is performed.

The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention usually contains a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution.
It is made by mixing in the presence of a water-soluble polymer solution, such as gelatin. The silver halide may be any of the silver halide materials used in ordinary silver halide photographic materials, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver halide can be used.

These silver halide emulsions are made according to known or commonly used methods (side-lit single or double jet method, controlled double jet method, etc.), or are made by mixing two or more types of silver halide photographic emulsions that have been separately formed. It's okay. Furthermore, even if the crystal structure of silver halide grains is uniform inside, there are also grains with a layered structure with different interior and exterior layers, so-called conversion emulsions, Lippmann emulsions, covered grain emulsions, or grains that have been optically or It may also be chemically fogged.

Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are produced using the generally accepted ammonia method,
It can be prepared by various methods such as a neutral method and an acidic method. Further, the type of silver halide, content and mixing ratio of silver halide, average grain size, size distribution, etc. are appropriately selected depending on the type and use of the photographic light-sensitive material.

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers include noble metal sensitizers (potassium aurithiocyanate, ammonium chloroparadate,
potassium chloroplatenate, etc.), sulfur sensitizers (allylthiocarbamide, thiourea, cystine, etc.), selenium sensitizers (active and inactive selenium compounds, etc.), and reduction sensitizers (g1 tin salts, polyamines, etc.) It is roughly divided into four types. Silver halide emulsions can be chemically sensitized using these sensitizers alone or in combination as appropriate.

Furthermore, the photographic emulsion according to the present invention may contain cyanine,
Spectral sensitization or superchromatic sensitization can be performed by using cyanine dyes such as merocyanine and carbocyanine alone or in combination, or in combination with steryl dyes and the like.

These color sensitization techniques have been known for a long time, and the combination of dyes can be selected arbitrarily depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the silver halide photographic material. is possible.

The above silver halide emulsion contains 1-phenyl-5-mercaptotetrazole, 3-methylbenzothiazole, Heterocyclic compounds such as 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene.

Various compounds such as mercapto compounds and metal salts can be added.

Hardening of the emulsion is carried out according to conventional methods. The hardeners used are conventional photographic hardeners, such as aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, derivative compounds thereof such as acetals or bisulfite adducts, and methanesulfonic acid ester compounds. , mucochloric acid, mucohalogen acid compounds, epoxy compounds, aziridine compounds,
Active halogen compounds, malein, include imide compounds, active vinyl compounds, carbonimide compounds, incyanate compounds, N-methylol compounds, incyanate compounds, or chrome bright bread, zirconium sulfate, etc. Examples include hardening agents.

The above silver halide emulsion contains a surfactant alone or as a surfactant.
It may be added after mixing. Sokura is application assistant 81IIl
Il ile, 4, J! Jj bob +>AF ri?
k #b J/4- ttz; I/r white 4t
Ra? ILt: Applied to prevent adhesion, etc.

These surfactants include natural surfactants such as saponins,
Nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, other heterocycles, cationic surfactants such as phosphonium or sulfonium, and carboxylic acids. , anionic surfactants containing acidic groups such as sulfonic acid, phosphoric acid, sulfuric ester groups, and phosphoric ester groups, and amphoteric surfactants such as amino acids, amino sulfones, and sulfuric or phosphoric esters of amino alcohols.

The formation of color photographic images of the present invention is realized in various forms of light-sensitive materials. One method is to process a light-sensitive material having a silver halide emulsion layer containing a diffusion-resistant coupler on a support with an alkaline developer containing an aromatic primary amine color developing agent to make it water-insoluble or diffusion-resistant. This method leaves the coloring matter in the emulsion layer. In another embodiment, a light-sensitive material having a layer of ml/Mk needle coupler, I-compatible t halogen 4V d 5i δ11 on a support is used as an aromatic first
treated with an alkaline developer containing a class amine color developing agent to form a dye that is soluble and diffusible in an aqueous medium;
The image is transferred to an image-receiving layer made of another hydrophilic colloid.

That is, it is a diffusion transfer color type.

The silver halide photographic material of the present invention includes all kinds of silver halide photographic materials such as color negative films, color positive films, color reversal films, and color papers.

An embodiment of the silver halide photographic light-sensitive material according to the present invention includes a green-sensitive silver halide emulsion layer containing the magenta coupler of the present invention, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a cyan coupler. There is a multilayer, multicolor silver halide photographic light-sensitive material having a red-sensitive silver halide emulsion layer on a support. As the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion and red-sensitive silver halide emulsion in such a light-sensitive material, known ones can be used as appropriate.

After exposure to the silver halide photosensitive material Fi according to the present invention, a color image can be obtained by a commonly used color development method.

The basic steps in the negative-positive method include color development, bleaching, and fixing steps. The basic steps in the reversal method include development with a first developer, followed by exposure to white light or treatment with a bath containing a fogging agent, color development, bleaching, and fixing steps.

Each of these basic steps may be performed independently, or two or more steps may be performed in a single treatment using a processing liquid that has these functions. For example, a one-bath Cassie processing method containing a color developing agent, a ferric salt base white component, and a thiosulfate fixing component, or ethylenediaminetetodiacetate iron g
i) A one-bath bleach-fixing method containing a complex salt bleaching component and a thiosulfate fixing component.

Further, each process system can be divided into two or more processes as necessary, or a combination of processes such as color development, first fixing, and bleach-fixing is also possible. In addition to the above steps, various steps such as a pre-hardening bath, a neutralization tower, an image stabilizing bath, and water washing may be combined as necessary in the developing process. Although the treatment temperature may be lower than 18°C, it is often higher than 18°C. Especially ↓〈
The temperature range used is 20°C to 60°C. Approximately 30C to 60C is suitable for rapid processing. Note that it is not necessary that the set temperatures for the series of treatment steps be the same.

The color developing solution is an alkaline aqueous solution containing a developing agent and having a pH of 8 or more, preferably 9 to 12. The above-mentioned developing agent means a compound having a -class amine group on an aromatic ring and having the ability to develop exposed silver halide, or a precursor for forming such a compound. Preferred are p-phenylenediamine-based compounds, such as 4-amino-N,
N-diethylaniline, 3-methy/I/+ 4-amino-N, N-dietheraniline, 4-amino-N-ethel-N-β-hydroxyethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamide etheraniline, 3-methyl-4
-Amino-N-ethyl-N-β-methoxyethyl Ryoji1
J-N, 'J-B-Jλnsulfonamidoethyl-4-amino-N,N-diethylaniline, 3-methoxy-4-
Amino-N-A/-N-β-hydroxyethylaniline.

3-methoxy-4-amino-N-ethyl-N-β-methoxyetheraniline, 3-acetamido-4-amino-
N,N-diethylaniline, 4-amino-N,N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl -N-β-1[β-methoxyethoxy]ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, p-
Such as toluene sulfonate.

Various additives are added to the color developing solution as necessary. Main examples are H alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates, phosphates, etc.), pn adjusting or buffering agents (e.g. acetic acid, weak acids and bases such as boric acid, their salts, etc.) , development accelerators (e.g. pyridinium compounds, cationic compounds, potassium nitrate and nitrate 11), polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, polymer compounds with sulfide esters , other pyridine, ethanolamine, etc., organic amines, benzyl alcohol, hydrazine fx), anti-capri agents (e.g. alkali bromide, alkali iodide, yanitrobenzi imiguzole, mercaptobenzimidazole, 5-methylbenzo Triazole, 1-phenyl-5
- mercaptotetrazoles, rapid processing liquid compounds, thiosulfonyl compounds, phenazine N-oxides, benzothiazolium nitrobenzoate derivatives, etc.), stain or sludge inhibitors, heavy effect promoters, preservatives (e.g. sulphites) , acid sulfites, hydroxylamine hydrochloride, form sulfide, alkanolamine sulfide adducts, etc.).

A silver halide light-sensitive material containing the coupler of the present invention can be subjected to color development without impairing its practicality even in the presence of a competing coupler such as citradinic acid.

The silver halide photographic light-sensitive material according to the present invention develops color.

After development, bleaching can be carried out by a conventional method. This treatment may be done simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary.

Various compounds are used as bleaching agents, among which red blood salts; dichromate; iron (III), cobal)
(III), polyvalent metal compounds such as copper(II), in particular complex salts of these polyvalent metal cations with organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diaminoglobanoltetraacetic acid,
Metal complex salts and peracids such as citric acid, tartaric acid, and malic acid,
For example, alkyl peracids, persulfates, permanganates, hydrogen peroxide, etc., hypochlorites, such as chlorine, bromine, saran powder, etc. alone or in appropriate combinations are common6.
Furthermore, various additives including a bleaching accelerator can also be added to this processing solution.

After the color development process, conventional photographic processing is carried out, such as a stop solution containing an organic acid, a stop-fix solution containing an organic acid and a fixing component such as no-wart or ammonium thiosulfate, or a fixing solution containing a fixing component such as hypo or ammonium thiosulfate. A bleaching solution containing a ferric salt of an aminopolycarboxylic acid and an alkali halide as its main components, a ferric salt of an aminopolycarboxylic acid and a bleach-fixing solution containing a fixing component such as ammonium thiosulfate. Treatments selected from treatment with treatment liquids such as liquid, other stabilizing liquids, and treatments such as washing and drying may be carried out in an appropriate combination.

The coupler according to the present invention has a silver halide content in the emulsion that is several times smaller than that of ordinary silver halide light-sensitive materials.
It can also be used in photosensitive materials with a low silver content, ranging from 1/100 to 1/100.

In this way, for white-colored light-sensitive materials with a small amount of silver halide, the developed silver produced by one-color development is subjected to halide bleeding, and then color development is performed again to increase the amount of produced dye, a development processing method, peroxide, and cobalt complex salt. Alternatively, a sufficient dye image can be obtained by applying a developing method utilizing color intensification using sodium chlorite.

The silver halide photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, such as a syn7-based precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a phosphorus compound. Examples include acid amide derivative precursors, sugar amine reactant precursors, and urethane type precursors. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
No. 99, No. 2,507,114, No. 2.69!1
4234, British Patent No. 3,719,4.92, British Patent No. 803,783 Specification 1%, Publication No. 53-135628, British Patent No. 54-79.035, Research Disk, o-jar Magazine No. 15.159, No. 12,146,
It is published in No. 14924.

These aromatic primary amine color developing agents or precursors must be added in amounts that will provide sufficient color development during development. Although this amount varies considerably depending on the type of photosensitive material, it is generally photosensitive silver halide 1
D per mole between 0.1 and 5 moles, preferably 0.
It is used in a range of 5 mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc. It can be added as an emulsified dispersion using a high boiling point organic solvent such as phate, or as a latex polymer impregnated as described in Research Disclosure No. 14850.

(2) Specific Examples of the Invention The present invention will be described in detail below, but the embodiments of the present invention are not limited thereto.

Example 1 Exemplary couplers (2), (2), (2) and comparative couplers (A) to (G) each at 2 x 10-2 moles,
Tricresyl phosphate 15 and ethyl acetate were dissolved in a mixture of 15 and ethyl acetate by heating, and this solution was mixed with Alkanol B (alkylnaphthalene sulfonate, DuPont FF) 1. s
The mixture was mixed with 300 ml of an aqueous solution of 5ti gelatin containing rl, and emulsified and dispersed using a colloid mill. A dispersion of this coupler was prepared using green-sensitive silver iodobromide (6 moles of silver iodide, 94 moles of silver bromide).
), 1kf photographic emulsion containing 0.2 mol and gelatin 401
20 td of a 2% solution of 1,2-bis(vinylsulfonyl)ethane was added as a fibrillation agent, and the mixture was coated on a cellulose triacetic acid film base and dried. A gelatin protective layer was applied on this layer to prepare samples (1) to 0 of silver halide color photographic light-sensitive materials. The amount of silver coated on each sample at this time is 2P/n? Met.

After each of these samples was wedge-exposed in a conventional manner, they were subjected to the following processing steps and processing using the processing liquid composition shown below.

[Processing process (38℃)] Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.751 Anhydrous sodium sulfite 4.25f Hydroxylamine 1/2 sulfate 2. Or anhydrous potassium carbonate 375 Sodium bromide 1.3 f Nitrilotriacetic acid trisodium salt (monohydrate) 2,5
Potassium hydroxide 1.02 Add water to make 1 t, and use potassium hydroxide to pH 10.
, adjust to 0.

[Bleach solution composition]

Ethylenediaminetetraacetic acid ammonium salt ioo,
or ethylenediaminetetraacetic acid diammonium salt 1
0.0f ammonium bromide 150.0f glacial acetic acid 10.0g Add water to make 1 t and adjust the pH to 6.0 using aqueous ammonia.

[Fixer composition]

Ammonium thiosulfate 175. Of Anhydrous sodium sulfite 8.61 Sodium metasulfite 2.39 Add water to make 1 t and adjust to I) H6.0 using acetic acid.

[Stabilizing liquid composition]

Formalin (37% aqueous solution) 1.5 1111! Konigusokusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 75-Add water to make Xt.

The magenta dye image obtained above was measured using a densitometer (PD-
7B (manufactured by Konishi Roku Photo Industry Co., Ltd.) under green light, the color development sensitivity (expressed as a relative value when the sensitivity of sample Q was 100), fog, and maximum density were all calculated. The results are shown in Table 1 below.

Table 1 From the results shown in Table 1 above, samples (1), (2), (3), and (4) using the couplers of the present invention showed better results than samples (5) to 0 using the comparative couplers. 7'C has high color development sensitivity and maximum sensitivity, and also shows improved color development performance without an increase in Capri.

Comparative coupler [A] (compound described in U.S. Pat. No. 3,227; 554) Comparative coupler CB] C% Kosho 53-340
44) INtlljυutsnst Comparative coupler [D] (compound described in JP-A-55-29805) 1 0 Comparative coupler [F] (% Compound described in JP-A-57-4044) Comparative coupler [G] ( Compound described in JP-A No. 57-3585) 1 Example 2 After coating the samples (1) to (b) prepared in Example 1, a 1% formaldehyde aqueous solution was added in a dark room while leaving them unexposed. The sample was left in a sealed container for 3 days without contact with the liquid. These samples and an untreated sample for comparison were exposed and developed in the same manner as in Example 1, sensitivity and maximum density were measured, and formalin resistance % (treated sample/untreated sample x loo ) was calculated. The results obtained are shown in Table 2.

(The following is a blank space) Table 2 From the results shown in Table 2, samples (1) to (4) using the couplers of the present invention are different from samples (5) to (5) using the comparative couplers.
It can be seen that, compared to aυ, it is a coupler that is less susceptible to adverse effects such as a decrease in sensitivity and a decrease in maximum concentration due to lumaline and has excellent properties in preserving raw samples.

Example 3 A durability test was conducted using the dye image samples of Samples (1) to (11) prepared in Example 1vc. That is, as a heat resistance test, the above samples were kept at 40% RH and 80° C. for 2 weeks. In addition, as a light resistance test, the sample was treated with a xenon fade meter (6! was measured using green light, and the amount of residual dye was calculated.

Here, the residual dye value is expressed as a percentage of the density after the durability test in the exposed area where the dye density before the durability test is 1.0. In addition, regarding heat resistance and light resistance, we simultaneously measured the area with a density of 1.0 using blue light to determine the yellow contamination%.
(Concentration after durability test/Concentration before durability test x 100
) f: Calculated. The results obtained are shown in Table 3.

(Leaving space below) Table 3 From the results shown in Table 3, samples (1), (2), (3) and (4) using the coupler sound of the present invention are different from sample (5) using the comparative coupler. It can be seen that the coupler according to the present invention is an excellent coupler that is stable in terms of durability and does not easily cause a decrease in image density even when stored at υ, since yellow staining occurs less compared to υ.

Example 4 Exemplary couplers (6), (9), (a), (g) and comparative couplers (H), (I) each in 5 x 10'' moles,
Heat and dissolve in a mixture of 4-tricresyl phosphate and 12-ethyl acetate, and add 1.5% of this solution to Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
The mixture was mixed with 70 d of a 5% Latin aqueous solution containing F, and emulsified and dispersed using a colloid mill. A dispersion of this coupler was prepared using green-sensitive silver iodobromide (silver iodide 6 mol%, silver bromide 94 mol%) 02
This product was mixed with 1 powder of photographic emulsion containing 30F of gelatin, added with 20% solution of 1,2-bis(vinylsulfonyl)ethane as a hardening agent, coated on a cellulose triacetate film base, and dried. Sample (2) of silver halide color photographic material with a gelatin retention layer applied on top of the layer
〜αη was created. At this time, the amount of silver applied to each sample was 1
It was 2/-. These samples were each subjected to wedge exposure using a conventional method, and then subjected to the same treatment using the treatment solution used in Example 1. The magenta dye image obtained by this process has a density i? 't (PD-7R Konishiroku Photo Industry Co., Ltd. M) was used for measurement under green light, and a color density of 1 was determined. Note that this color density is expressed as a relative value, with the color density in sample) being 100. In addition, using a microdensitometer (PDM-5, manufactured by Konishiroku Photo Industry Co., Ltd.), the densities were 0.3 and 0.3 with a scanning aperture of 5 x 50μ.
6 part was scanned and the RM8 granularity at that time was determined from "Chemistry of Photography" (Shashin Kogyo Publishing), pp. 420-425, 198.
Transfer 100 samples (transfer) using the method described in 2015.
The relative granularity was calculated when The results show that the color development sensitivity is higher than that of the sample (A) and the sample used. Therefore, it can be seen that the magenta coupler of the present invention has high sensitivity and good granularity.

Comparative coupler (H) (compound described in JP-A-57-17950) Comparative coupler (I) Mu H3

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer provided on a support, wherein the silver halide emulsion layer contains at least a magenta coupler represented by the following general formula CI). A silver halide photographic light-sensitive material characterized by containing one type of silver halide photographic material. General formula CI) Ar (wherein, R8 represents an alkyl group, an aryl group, or a heterocyclic group, R2 and R3 each represent an alkyl group, and Ar represents an aryl group.)