JP2663355B2 - Silver halide color photographic light-sensitive material containing magenta coupler - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material containing a novel magenta dye-forming coupler. More specifically, a novel magenta dye having excellent solubility, dispersion stability, and spectral absorption characteristics, excellent raw sample preservation, high color density in the color development process, and excellent image preservation. The present invention relates to a silver halide color photographic light-sensitive material containing a neutral coupler.

[Background of the Invention]

As is well known, color subtraction color photography is based on the oxidation product of a color developing agent formed by reducing an exposed silver halide particle with an aromatic primary amine-based color developing agent and a yellow, cyan, or magenta dye. A color image is formed by oxidative coupling of a coupler that forms a silver halide emulsion in a silver halide emulsion. In these cases, as a yellow coupler for forming a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler for forming a magenta dye, pyrazolone-based, pyrazolinobenzimidazole-based, Compounds such as pyrazolotriazoles and indazolones are used, and compounds having phenol and naphtholic hydroxyl groups are used as cyan couplers for forming cyan dyes.

Among these couplers, the basic properties required for magenta couplers are not only that they form dyes but also that they have high solubility in high-boiling organic solvents or alkalis, and that they disperse in silver halide photographic emulsions. That the emulsion prepared has good storage stability, that the dye formed thereby has fastness to light, heat, moisture, etc., that the spectral absorption characteristics are good, It has various characteristics such as good transparency, high color density, and sharpness of the obtained image, but as far as the present inventors know, the conventionally known magenta No coupler has yet been found which satisfies all of the above required properties.

Various pyrazolone derivatives are known as magenta couplers, but these couplers have low coloring efficiency,
In the so-called four-equivalent coupler where the coupling active site is unsubstituted, the ratio of the coupler used for dye formation is about half,
The rest does not contribute to pigment formation.

As a method for improving the color-forming efficiency, a so-called two-equivalent magenta coupler in which a substituent (leaving group) that can be split off at the time of color development is introduced into the active position of the pyrazolone derivative is known. As these two-equivalent magenta couplers, for example, couplers having an acyloxy group as a leaving group are described in U.S. Pat.No. 3,311,476, and many other couplers having an aryloxy group, a thiocyano group, a 2-triazolyl group, an acylthio group or a thioacylthio group, etc. The use of these two-equivalent magenta couplers can cause significant color fogging, low coupling activity, and chemically unstable couplers. It changes to a substance that cannot develop color with the passage of time, and further involves any inconvenience such as many difficulties in synthesis.

Also, as previously described, as a two-equivalent coupler, U.S. Pat.
As disclosed in US Pat. Nos. 7,554 and 3,701,783, compounds in which the 4-position, which is the active position of a pyrazolone derivative, is substituted by an arylthio group or a heterocyclic thio group are also known. However, many of these known thio-substituted pyrazolone compounds include so-called development inhibitor releasing couplers (DIR
A mercaptan produced as a result of the coupling reaction, interacts with silver halide and has a function of delaying development.

For the purpose of preventing the strong development inhibiting effect of mercaptan, thio-substituted pyrazolone couplers having a mercaptan compound having a diffusion-resistant group as a leaving group are described in JP-B-53-34044 and JP-A-54-80744. However, such couplers have insufficient coupling activity, have a problem in the storage stability of the magenta dye formed, and have difficulty in application to general color photographic light-sensitive materials.

JP-A-55-62454 discloses a pyrazolone derivative.
Magenta couplers substituted at the position R'-S- (R 'represents straight or branched chain alkyl or aralkyl) are described. In these couplers, although the mercaptan compound which is eliminated after coupling has substantially no development inhibitory effect, it still has the disadvantage that the coupling activity of the coupler is low or the image storability, particularly the light resistance is poor. Have.

Further, magenta couplers capable of releasing certain arylthio groups described in JP-A-57-35858 and JP-A-63-25655 have improved coupling activity, image preservability, light resistance and the like to some extent. , And not enough,
Further improvements are desired.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide color photographic photosensitive material using a novel two-equivalent magenta coupler which has sufficient reaction activity and forms a dye in high yield without generating unnecessary fog or stain. It is to provide materials.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which a coupler is stable, and a color photograph having good coloring properties can be obtained even after storage for a long period of time. .

A third object of the present invention is to provide a color photographic light-sensitive material having a reduced amount of silver halide in a photographic emulsion layer containing the same and a reduced amount of the coupler by using a novel two-equivalent magenta coupler. An object of the present invention is to provide a color photographic light-sensitive material.

A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in image sharpness and graininess by forming a thin emulsion layer using a novel two-equivalent magenta coupler. .

A fifth object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining a robust dye image excellent in light resistance, heat resistance and moisture resistance using a novel two-equivalent magenta coupler. .

A sixth object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining a dye image having no influence on silver halide after color development processing.

A seventh object of the present invention is to provide a silver halide color photographic light-sensitive composition containing a novel two-equivalent magenta coupler which is excellent in solubility in an alkali or a high-boiling organic solvent and the like, dispersibility and stability in a silver halide color photographic emulsion. It is to provide materials.

An eighth object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent storage stability which does not cause abnormal color development by development even when left in a place where formalin is present before development.

A ninth object of the present invention is to provide a silver halide color photographic material using a novel two-equivalent magenta coupler which can be obtained by a simple production method.

[Configuration of the invention]

As a result of intensive studies, the present inventors have found that the above object can be achieved by a silver halide color photographic light-sensitive material containing a magenta dye-forming coupler represented by the following general formula [I].

Wherein R ₁ represents an aryl group, R ₂ represents an anilino group, an acylamino group, a ureido group or a carbamoyl group; R ₃ represents a sulfonyloxy group, an acyloxy group, a sulfamoyl group, a sulfonate group, an unsubstituted or R ₄ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, a sulfonyloxy group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfone Represents an acid ester group, a nitro group and a sulfonamide group. n represents an integer of 1 to 4. Hereinafter, R ₁ , R ₂ , R ₃ and R ₄ in the general formula [I] will be described in detail.

R ₁ represents an aryl group, including an aryl group having a substituent, and is preferably a phenyl group. Examples of the substituent introduced into the phenyl group include a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group (eg, methyl, ethyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), aryloxy Groups (eg, phenyloxy, naphthyloxy, etc.), acylamino groups (eg, benzamide, α- (2,4-di-t-amylphenoxy) butyramide, etc.), and sulfonylamino groups (eg, benzenesulfonamide, n-hexadecane) A sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (eg, n-butylcarbamoyl, phenylcarbamoyl, etc.), a sulfonyl group (eg, methylsulfonyl, n-dodecylsulfonyl, Benzenesulfonyl, etc.), acylo Shi group, an ester group, a carboxyl, sulfo, cyano, nitro, and the like.

Further specific examples of R ₁ include phenyl, 2,4,6-trichlorophenyl, pentachlorophenyl, pentafluorophenyl, 2,4,6-trimethylphenyl, 2-chloro-4,6-dimethylphenyl 2,6-dichloro-4-methylphenyl, 2,4-dichloro-6-methylphenyl, 2,5
-Dichlorophenyl, 2,3-dichlorophenyl, 2,4-dichloro-6-methoxyphenyl, 2,6-dichloro-4-
Methoxyphenyl, 2,4-dichloro-4- [α- (2,4-
Di-t-amylphenoxy) acetamido] phenyl and the like.

R ₂ is an anilino group (eg, anilino, 2-chloroanilino, 2,4-dichloroanilino, 2,4-dichloro-5-methoxyanilino, 4-cyanoanilino, 2-chloro-5
-[Α- (2,4-di-t-amylphenoxy) butylamide] anilino, 2-chloro-5- (3-octadecenylsuccinimide) anilino, 2-chloro-5-n-tetradecanamidoanilino , 2-chloro-5- [α-
(3-t-butyl-4-hydroxyphenoxy) tetradecanamido] anilino, 2-chloro-5-n-hexadecanesulfonamidoanilino, 2-chloro-5- [α
-(4-t-octylphenoxy) butanamide] anilino, etc.), acylamino group (for example, n-tetradecaneamide, α- (3-pentadecylphenoxy) butylamide, 3- [α- (2,4-di-t- Amylphenoxy)
Acetamide] benzamide, benzamide, 3-acetamidobenzamide, 3- (3-n-dodecylsuccinimide) benzamide, 3- (4-n-dodecyloxybenzenesulfonamido) benzamide and the like, a ureido group (for example, methylureido, phenyl) Ureido, 3
-[Α- (2,4-di-t-amylphenoxy) butylamido] phenylureido or the like or an alvamoyl group (for example, n-tetradecylcarbamoyl, phenylcarbamoyl, 3- [α- (2,4-di-t -Amylphenoxy)
Acetamido] phenylcarbamoyl etc.].

R ₃ is a sulfonyloxy group (for example, methanesulfonyloxy group, t-butylsulfonyloxy group, benzenesulfonyloxy group, etc.), an acyloxy group (for example, acetoxy group, benzoyloxy group, ethoxycarbonyloxy group, t-butylcarbamoyloxy group) Etc.), a sulfamoyl group (eg, t-butylaminosulfonyl group, phenylaminosulfonyl group, etc.), a sulfonic acid ester group (eg, ethoxysulfonyl group, t-octylsulfonyl group, phenoloxysulfonyl group, etc.) and unsubstituted or 4-position Only represents a sulfonamide group having a substituent only (for example, a p-toluenesulfonamide group or the like).

Desirable R ₃ is a sulfamoyl group, an unsubstituted or sulfonamide group having a substituent only at the 4-position.

R ₄ is a hydrogen atom, a halogen atom (eg, chlorine, bromine, iodine, etc.), a hydroxy group, or an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, -Butyl group, tetradecyl group, etc.),
An alkoxy group (eg, methoxy group, ethoxy group, tetradecyloxy group, etc.), an aryl group (eg, phenyl group,
Naphthyl group), nitro group, sulfonyloxy group (for example, methanesulfonyloxy group, t-butylsulfonyloxy group, benzenesulfonyloxy group, etc.), acyloxy group (for example, acetoxy group, benzoyloxy group, ethoxycarbonyloxy group, t Butylcarbamoyloxy group, etc.), carbamoyl groups (eg, methylcarbamoyl group, ethylcarbamoyl group, n-butylcarbamoyl group, t-butylcarbamoyl group, t-amylcarbamoyl group, n-octylcarbamoyl group, phenylcarbamoyl group, etc.), Sulfamoyl group (for example, t-butylaminosulfonyl group, phenylaminosulfonyl group, etc.), sulfonic acid ester group (for example, ethoxysulfonyl group, t
-Octylsulfonyl group, phenoxysulfonyl group, etc.)
And a sulfonamide group (for example, a methanesulfonamide group, a t-butylsulfonamide group, an n-decylsulfonamide group, a toluenesulfonamide group, etc.).

Wherein R ₃ and R ₄ include those having a substituent,
Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a hydroxyl group, a nitro group, a cyano group, a hydroxycarbonyl group, and an alkyl group (a linear or branched alkyl group; Group, ethyl group, propyl group, butyl group, amyl group, octyl group,
Decyl 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.), alkylcarbonyl Amino group (eg, undecylcarbonylamino group, dodecylcarbonylamino group, etc.), arylcarbonylamino group (eg, naphthoylamino group, toluoylamino group, benzoylamino group, etc.), alkylsulfonamide group (eg, dodecylsulfone Amide group), an arylsulfonamide group (eg, a benzenesulfonamide group), an alkylaminosulfonamide group (eg, a dimethylaminosulfonamide group), an arylaminosulfonamide group (eg,
Anilinosulfonamide group, etc.), alkylcarbamoyl group (eg, hexadecylcarbamoyl group, etc.), arylcarbamoyl group (eg, phenylcarbamoyl group, etc.), sulfonyl group (eg, methylsulfonyl group, n
-Dodecylsulfonyl group and the like), alkyloxycarbonyl group (for example, dodecyloxycarbonyl group and the like), aryloxycarbonyl group (for example, phenoxycarbonyl group and the like), alkylsulfamoyl group (for example, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group), arylsulfamoyl group (eg, phenylsulfamoyl group) and the like.

Further, n in the general formula [I] is an integer of 1 to 4, preferably an integer of 1 to 2. When n is 1, the substituent represented by R ₄ can be located at any position of the phenyl group with respect to R _{3 in the} general formula [I], but is preferably in the para position. When n is 2, the R ₄ may be the same or different and are preferably the same, and in this case, the substituent represented by R ₄ may be located at any position relative to R _{3 of} the phenyl group. And preferably in positions 2 and 4.

Specific examples of typical compounds of the magenta coupler represented by the general formula [I] and used in the present invention are shown below, but the present invention is not limited thereto.

The coupler of the present invention represented by the above general formula can be synthesized by a conventionally known method. In particular, the following is a synthetic method for introducing a thio group as a leaving group at the 4-position of pyrazolone. That is, according to the synthesis method of DIR magenta coupler having an arylthio group or a heterocyclic thio group as a leaving group described in U.S. Pat.Nos. 3,227,554 and 3,701,783, 4-equivalent pyrazolone having sulfenyl chloride and an active methylene group. Method for reacting a coupler, JP-A-49
As described in -62464, a method in which the 4-position of a pyrazolone coupler is dibrominated and reacted with about three-fold mol of mercaptan, as described in Research Disclosure 13806 (1975). A method of dropping bromine in the presence of a four-equivalent pyrarozone coupler and a mercaptan or disulfide.

The magenta coupler of the present invention can be similarly easily produced according to the following synthesis method of compound (1).

Synthesis Example-1 [Synthesis of Compound (1)] 1- (2,4,6-trichlorophenyl) -3- [2-chloro-5- (3-octadecenylsuccinimide) anilino] -4- ( Synthesis of 2-tert-butylcarbamoylphenylthio) -5-pyrazolone 1- (2,4,6-trichlorophenyl) -3- [2-chloro-5- (3-octadecenylsuccinimide) anilino]- 73.7 g (100 mmol) of 5-pyrazolone and 3-tert-
Butylcarbamoylphenyl disulfide 20.8g (50mmo
l) 16.8 g (105 mmo) in 400 ml of dimethylformamide solution
A solution obtained by dissolving the bromine in l) in 100 ml of dimethylformamide is added dropwise and reacted at 90 ° C. for 4 hours. After completion of the reaction, the reaction solution is poured into cold water, and the generated precipitate is separated by filtration. Further recrystallization of this precipitate with 300 ml of acetonitrile 73.6 g
(78 mmol) of the compound (1) is obtained.

¹ H-NMR spectrum and mass spectrum (M ⁺ = 941)
Confirmed the above structure.

Synthesis Example-2 [Synthesis of Compound (2)] 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-tetradecylamidoanilino) -4- (2-
Synthesis of tert-butylsulfonamido-5-methylphenylthio) -5-pyrazolone 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-tetradecylamidoanilino) -5-pyrazolone 61.4 g (100 mmol) and 25.8 g (50 mmol) of 2-tert-butylsulfonamido-5-methylphenyl disulfide
16.8g (105mmol) in 400ml of dimethylformamide solution
Of bromine in 100 ml of dimethylformamide was added dropwise and reacted at 90 ° C. for 5 hours. After completion of the reaction, the reaction solution is poured into cold water, and the generated precipitate is separated by filtration. further,
The precipitate was recrystallized with 300 ml of ethanol to give 65.4 g (75
mmol) of the compound (2).

¹ H-NMR spectrum and mass spectrum (M ⁺ = 869)
Confirmed the above structure.

As described above, the coupler used in the present invention can be easily produced by applying a conventionally known method.

In order to produce a silver halide photographic material, even if only one type of coupler used in the present invention is used alone,
Also, two or more kinds may be used in combination. The coupler used in the present invention is used in any of the inner method and the outer method,
In particular, good results can be obtained when used in a photographic component layer. In the present invention, the "photographic constituent layer" refers to a silver halide emulsion layer and non-photosensitive hydrophilic colloid layers such as an intermediate layer, an undercoat layer and a protective layer. The coupler used in the present invention is preferably contained in a silver halide emulsion layer among these photographic constituent layers.

When the couplers used in the present invention are contained in a silver halide emulsion layer of a photographic light-sensitive material of the internal formula, a solution or dispersion of these couplers is used by mixing with a silver halide emulsion. The timing of the addition is arbitrary, but it is usually preferable to add it to the emulsion after the completion of the second ripening.

When at least one of the couplers used in the present invention is contained in the silver halide emulsion layer, the content is usually 0.007 to 0.7 mol, preferably 0.01 to 0.7 mol per mol of silver halide.
~ 0.1 mol. Further, the couplers used in the present invention can also be contained in the non-photosensitive layer adjacent to the silver halide emulsion layer, in which case, the gelatin 1 m ² per 0.001 to 10 mmol, containing preferably a range of 0.1 to 0.01 millimoles Let it.

As a method for adding the coupler used in the present invention to the photographic constituent layer, a conventionally known method can be adopted. That is, the coupler used in the present invention is dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, N, N-diethylcaprylamido, N, N-diethyllauramide, N, N-dibutyllauryl. High-boiling organic solvents that are immiscible with water, such as amides, low-boiling organic solvents such as ethyl acetate and butyl acetate, or aqueous organic solvents such as methanol, ethanol, acetone, dioxane, and tetrahydrofuran It is advantageously added to photographic emulsions by dissolving in organic solvents and / or low boiling and / or water-soluble organic solvents.

It is advantageous to use a surfactant to help the coupler solution or dispersion used in the present invention finely disperse in the hydrophilic colloid used in the photographic emulsion. After dissolving the coupler in a suitable organic solvent, it is mixed with a gelatin aqueous solution containing a surfactant, and then emulsified and dispersed by a high-speed rotary mixer or a colloid mill, and then directly added to a silver halide emulsion, or After the dispersion is set, the dispersion is cut, and the low boiling organic solvent is removed by washing with water or the like, and then added to the silver halide emulsion. Further, the magenta coupler used in the present invention can be added by a Fischer dispersion method.

As the surfactant that can be used in the present invention, those usually used in this technical field are used, for example, an anion such as an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, an alkyl sulfonate, or an alkyl sulfate. Surfactants, nonionic surfactants such as steroidal saponins, alkyl oxide derivatives and glycidol derivatives, amino acids,
Amphoteric surfactants such as aminoalkylsulfonic acids and alkylbetaines, and cationic surfactants such as quaternary ammonium salts can be used. Specific examples of these surfactants are described in "Surfactant Handbook" (Sangyo Tosho, 1966) and "Emulsifiers / Emulsifiers, Research and Technical Data Collection" (Science & Technology, 1978).

The magenta coupler, cyan coupler, and yellow coupler according to the present invention are usually used in this technical field.For example, a silver halide photographic light-sensitive material using a magenta coupler may optionally include other conventionally known magenta couplers. Specifically, pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, indazolone-based couplers and the like may be used in combination.

Among such magenta couplers, as the colored magenta coupler, an arylazo-substituted or heteroarylazo-substituted compound at the active site of the colorless magenta coupler is used.

The silver halide photographic light-sensitive material used in the present invention includes:
In addition to the magenta coupler of the present invention for forming a multicolor image, other dye-forming couplers such as a yellow coupler and a cyan coupler can be contained. Examples of the yellow coupler that can be used together with the magenta coupler of the present invention include benzoylacetanilide-type and pivaloylacetoanilide-type yellow couplers, and further, the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction. Equivalent yellow couplers and the like can be mentioned.

Examples of the cyan coupler include phenol or naphthol derivatives, and examples of the colored cyan coupler include compounds in which an arylazo-substituted phenoxy group is directly or via an alkoxy group substituted at the coupling position of the colorless cyan coupler. Can be. Further, a colored cyan coupler as a masking coupler or a type of a colored cyan coupler in which a dye flows out into a processing bath by a reaction with an oxidation product of a color developing agent can be used.

The above-mentioned yellow and cyan couplers other than the magenta coupler used in the present invention generally contain silver halide 1 in the emulsion layer.
0.007 mol to 0.7 mol, preferably 0.01 mol to 0.
Use 1 mole.

Furthermore, in order to improve the sharpness and granularity of a color image, a development in which a dye is not formed by a reaction with a so-called competing coupler, a coupler which releases a development inhibitor (a so-called DIR coupler) or an oxidized developing agent. It is also possible to use inhibitor releasing substances. These may be used alone or in combination of two or more.

The magenta coupler used in the present invention is a Research Disclosure 1204.
4, 12840, etc. can also be used. That is, the magenta coupler of the present invention and an aromatic primary amine developing agent are both contained in a photosensitive material, and after imagewise exposure, processing with an alkaline bath and a black and white developer,
Alternatively, by performing a heat treatment, color development can be performed, and a dye image having a uniform gradation can be obtained.

The silver halide photographic light-sensitive material applied to the present invention basically comprises a support and a light-sensitive emulsion layer. However, depending on the type of the silver halide photographic light-sensitive material, an undercoat layer, an intermediate layer, a filter layer In general, auxiliary layers such as an antihalation layer, an anti-curl layer, a back layer, and a protective layer are appropriately combined and laminated. The photosensitive layer itself is, for example, a layer containing a relatively high-sensitivity silver halide and a layer containing a relatively low-sensitivity silver halide spectrally sensitized to the same wavelength region or different wavelength regions. May be configured.

It is preferable to use a reducing agent or an antioxidant in the emulsion layer containing a coupler, other emulsion layers, or other auxiliary layers used in the present invention in order to sufficiently exert the effects of the present invention.

Further, for the purpose of increasing the stability of the formed dye image, an emulsion layer containing the coupler used in the present invention, or
In the adjacent layer, alkyl-substituted hydroquinones and alkoxy derivatives thereof, bishydroquinones, polymer hydroquinones, and the like can be contained alone or in combination of two or more. Furthermore, p-alkoxyphenols, 6-chromanol, 6,6'-dihydroxy-2,2'-spirochroman and their alkoxy or acyloxy derivatives are likewise used.

The silver halide photographic light-sensitive material according to the present invention comprises, in its constituent layers (for example, a protective layer, an intermediate layer, an emulsion layer, and a back layer).
Benzotriazoles, triazines, benzophenone-based compounds or acrylonitrile-based compounds as ultraviolet absorbers.

In order to form a light-sensitive material, silver halide is dispersed in a suitable protective colloid to constitute a photographic constituent layer of a light-sensitive silver halide emulsion layer. In addition, it may have a non-photosensitive layer, for example, a photographic component layer such as an intermediate layer, a protective layer, and a filter layer. As the protective colloid forming these photographic constituent layers, alkali-treated gelatin is generally used, and other acid-treated gelatin, derivative gelatin, colloidal albumin, cellulose derivative or polyvinyl alcohol, synthetic resins such as polyvinylpyrrolidone, and the like are used. These may be used alone or in combination of two or more.

The silver halide photographic light-sensitive material according to the present invention is produced by coating on a support having good flatness and having little dimensional change during the production process or processing. As the support in this case, a plastic film, plastic laminated paper, baryta paper, synthetic paper, or a hard material such as a glass plate, metal, or ceramics can be used.
These supports can be subjected to various surface treatments such as a hydrophilic treatment for the purpose of improving the adhesion to the photographic emulsion layer, for example, saponification treatment, corona discharge treatment, undercoating treatment, set treatment. Are performed.

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

These silver halide emulsions are prepared according to known and conventional methods (eg, single or double jet method, control double jet method, etc.). Further, two or more kinds of silver halide photographic emulsions formed separately may be mixed.
Further, the crystal structure of silver halide grains may be uniform to the inside, or may have a heterogeneous layer structure between the inside and the outside, or may be called a conversion emulsion, a Ritzmann emulsion, a covered grain emulsion, or an optical or grain emulsion. It may be chemically fogged. In addition, 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 a particle may be used. These photographic emulsions can be prepared by various methods such as generally accepted ammonia method, neutral method, and acidic method. The type of silver halide, silver halide content and mixing ratio, average grain size, size distribution and the like are appropriately selected according to 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 chloroparatinate, etc.), sulfur sensitizers (allylthiocarbamide, thiourea, cystine, etc.), selenium sensitizers (activity and Inert selenium compounds) and reduction sensitizers (stannous salts, polyamines, etc.). The silver halide emulsion can be chemically sensitized with these sensitizers alone or in combination as appropriate.

Further, the photographic emulsion according to the present invention performs spectral sensitization and supersensitization by using cyanine dyes such as cyanine, merocyanine, and caribocyanine, alone or in combination, or in combination with a styryl dye, if necessary. be able to.

These color sensitization techniques have been known for a long time, and the selection of the combination of the dyes depends on the wavelength range to be sensitized,
The sensitivity can be arbitrarily determined according to the purpose and use of the silver halide photographic material.

In the above silver halide emulsion, 1-phenyl-5-mercaptotetrazole, 3-methylbenzothiazole, and the like are used in the production process of the silver halide photographic light-sensitive material, in order to prevent a decrease in sensitivity and generation of fog during storage or processing. Various compounds such as heterocyclic compounds such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, mercapto compounds and metal salts can be added.

Hardening of the emulsion is carried out according to a conventional method. Hardening agents used are ordinary photographic hardening agents, for example, aldehyde compounds such as formaldehyde, glyoxal, glutaraldehyde and derivatives thereof such as acetal or sodium bisulfite adducts, and methanesulfonic acid ester compounds. , Mucochloric acid, mucohalic acid compounds, epoxy compounds, aziridine compounds,
Inorganic hardeners such as active halogen compounds, maleic imide compounds, active vinyl compounds, carbonimide compounds, isoxazole compounds, N-methylol compounds, isocyanate compounds, or chromium ban or zirconium sulfate. I can give it.

Surfactants may be added alone or in combination to the silver halide emulsion. They are used for coating aids, emulsification / dispersion, sensitization, improvement of photographic properties, antistatic, antiadhesion and the like.

In the present invention, formation of a color photographic image is realized in various forms of photosensitive materials. One of the methods is to treat a light-sensitive material having a silver halide emulsion layer containing a diffusion-resistant coupler on a support with an alkaline developing solution containing an aromatic primary amine color developing agent to form a water-insoluble or diffusion-resistant material. This is a method in which an acidic dye is left in the emulsion layer. In another embodiment, a light-sensitive material having a silver halide emulsion layer combined with a diffusion-resistant coupler on a support is treated with an alkaline developer containing an aromatic primary amine color developing agent to form an aqueous medium. The dye is solubilized to form a diffusible dye, which is transferred to an image receiving layer made of another hydrophilic colloid. That is, it is a diffusion transfer color system.

The silver halide color photographic light-sensitive material of the present invention includes all kinds of silver halide photographic light-sensitive materials such as a color negative film, a color positive film, a color reversal film, and a color paper.

As one embodiment of the silver halide color photographic light-sensitive material of the present invention, a green-sensitive silver halide emulsion layer containing a magenta coupler, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a cyan coupler used in the present invention. There is a multilayer multicolor silver halide photographic material having a red-sensitive silver halide emulsion layer on a support. Known blue-sensitive silver halide emulsions, green-sensitive silver halide emulsions and red-sensitive silver halide emulsions in such light-sensitive materials are appropriately used.

The silver halide color photographic light-sensitive material of the present invention, after exposure,
A color image can be obtained by a commonly used color developing method. The basic steps in the negative-positive method include color development, bleaching and fixing steps. The basic steps in the reversal method include developing with a first developer and then giving white light exposure, or processing in a bath containing a fogging agent, and color developing, bleaching and fixing steps.

Although each of these basic steps may be performed independently,
In some cases, one or more steps may be performed in a single process using a processing solution having these functions. For example, a one-bath color processing method containing a color developing agent and a ferric salt bleaching component and a thiosulfate fixing component, or a one-bath bleach-fixing containing an ethylenediaminetetraacetate (III) complex salt bleaching component and a thiosulfate fixing component. There are methods.

In addition, each step can be processed two or more times as required, or a combination of processing such as color development, first fixing, and bleach-fixing is also possible. In the developing step, various steps such as a pre-hardening bath, a neutralizing bath, an image stabilizing bath, and a washing with water are combined as necessary. The processing temperature may be lower than 18 ° C, but is often higher than 18 ° C. Particularly, the range of 20 ° C to 60 ° C is often used. About quick processing
30 ° C to 60 ° C is suitable. It is not necessary that the set temperatures of a series of processing steps be the same.

The color developing solution is an aqueous alkaline solution containing a developing agent and having a pH of 8 or more, preferably 9 to 12.

If necessary, various additives commonly used in this technical field are added to the color developing solution. Examples thereof include an alkali agent, a pH adjusting or buffering agent, a development accelerator, an antifoggant, a stain or sludge inhibitor, a multilayer effect accelerator, and a preservative.

The silver halide photographic light-sensitive material containing a coupler used in the present invention can be subjected to color development processing without impairing the practicality even in the presence of a competitive coupler such as citrazic acid.

The silver halide color photographic light-sensitive material of the present invention can be subjected to bleaching processing by a conventional method after color development processing. This process may be performed simultaneously with or separately from fixing. This processing solution can be used as a bleach-fix bath by adding a fixing agent as needed. Further, various additives such as a bleaching accelerator can be added to the treatment liquid.

After the color development processing, it is selected from ordinary photographic processing, for example, processing with a processing solution such as a stop solution containing an organic acid, a fixing solution, a bleaching solution, a bleach-fixing solution, other stabilizing solutions, and washing and drying. What is necessary is just to perform each process suitably combining.

The coupler used in the present invention can be used for a light-sensitive material having a low silver content in which the amount of silver halide in the emulsion is several-hundredth to one-hundredth of that of a normal silver halide light-sensitive material. Can be used.

For a color photosensitive material having a reduced amount of silver halide as described above, after a developed bleaching of the developed silver produced by the color developer, a color developing is performed again to increase a generated dye amount, and a developing method of peroxide, cobalt, A sufficient dye image can be obtained by applying a development processing method utilizing color intensification using complex silver or sodium chlorite.

The silver halide color photographic light-sensitive material of the present invention may contain the above-described color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof.

The color developing agent precursor is a compound capable of generating a color developing agent under alkaline conditions, a Schiff-based precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a butyric imide derivative precursor, a phosphoric amide derivative precursor, Sugar amine reactant precursors and urethane type precursors are exemplified.

[Examples] Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to the examples.

Example 1 2 × 10 ^-2 mol of the exemplified coupler (9) was dissolved by heating in a mixture of 15 ml of dibutyl phthalate and 30 ml of ethyl acetate, and this solution was dissolved in 5% containing 1.5 g of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). Gelatin aqueous solution 300m
l and emulsified and dispersed in a colloid mill. A dispersion of this coupler is treated with green-sensitive silver iodobromide (silver iodide 6 mol%,
Photographic emulsion containing 0.2 mol of silver bromide (94 mol%) and 40 g of gelatin
After mixing with 1 kg, 20 ml of a 2% solution of 1,2-bis (vinylsulfonyl) ethane was added as a hardening agent, and the mixture was applied on a cellulose triacetate film base and dried. Sample 1 of silver halide photographic material was prepared by coating a gelatin protective layer on this layer.
Was prepared. At this time, the coating amount of silver of Sample 1 was 2 g / m ² . Further, Comparative Samples 2 and 3 were prepared in exactly the same manner as described above, except that Comparative Couplers (A) and (B) described later were used instead of the above-described exemplary coupler (9).

These samples 1, 2 and 3 were each subjected to wedge exposure by a conventional method, and then processed with the following processing steps and a developing solution having the following processing solution composition.

[Processing process (38 ° C)] Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization bath 1 minute 30 seconds [Color developer composition] 4-amino- 3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylami 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g nitrilotriacetic acid · 3 Sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 and adjust to pH 10.0 with potassium hydroxide.

[Composition of bleaching solution] Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water is added to adjust the pH to 1, and the pH is adjusted to 6.0 using aqueous ammonia.

[Fixing solution composition] Ammonium thiosulfate (5% aqueous solution) 162.0 g Anhydrous sodium sulfite 12.4 g Water was added to 1 and the pH was adjusted to 6.5 using acetic acid.

[Composition of stabilizing solution] Formalin (37% aqueous solution) 5.0 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

The magenta dye image obtained as above is measured with a densitometer (PDA
-65 Konica Corporation) with green light.
The color development sensitivity (expressed as a relative value when the sensitivity in sample 4 is 100), fog and maximum density were calculated, and the results are shown in Table 1.

Comparative Coupler (A) (Compound described in US Pat. No. 3,227,554) Comparative coupler (B) (compound described in JP-A-55-62454) From the results shown in Table 1, the sample (1) using the coupler of the present invention has higher coloring sensitivity and the highest density as compared with the samples (2) and (3) using the coupler for comparison.
In addition, it was found that the color developing performance was improved without any increase in fog.

Example 2 Illustrative coupler (1) and comparative couplers (C) and (D) 2 × 10 ^-2 mol each were dissolved in a mixture of 15 ml of dibutyl phthalate and 30 ml of ethyl acetate by heating, and this solution was dissolved in alkanol B (alkyl). Naphthalene sulfonate, manufactured by DuPont) 1.5m, 5% gelatin aqueous solution 300m
l and emulsified and dispersed in a colloid mill.

This coupler dispersion was mixed with 5 × 10 ^-2 mol of green-sensitive silver chlorobromide (20 mol% of silver chloride and 80 mol% of silver bromide) and 3 kg of a photographic emulsion containing 110 g of gelatin, and 1 was used as a hardener. 80 ml of a 2% solution of 2-bis (vinylsulfonyl) ethane was added, coated on a polyethylene-coated paper support and dried. Samples 4 to 6 of color photographic light-sensitive materials were prepared by coating a gelatin protective layer on this layer. Samples 4-6 at this time
Was 0.5 g / m ² . These samples 4, 5
After wedge exposure of each of 6 and 6 in the usual manner,
Processing was performed using the following processing steps and a developing solution having the following processing solution composition.

[Processing step (33 ° C)] Color development 3 minutes 30 seconds Bleaching and fixing 1 minute 30 seconds Water washing 3 minutes [Color developing solution composition] 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl ) -Aniline sulfate 4 g Benzine alcohol 10.0 ml Hydroxyamine sulfate 2 g Potassium carbonate 25.0 g Potassium bromide 0.2 g Anhydrous sodium sulfite 2.0 g Diethylene glycol 3 ml Add water to 1 to adjust the pH to 10.0.

[Bleach-fixing solution composition] Ethylene diaminetetraacetate sodium salt 60.0 g Ammonium thiosulfate 100 g Sodium bisulfite 100 g Sodium metabisulfite 3.0 g Water was added to 1 to adjust the pH to 6.6.

The obtained magenta dye image was measured with green light in the same manner as in Example 1, and the color development sensitivity (indicated by the relative sensitivity with the sample (10) being 100) fog and the maximum density were calculated. In addition, a test for light resistance was performed. The light fastness was measured by applying an ultraviolet absorption filter to each of the obtained images and applying it to a xenon fade meter.
The residual concentration after the time exposure was expressed as 100 before the exposure. Table 2 shows the results.

Comparative coupler (C) (compound described in JP-B-53-34044) Comparative coupler (D) (compound described in JP-A-53-34044) From the results shown in Table 2, the samples (6), (7) and (8) using the magenta coupler of the present invention had higher color sensitivity and the highest density than the samples (9) and (10) using the comparative coupler. It can be seen that there is no increase in fog and the light resistance is excellent.

Example 3 Samples 1 to 3 prepared in Example 1 were applied and left unexposed for 3 days in a sealed container containing a 1% aqueous formaldehyde solution without exposure to light in a dark room. These samples and an untreated sample for comparison were exposed and developed in the same manner as in Example 1 to measure the sensitivity and the maximum density, and the% formalin resistance (treated sample / untreated sample ×
100) was calculated. Table 3 shows the obtained results.

From the results shown in Table 3 above, Sample 1 using the coupler according to the present invention is less susceptible to adverse effects such as a decrease in sensitivity and a maximum concentration due to formalin than Samples 2 and 3 using the comparative coupler. It can be seen that the coupler has excellent sample storability.

Example 4 (Preparation of silver halide emulsion) Six kinds of silver halide emulsions shown in Table 4 were prepared by a neutral method and a simultaneous mixing method.

After the completion of chemical sensitization, each of the silver halide emulsions was prepared by using STB-1 shown below as an emulsion stabilizer in a silver halide emulsion.
5 × 10 ^-3 mol was added per mol.

(Preparation of silver halide color photographic light-sensitive material sample) Next, a silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on polyethylene resin coated paper containing anatase type titanium oxide.

(1) 20 mg of gelatin, 5 mg of silver-sensitive silver halide emulsion (Em-1) in silver amount, and 3 mg of dioctyl in which 8 mg of Y-coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved A layer containing a phthalate coupler solvent.

(2) 12 mg of gelatin, 0.5 mg of 2,5-di-t-octylhydroquinone and 4 mg of an ultraviolet absorber (U-1 and U
-2) An intermediate layer containing 2 mg of a dibutyl phthalate ultraviolet absorbent solvent in which is dissolved.

(3) 18 mg of gelatin, 4 mg of silver-sensitive silver halide emulsion (Em-2) in terms of silver amount, 5 mg of the exemplified coupler shown in Table 5 as M-coupler, 2 mg of antioxidant and 0.2 mg of A layer containing 2.5 mg of dioctyl phthalate coupler solvent in which 2,5-di-t-octylhydroquinone is dissolved.

(4) An intermediate layer containing the same composition as in (2).

(5) 16 mg of gelatin, 4 mg of silver-sensitive silver halide emulsion (Em-3) in terms of silver amount, and 2.0 mg of 3.5 mg of C-coupler and 0.1 mg of 2,5-di-t-octylhydroquinone dissolved therein A layer containing a tricresyl phosphate coupler solvent.

(6) A gelatin protective layer containing 9 mg of gelatin.

A coating aid was added to each of the layers (1) to (6), and a gelatin crosslinking agent was further added to the layers (4) and (6).

As the ultraviolet absorbers of (2) and (4), U-1 and U
An equimolar mixture of -2 was used.

As the antioxidant of (3), di-t-pentylhydroquinone-di-octyl ether was used.

Each of the obtained samples was subjected to wedge exposure by a conventional method, and then processed according to the following color development processing steps.

The obtained magenta dye image was measured with green light in the same manner as in Example 1, and the color development sensitivity (display by relative sensitivity with sample 20 being 100, fog and maximum density were calculated).

The obtained sample was irradiated with a xenon fade meter for 15 days, and the light fastness was evaluated by determining the residual ratio (%) of the dye image at an initial density of 1.0.

[Processing process] Color development 34.7 ± 0.3 ° C 45 seconds Bleaching and fixing 34.7 ± 0.5 ° C 45 seconds Stabilization 30 ° C to 34 ° C 90 seconds Drying 60 ° C to 80 ° C 60 seconds [Color developing solution] Pure water 800 ml Triethanolamine 8 g N, N-diethylhydroxylamine 5 g Potassium chloride 2 g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline / sulfate 5 g Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1 g Set to 1 and adjust to pH 10.2.

[Bleaching-fixing solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Add water to make the total volume 1 and add potassium carbonate or Adjust to pH 5.7 with glacial acetic acid.

[Stabilizing solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 g Add water to make 1 and adjust to pH with sulfuric acid or potassium hydroxide.
Adjust to 7.0.

Table 5 shows the M-couplers used in the layer (3) and the results.

From the results shown in Table 5, Samples 7 and 8 using the magenta coupler of the present invention had higher color sensitivity and maximum density than Samples 9 and 10 using the comparative coupler, and showed no increase in fog. It can also be seen that the light resistance is excellent.

Example 5 The blue-sensitive silver halide emulsion of (1) of the silver halide color photographic light-sensitive material prepared in Example 4 was emulated with Em-4 in Table 4.
Next, the green-sensitive silver halide emulsion of (3) was added to Em-5 of Table 4
Then, the red-sensitive silver halide emulsion of (5) was added to Em-6 shown in Table 4.
Samples 11 to 16 of silver halide color photographic light-sensitive materials were produced in the same manner as in Example 4 except that the couplers shown in Table 6 were used as M-couplers.

The obtained sample was used as a sensitometer KS-7 (manufactured by Konica Corporation).
After performing the same exposure as in Example 2 after the wafer exposure, the same measurement as in Example 4 was performed. The results are shown in Table 6.

From the results shown in Table 6, Samples 11 to 14 using the magenta coupler of the present invention have higher color developing sensitivity and maximum density than Samples 15 and 16 using the comparative coupler, and have no increase in fog and light fastness. It can be seen that the properties are also excellent.

[Effects of the Invention] In the present invention, by using a specific magenta coupler, a high color sensitivity and a maximum density can be obtained, the raw sample preservability is excellent, and the light fastness of the obtained image is improved. A silver halide color photographic light-sensitive material can be obtained.

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Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material containing a magenta dye-forming coupler represented by the formula [I]. General formula [I] Wherein R ₁ represents an aryl group, R ₂ represents an anilino group, an acylamino group, a ureido group or a carbamoyl group; R ₃ represents a sulfonyloxy group, an acyloxy group, a sulfamoyl group, a sulfonate group, an unsubstituted or R ₄ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, a sulfonyloxy group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfone Represents an acid ester group, a nitro group and a sulfonamide group. n represents an integer of 1 to 4. ]