JPH02151857A - Silver halide color photographic sensitive material containing magenta coupler - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having high sensitivity for color development, and high maximum density as well as improved preservability of green sample and improved light resistance by using a specified magenta coupler in a silver halide color photographic sensitive material. CONSTITUTION:A coupler expressed by the formula I and being capable of forming a magenta dye stuff is incorporated into a silver halide color photographic sensitive material. In the formula I, R1 is an aryl group R2 is an anilino, acylamino, ureido group, etc.; R3 is a sulfonyloxy, acyloxy, carbamoyl group, etc.; R4 is an H atom, halogen atom, hydroxy group, alkyl group, etc.; n is an integer 1-4. Thus, a silver halide color photographic sensitive material having high reaction activity, being capable of forming a dye stuff in high yield without generating unnecessary fog nor stain, and forming a stable coupler, is obtd., which provides a color photograph with superior color developability just as it is used immediately after manufacture even if it is used after preservation for a long time.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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, solubility,
A halogenated compound containing a novel magenta dye-forming coupler that has good dispersion stability and spectral absorption characteristics, excellent raw sample preservation, high color density in the color development process, and excellent image preservation. This invention relates to silver color photographic materials.

[Background of the invention]

As is well known, in subtractive color photography, an aromatic primary amine color developer reduces exposed silver halide grains to produce oxidation products of the color developer and yellow color.
Color images are formed by oxidative coupling of cyan and magenta dye-forming couplers in silver halide emulsions. In these cases, as a yellow coupler for forming a yellow dye, a compound having an active methylene group at -r is used, and as a magenta coupler for forming a magenta dye, a pyrazurone type, a bilazolino hentzi Compounds such as midazole, pyrazolotriazole, and indasilone are used, and as cyan couplers for forming cyan dyes, compounds having phenol and naphtholic hydroxyl groups are used.

Among these couplers, the basic properties required for magenta couplers are not only to form a dye, but also to have high solubility in high-boiling press solvents or alkalis, and to be compatible with silver halide photographic emulsions. Good dispersibility and stability; the produced emulsion has good storage stability; the dye formed thereby has fastness to light, heat, moisture, etc.; and good spectral absorption characteristics. It has various characteristics such as good transparency, high color density, and clear images, but to the best of the inventors' knowledge, it has not been known in the past. No magenta coupler has yet been found that satisfies all of the two required properties.

Various pyrazolone derivatives are known as magenta couplers, but these couplers have low coloring efficiency, and in the case of so-called four-equivalent couplers in which the camping active site is unsubstituted, the ratio 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-equivalent 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-equivalent magenta couplers, for example, couplers having an acylthio group as a leaving group are described in U.S. Pat. Many U.S. patents disclose couplers having a However, they are physically unstable and change over time into substances that cannot develop color, and furthermore, they have many disadvantages in synthesis.

Additionally, as a two-equivalent coupler, U.S. Patent No. 3,
227, No. 554 and No. 3.7OL783, compounds in which the active position 4 of a pyrazolone derivative is substituted with an arylthio group or a heterocyclic thio group are also known. However, many of these known thio-substituted pyrazolone compounds are so-called development inhibitor-releasing couplers (DIR couplers), in which the mercaptan produced as a result of the coupling reaction interacts with silver halide and has the function of delaying development. It is something.

In order to prevent the strong development-inhibiting effect of mercapkun, a thio-substituted pyrazolone coupler having a mercaptan compound having a diffusion-resistant group as a leaving group was published in Japanese Patent Publication No. 53-34044.
No. 54-80744, but
Such couplers do not have sufficient coupling activity, and the resulting magenta dye has problems in storage stability, 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'-3- (R' represents a straight or branched alkyl or aralkyl). In these couplers, the mercaptan compound released after coupling does not have a substantial development inhibitory effect, but they have drawbacks such as low coupling activity of the puller and poor image storage stability, especially light resistance. have.

Furthermore, JP-A-57-35858 and JP-A-63-25
Although the magenta coupler that leaves a certain arylthio group described in No. 655 has some improvement in coupling activity, image storage stability, light resistance, etc., it is still not sufficient, and further improvements are desired. There is.

[Object of the invention] Therefore, the first object of the present invention is to have sufficient reaction activity,
The object of the present invention is to provide a silver halide color photographic light-sensitive material using a novel two-equivalent magenta coupler that forms a dye in high yield without causing unnecessary fog or staining.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which the coupler is stable and, even when stored for a long period of time, it is possible to obtain color photographs with good color development properties, just as they were immediately after production. .

A third object of the present invention is to use a novel two-equivalent magenta coupler to obtain a color photographic light-sensitive material in which the amount of silver halide in the photographic emulsion layer containing the coupler and the amount of coupler used are reduced. Our objective is to provide color photographic materials.

A fourth object of the present invention is to provide a silver halide color photographic material with excellent image sharpness and graininess by thinning the emulsion layer using a new two-equivalent magenta coupler. .

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

A sixth object of the present invention is to provide a silver halide color photographic light-sensitive material from which a dye image unaffected by silver halide can be obtained after color development.

A seventh object of the present invention is to provide a silver halide color photographic sensitizer containing a novel equivalent magenta coupler which has excellent solubility in alkali or high boiling point solvents, etc., and excellent dispersibility and stability in silver halide color photographic emulsions. The purpose is to provide materials.

An eighth object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent storage stability and does not develop abnormal color during development even if it is left in a place where Polmarine 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 that can be obtained by a simple manufacturing method.

[Structure of the invention]

As a result of extensive research, the present inventors have discovered 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 formula (1).

- Formula (1) [wherein R1 represents an aryl group, R2 represents an anilino group, an acylamino group, a ureido group, or a carbamoyl group, and R3 represents a sulfonyloxy group, an acyloxy group,
It represents a carbamoyl group, a sulfamoyl group, a sulfonic acid ester group, a sulfonamide group, and R4 is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, a sulfonyloxy group, an acyloxy group,
Represents a carbamoyl group, sulfamoyl group, sulfonic acid ester group, 21, colloquial term, sulfonamide group.

n represents an integer from 1 to 4. ] Hereinafter, R1, R2, R3, and R6 in -formula CI) will be explained in detail.

R4 represents an aryl group, which may have a substituent, and is preferably a phenyl group. Examples of substituents introduced into the phenyl group include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (
(e.g., methyl, ethyl, etc.), alcohol-1 di groups (e.g., methoxy, ethoxy, etc.), aryloxy groups (e.g., phenyloxy, naphthyl tertiary, etc.), acylamino groups (e.g., henzamide, α-(24 -di-L-amylphenoxy)butyramide, etc.), sulfonylamino groups (e.g., Hensensulfonamide, n-hexadecanesulfonamide, etc.), sulfamoyl groups (e.g., methylsulfamoyl, phenylsulfamoyl, etc.), Carbamoyl groups (e.g. n-)ethylcarbamoyl, etc.), sulfonyl groups (e.g. methylsulfonyl,
rl-dodecylsulfonyl, Hensensulponyl, etc.),
Acyloxy group, ester group, carboxyl, sulfo,
Examples include cyano and nitro.

Furthermore, specific examples of R1 include phenyl, 24.6-
1-'J chlorphenyl, pentachlorphenyl, pentafluorophenyl, 2,4.6-1-limethylphenyl, 2-chloro-4,6-dichlorophenyl, 26-dichloro-4-methylphenyl, 24 -dichloro-6-methylphenyl, 2.5-dichlorophenyl, 23-dichlorophenyl, 24-dichloro-6-methoxyphenyl, 26-dichloro-4-methoxyphenyl, 2.6-dichlorphenyl-4-[α -(2,4-di-monoamylphenoxy)acetamido]phenyl and the like.

R2 is an anilino group (e.g., anilino, 2-chloroanilino, 2,4-dichloroanilino, 24-dichloro-5
-methoxyanilino, 4-cyanoanilino, 2-chloro-5-[α-(2,4-di-L-amylphenoxy)butyramide]anilino, 2-chloro-5-(3-occudecenylsuccinimito)anilino , 2-chloro-5-n
Tetradecanamide anilino, 2-chloro-5[α-(
3-Butyl-4-hydroxyphenoxy)tetradecanamide]anilino, 2-chloro-5-n-hexadecanesulfonamideanilino, 2-chloro-5-(α-
(4-L-octylphenoxy)butanamide]anilino, etc.), acylamino groups (for example, n-tetradecanamide, α-(3-pentadecylphenoxy)butyramide, 3-[α-(2,4-di-t-amyl) phenoxy)
Acetamide benzamide, henzamide, 3-acetamidobenzamide, 3-(3n-dodecylnaxinimide) henzamide, 3(4-n-dodecyloxybenzenesulfonamide) henzamide, etc.), ureido group (
For example, methylureido, phenylureido, 3-[α
(2,4-di-t-amylphenoxy)butyramide]
phenylureido, etc.) or carbamoyl group (e.g., n
-tetradecylcarhamoyl, phenylcarbamoyl,
3-[α-(2,4-Gs.

amylphenoxy)acetamide [phenylcarbamoyl, etc.].

R3 is an acyloxy group (e.g., a sulfonylonylbonyloxy group, a butylsulfonyloxy group, a benzenesulfonyloxy group, etc.) (e.g., an acetonyloxy group, a benzoyloxy group, an ethoxycarbonyloxy group, an L-butylcarbamoyloxy group, etc.) , carbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, n-butylcarbamoyl group, L-
Butylcarbamoyl group, cycloamylcarbamoyl group, n
-octylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (e.g. L-butylaminosulfonyl group, phenylaminosulfonyl group, etc.), sulfonic acid ester group (e.g. ethoxysulfonyl group, -octylsulfonyl group, phenoxysulfonyl crystal, etc.) ) and sulfonamide groups (e.g. methanesulfonamide) groups,
L-butylsulfonamide group, n-decylsulfonamide group, toluenesulfonamide group, etc.).

Preferred R3 is a carbamoyl group, a sulfamoyl group,
It is a sulbonamide group.

R4 is a hydrogen atom, a halogen atom (e.g., chlorine, bromine, iodine, etc.), a hydroxy group, an alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, or a t-butyl group). group, tetradecyl group, etc.),
Alkoxy groups (e.g. methoxy group, ethoxy group,
radecyloxy group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, t-butylsulfonyloxy group, benzenesulfonyloxy group) etc.) Acyloxy groups (e.g., acetoxy group, benzoyloxy group, hydroxycarbonyloxy group, L-butylcarbamoyloxy group, etc.), carbamoyl groups (e.g., methylcarbamoyl group, ethylcarbamoyl group, n-butylcarbamoyl group, L- butylcarbamoyl group, L-amylcarbamoyl group, n-octylcarbamoyl group, phenylcarhamoyl group, etc.), sulfamoyl group (e.g. t-butylaminosulfonyl group, phenylaminosulfonyl group, etc.), sulfonic acid ester group (e.g. ethoxysulfonyl group, L-octylsulfonyl group, phenonitocissulfonyl group, etc.) and sulfonamide groups (e.g. methanesulfonamide group, L-butylsulfonamide group, n-decylsulfonamide group, toluenesulfonamide group, amide group, etc.).

The above R3 and R4 further include those having a substituent, and examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a human 1:J xyl group, a 21.4 group, a cyano group, Hydroxycarbonyl group, alkyl group (
A straight-chain or branched argyl group, such as a methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, decyl group, dodecyl group, he-1-zabutyl group,
octadecyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc.), alkylcarbonylamino group (e.g., undecylcarbonylamino group), group, dodecylcarbonylamino group, etc.), arylcarbonylamino group (e.g.
(naphthoylamino group, toluoyl amino group, hendiylamino group, etc.), alkylsulponamide group (e.g.
dodecylsulfonamide group, etc.), arylsulfonamide group (e.g., Hensensulfonamide group, etc.), alkylaminosulfonamide group (e.g., dimethylaminosulfonamide group, etc.), arylaminosulfonamide group (e.g., anilinosulfonamide group, etc.), alkylcarbamoyl group (e.g., hexadecyl hamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), sulfonyl group (e.g., methylsulfonyl%, n-dodecylsulfonyl group, etc.), Argyloxycarbonyl group (e.g. dodecyloxycarbonyl group, etc.)
, aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylsulfamoyl group (e.g.,
N-methylsulfamoyl group, NN-dimethylsulfamoyl group, etc.), arylsulfamoyl group (eg, phenylsulfamoyl group, etc.), and the like.

Moreover, rl in the above formula [I] is an integer of 1 to 4, preferably an integer of 1 to 2. When n is 1, R4
The substituent represented by can be located at any position of the phenyl group with respect to R3 in formula (1) above, but is preferably at the rose position.

When n is 2, R4 may be the same or different, preferably the same, and the substituent represented by R4 in this case may be located at any position relative to R1 of the phenyl group. possible, preferably 2nd and 4th place.

Specific examples of typical magenta couplers represented by general formula [I] 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 formula can be synthesized by 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, U.S. Patent No. 3,227.554, U.S. Patent No. 3.7
A method for reacting a sulfenyl chloride with a four-equivalent pyrazolone coupler having an active methylene group in accordance with the method for synthesizing a DIR magenta coupler having an arylthio group or a heterocyclic thio group as a leaving group described in OL783, JP-A No. As described in No. 49-62464, a method in which the 4-position of a pyrazolone coupler is dibrominated and reacted with about 3 times the molar amount of mercapkun, Research Discl.
13806 (1975), in which bromine is added dropwise in the presence of a four-equivalent pyrazolone coupler and a mercaptan or disulfide.

Typical synthesis examples of the magenta coupler of the present invention will be shown below, but the present invention is not limited thereto.

Synthesis Example-1 (Synthesis of Exemplary Compound (1)) 1-(2,4,
6-dolychlorphenyl)-3[2-chloro-5-(3
-octadecenylsuccinimide)anilino) 4
(2tert-butylcarhamoylphenylthi 15th
-Synthesis of pyrazolone■-(2,4,6-1-lychlorphenyl)-312-
Chlor-5-(3-octadecenylsuccinimide)anilino]-5-pyrazolone 73.7g (100mmol
l) and 3 20.8 g of tert-butylcarbamoyl phenyl disulfide (50 mmol of dimethylpolamide g (105 mmoffi) of bromine at 100 mI!
．． Drop the solution dissolved in dimethylborumamide at 90°C.
React for 4 hours at °C. After the reaction is complete, the reaction solution is poured into cold water, and the precipitate formed is filtered off. Further, this precipitate was recrystallized with 300 mρ of acetonitrile.7 3.
6 g (70 mmol) of Exemplary Compound (1) is obtained.

’　Ii　-　NMR spectrum (M'=941) confirmed the above structure.

Synthesis Example (2) (Synthesis of Exemplary Compound (13)) 1 (2,4
, 6-dolychlorphenyl)-3(2-chloro-5-tetradecylamide anilino) 4-(2-tert
-butylsulfonamide 5-methylphenylthio)-5
-Synthesis of pyrazolone 1-(2,4,6-1-lychlorphenyl)-3(2-
61.4 g (100 mmof) of chloro-5-tetradecylamidoanilino)-5-pyrazolone and 2 te
A solution of 25.8 g (50 mmol!,) of rt-butylsulfonamide-5-methylphenyl disulfide in 400 ml of dimethylformamide! , 16.8 g (1
05mmoI! , ) dissolved in 100 mff1 of dimethylformamide was added dropwise and reacted at 90°C for 5 hours. After the reaction is complete, the reaction solution is poured into cold water, and the precipitate formed is filtered off. Furthermore, this precipitate was recrystallized with 300 rnl of ethanol to give 65°4 g (
Exemplary compound (13) of 75 mmoffi) is obtained.

'H-NMR spectrum and mass spectrum (
The above structure was confirmed by M''=869).

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

In order to produce a silver halide photographic light-sensitive material, one type of coupler used in the present invention may be used alone or two or more types may be used in combination. The coupler used in the present invention can be used in either an internal or external method, but particularly good results can be obtained when it is incorporated in a photographic constituent layer. In the present invention, the term "photographic constituent layers" refers to non-photosensitive hydrophilic colloid layers such as silver halide emulsion layers, interlayers, subbing layers, and protective layers. The coupler used in the present invention is preferably contained in the silver halide emulsion layer among these photographic constituent layers.

When the couplers used in the present invention are incorporated into the silver halide emulsion layer of an internal photographic light-sensitive material, a solution or dispersion of these couplers is mixed with the silver halide emulsion. Although the timing of its addition is arbitrary, it is usually preferable to add it to the emulsion after the second ripening is completed.

When at least one kind of coupler used in the present invention is contained in the silver halide emulsion layer, the content is usually 0.007 to 7 mol, preferably 0.07 to 0.07 mol, preferably 0.07 to 0.07 mol, per mol of silver halide. O1 to 0.1 mole. The coupler used in the present invention can also be contained in a non-light-sensitive layer adjacent to the silver halide emulsion layer, in which case 1 m2 of gelatin
0.001 to 10 mmol, preferably 0.1 to 0
．． It is contained in a range of 0.1 mmol.

When the coupler used in the present invention is incorporated into the photographic constituent layer, conventionally known methods can be employed. That is, the couplers used in the present invention include dibutyl phthalate, dibutyl phthalate, triphenyl phosphate, triccidyl phosphate, dioctyl butyl phosphate, N,N-diethyl laurylamide,
Water-immiscible high-boiling organic solvents such as N,N-diethyl laurylamide, N,N-dibutyl laurylamide, low boiling point organic solvents such as ethyl acetate, butyl acetate, or aqueous solvents such as methanol, ethanol, acetone, dioxane, and tetrahydrofuran. It is advantageously added to the photographic emulsion by dissolving it either in an organic solvent or in a water-immiscible high-boiling organic solvent and/or a low-boiling and/or water-soluble organic solvent.

It is advantageous to use surfactants to assist in finely dispersing the coupler solution or dispersion used in the invention into 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 means such as washing with water, it may be added to the silver halide emulsion. The magenta coupler used in the present invention can also be added by the Fischer dispersion method.

Surfactants that can be used in the present invention include:
Usually used in this technical field,
The list includes anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfate esters, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives, and glycidol conductors. Surfactants, amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids and alkyl betaines, 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 and Emulsification Equipment, Research and Technical Data Collection'' (Science Panronsha, 1978).

The magenta coupler, cyan coupler, and yellow coupler according to the invention are those commonly used in this technical field. Specifically, magenta couplers may be used in combination with pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, indasilone-based couplers, and the like.

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

The silver halide photographic material used in the present invention may contain other dye-forming couplers, such as yellow couplers and cyan couplers, in addition to the magenta coupler of the present invention in order to form multicolor images. Examples of yellow couplers that can be used with the magenta coupler of the present invention include penzoylacetanilide F-type and pivaloylacetanilide-type yellow couplers, and those in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction. Examples include 2-equivalent yellow couplers.

Examples of the cyan coupler include phenol or naphthol conductors, and examples of the colored cyan coupler include compounds in which an arylazo-substituted phenoxy group is substituted directly or via an alkoxy group at the coupling position of the colorless cyan coupler. be able to.

It is also possible to use a colored cyan coupler as a masking coupler or a type of colored cyan coupler in which a dye flows out into the processing bath by reaction with an oxidation product of a color developing agent.

The above yellow color other than the magenta coupler used in the present invention,
The cyan coupler generally contains Q, OG 7 to 0.7 mole, preferably 0.01 mole per mole of silver halide in the emulsion layer.
mol to 0.1 mol is used.

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

Furthermore, the magenta coupler used in the present invention is disclosed in Research Disclosure (Research Disclosure).
12044, 12840, and the like. That is,
The magenta coupler of the present invention and the aromatic primary amine developing agent are both contained in a light-sensitive material, and after imagewise exposure, color development is carried out by processing with an alkaline bath, black and white developer, or heat treatment, A dye image with good lsi tonality can be obtained.

The silver halide photographic material applied to the present invention basically consists of a support and a light-sensitive emulsion layer, or depending on the type of silver halide photographic material, a subbing layer, an intermediate layer,
Generally, auxiliary layers such as a filter layer, an antihalation layer, an anticurl layer, a backing layer, and a protective layer are appropriately combined and layered. In addition, the photosensitive layer itself may be overlaid with, for example, 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. It may be configured as follows.

In order to fully exhibit the effects of the present invention, it is preferable to use a reducing agent or antioxidant in the emulsion layer containing the coupler used in the wood invention, other emulsion layers, or other auxiliary layers.

Furthermore, for the purpose of increasing the stability of the dye image formed, alkyl-substituted hydroquinones and their alkoxy derivatives, bishydroquinones, and polymeric hydroquinones may be present in the emulsion layer containing the coupler used in the present invention or in a layer adjacent thereto. etc. may be contained alone or in combination of 2ff1 or more. 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, benzophenone compounds, or acrylonitrile-based compounds as ultraviolet absorbers in its constituent layers (e.g., protective layer, intermediate layer, emulsion layer, pack layer, etc.). It may also contain a compound.

Form a photosensitive material. Therefore, silver halide is dispersed in a suitable protective colloid to constitute a photographic constituent layer of a light-sensitive silver halide emulsion layer. It may have photographic constituent layers such as optical layers, such as intermediate layers, protective layers, filter layers, etc. As protective colloids forming these photographic constituent layers, alkali-treated gelatin is generally used, as well as acid-treated gelatin, derivative gelatin, colloidal albumin, cellulose derivatives, or synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. These may be used alone or in combination of two or more.

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, plastic 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, and setting treatment. Processing such as the following 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 solution of a water-soluble polymer such as gelatin. The silver halide may be any halogen compound used in ordinary silver halide photographic materials, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Silver can be used.

These silver halide emulsions are prepared according to known and commonly used methods (for example, single or double jet method, controlled double jet method, etc.). Further, separately formed silver halide photographic emulsions of 2ffI or more may be mixed. Furthermore, even if the crystal structure of the silver halide grains is similar to the inside, there are also grains with a layered structure in which the inside and outside are different, so-called conversion emulsions, Lippmann emulsions, etc.
It may be a covered grain emulsion or one that has been optically or chemically fogged in advance. 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 can be prepared by various generally accepted methods such as an ammonia method, a neutral method, and an acid 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 silver herodanide emulsion described above can be sensitized with a chemical sensitizer. Chemical sensitizers include noble metal sensitizers (potassium aurithiocyanate, ammonium chloroparadate,
(potassium chloroplatinate, etc.), before sulfur sensitization (furyl≠ocarbamide, thiourea, cystine, etc.)'L selenium sensitizers (active and inactive selenium compounds, etc.) and reduction sensitizers (stannic salts, polyamines, etc.) ) is roughly divided into 4 fl. 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 by using them in combination with styryl dye or the like.

These color sensitization techniques have been known for a long time, and the combination of dyes can be arbitrarily determined 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, Various compounds such as heterocyclic compounds such as 4-hydroxy-6-methyl 1.3,3a and 7-chitrazaindene, 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 sodium bisulfite adducts, and methanesulfonic acid ester compounds. , mucochloric acid, mucohalogen acid compounds, epoxy compounds, aziridine compounds, active halogen compounds, maleic acid imide compounds, active vinyl compounds, carbonimide compounds, isoxazole compounds, N-methylol compounds, Examples include isocyanate compounds and inorganic hardeners such as chromium chloride and zirconium sulfate.

A surfactant may be added alone or in combination to the above silver halide emulsion. They are coating aids, emulsifying and dispersing agents,
It is applied for sensitization, improvement of photographic properties, antistatic, and antiadhesion.

In the present invention, the formation of color photographic images is realized in various forms of photosensitive 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 dye in the emulsion layer. In another form, a light-sensitive material having a silver halide emulsion layer in combination with a diffusion-resistant coupler on a support is processed with an alkaline developer containing an aromatic primary amine color developing agent into an aqueous medium. A soluble and diffusible dye is formed and transferred to an image-receiving layer made of another wood-philic colloid. That is, it is a diffusion transfer color type.

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

An embodiment of the silver halide color photographic light-sensitive material of the present invention includes a green-sensitive silver halide emulsion layer containing a magenta coupler used in 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 of the silver halide color photographic material of 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 color processing method containing a color developing agent, a ferric salt bleaching component, and a thiosulfate fixing component, or an ethylenediaminetetraacetate (iron
II+) -bath bleach-fixing method containing a complex salt bleaching component and a thiosulfate fixing component.

Further, each step can be divided into two or more times as necessary, or a combination of color development, first fixing, and bleach-fixing can be performed. Incidentally, in the development process, the above-mentioned various processes such as a pre-hardening bath, a neutralization tower, an image stabilizing bath, and water washing are combined as necessary. Processing temperature is 1.8
Although it may be less than 18°C, it is often 18°C or higher. A temperature range of 20°C to 60°C is particularly frequently used. A temperature of about 30°C to 60°C is suitable for rapid processing. Note that it is not necessary that the set temperatures of the consecutive 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.

If necessary, various additives commonly used in this technical field are added to the color developing solution.

Examples include alkaline agents, pH adjusting or buffering agents, development accelerators, antifoggants, stain or sludge inhibitors, genus 1 effect accelerators, and preservatives.

The silver halide photographic material containing the coupler used in 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.

After the color development process, the silver halide color photographic light-sensitive material of the present invention can be subjected to a bleaching process in a conventional manner. 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. Furthermore, various additives including a bleaching accelerator can be added to the processing solution.

After the color development process, the photographic material is selected from ordinary photographic processing, such as processing using a stop solution containing an organic acid, a fixing solution, a bleaching solution, a bleach-fixing solution, and other processing solutions such as a stabilizing solution, washing with water, and drying. Each process may be performed in an appropriate combination.

The coupler used in the present invention can also be used in light-sensitive materials with a low silver content, where the amount of silver halide in the emulsion is several to one-hundredth of that of ordinary silver halide light-sensitive materials. Can be used.

For color light-sensitive materials with a reduced amount of silver halide, the developed silver produced by color development is subjected to halide bleaching, and then color development is performed again to increase the amount of dye produced.IAI! l! A sufficient dye image can be obtained by applying a method, a development process using color intensification using peroxide, a cobalt silver complex, or sodium chlorite, and a method.

The silver halide color 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 capable of producing a color developing agent under alkaline conditions, such as a Schiff base type precursor ζ polyvalent metal ion complex precursor with an aromatic aldehyde derivative, a butaric acid imide derivative precursor, a phosphoric acid amide derivative precursor, Sugar amine reactant precursors include usetan type precursors.

[Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the Examples.

Example 1 2 x 10 i moles of exemplary coupler (7) were heated and dissolved in a mixture of 15 mJ2 of dibutyl phthalate and 30 mJ2 of ethyl acetate, and this solution was added to 5% gelatin containing 1.5 g of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). It was mixed with an aqueous solution of 300n+42 and emulsified and dispersed in a colloid mill. A dispersion of this coupler was mixed with I kg of a photographic emulsion containing 0.2 mol of green-sensitive silver iodobromide (6 mol % silver iodide, 94 mol % silver bromide) and 40 g gelatin. - 20n+J2 of a 2% solution of bis(vinylsulfonyl)ethane was added, coated on a cellulose triacetate film base, and dried. A gelatin protective layer was coated on this layer to prepare Sample 1 of a silver halide photographic material. At this time, the amount of silver coated on Sample 1 was 2 g/
It was m2. Furthermore, Sample 2 and Sample 3 were prepared in exactly the same manner as above using Example Couplers (15) and (20) in place of Example Coupler (7).

Further, as comparative samples, Comparative Samples 4 and 5 were prepared in exactly the same manner as above, using Comparative Couplers (A) and (B) described below in place of the Exemplary Coupler (7).

These samples 1.2.3.4 and 5 were each wedge exposed in a conventional manner and then processed in the next processing step and with a developer having the processing solution composition shown below.

[Processing process (38℃)] Color development bleaching water washing fixing water landing washing stabilization Bath 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30 seconds [Color developer composition] Aniline sulfate 4.75 g Anhydrous sodium sulfite Hydroxylamine 1/2 sulfate Anhydrous potassium carbonate 1-lium nitrilotriacetic acid trisodium salt (monohydrate) 5 g 5 g 5 g 5 g Potassium hydroxide 1.0 g Water The temperature was then adjusted to 1°C, and the pH was adjusted to 1°C using potassium hydroxide.
Adjust to 0,0.

[Bleach solution composition Coethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt to, o g Ammonium bromide 150.0 g Glacial acetic acid 10.0 mA Add water to bring the temperature to 1°C, and use ammonia water. Adjust to pt, D.

[Fixer composition] Ammonium thiosulfate (5% aqueous solution) 162.0
g Anhydrous sodium sulfite 12.4 g
Add water to 1 and adjust to pH 8.5 using acetic acid.

Stabilizing liquid composition Coformalin (37% aqueous solution) 5.0 m
j2 Konidax (manufactured by Konica Corporation) 7.5
mf! .

Add water to make β.

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

Comparative coupler (A) (Compound described in U.S. Pat. No. 3,227,554) Comparative coupler (B) (Compound described in JP-A-55-52454) Based on the results in Table 1, the coupler of the present invention was used. Samples (1), (2),
Samples (3) and (3) have higher color sensitivity and highest density than samples (4) and (5) using comparative couplers, and show improved color performance with no increase in capri. I found out that it is.

Example 2 Example 2 Exemplary couplers (1), (8) and (12) and 2 x 101 moles of comparative couplers (C') and (D) described below were each mixed with 15 mj2 of dibutyl phthalate and 30 mj2 of ethyl acetate.
ml of mixed solution by heating, and add this solution to alkanol B.
(Alkylnaphthalene sulfonate, manufactured by DuPont) 1
．． mixed with 300 mu of 5% gelatin aqueous solution containing 5 g,
It was emulsified and dispersed in a colloid mill.

A dispersion of this coupler was mixed with 1.g of green-sensitive silver chlorobromide (silver chloride 20 mole %, silver bromide 80 mole %) in photographic emulsion 3 containing 5 x 10'' moles and 110 g gelatin as a hardener. 2-bis(vinylsulfonyl)ethane coated with 2% mt BO+nu and coated onto a polyethylene coated paper support1. Dry.

A gelatin protective layer was applied on this layer to prepare color photographic materials Samples 6 to 10, respectively.

At this time, the amount of silver applied for samples 6 to 10 was 0.5 g/m2
Met. These samples 6.7.8.9 and 10 were each wedge-exposed in a conventional manner and then processed in the following processing steps and using a developer having the following processing solution composition.

[fi processing step 33°C)] Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 3 minutes [Color developer composition: 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamide Ethyl)-Aniline sulfate Benzyl alcohol Hydroxyamine sulfate Potassium carbonate Potassium bromide Anhydrous sodium sulfite Diethylene glycol Add water and bring to 1°C [Bleach-fix solution composition] g 10.0 mal g 25.0 g 0.2 g 2.0 g 3m pH Adjust to pH 10.0 Ethylenediaminetetraacetic acid sodium salt ao,og Sodium bisulfite 1001g Sodium metabisulfite 3.0g Add water to make tiL, p) Adjust to 16.6.

The obtained magenta dye image was measured using green light in the same manner as in Example 1, and the color development sensitivity (expressed as relative sensitivity with sample (10) as 100) fog and maximum density were calculated. I also have to do a lightfastness test.

Light resistance was expressed as the residual density after exposure to a xenon fade meter for 100 hours with an ultraviolet absorption filter attached to each image obtained, with the density before exposure being 100. The results are shown in Table 2.

Comparative coupler (C) (Compound described in JP-A No. 53-34044) Ammonium thiosulfate 00g Comparative coupler (D) (Compound described in JP-A-53-34044)! From the results in Table 2, samples (6), (7) and (8) using the magenta coupler of the present invention have higher coloring sensitivity and highest density than samples (9) and (10) using the comparative coupler. It can be seen that there is no increase in fog and the light resistance is also excellent.

Below is the margin Example 3 After coating samples 1 to 5 prepared in Example 1, the samples were left unexposed in a dark room and placed in a sealed container containing a 1% formaldehyde aqueous solution for 3 days without contact with the solution. I left it alone. These samples and untreated samples for comparison were exposed and developed in the same manner as in Example 1, sensitivity and maximum density were measured, and formalin resistance % (IA physical sample/untreated sample X100) was calculated. The results obtained are shown in Table 3.

Compared to sample 4.5 in Table 3, the sensitivity decreases due to formalin.
It can be seen that this coupler has excellent properties in preserving raw samples and is not susceptible to adverse effects such as a decrease in maximum concentration.

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

In addition, each silver halide emulsion was prepared by adding 5TB-1 shown below as an emulsion stabilizer after chemical sensitization.
5 x 10-3 liters were added per mole.

From the results shown in Table 3 above, Samples 1 to 3 using the couplers according to the present invention, SD-1 SD TB-1 using the comparative couplers (Preparation of silver halide color photographic light-sensitive material samples) Then, A silver halide color photographic 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 as a blue-sensitive silver halide emulsion (Em-1), and 1 g of dioctyl 3II in which 8 mg of Y-coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing phthalate coupler solvent.

(2) 12 mg gelatin, 0.5 mg 2.5-di-
Interlayer containing 2 mg dibutyl phthalate UV absorber solvent in which t-octylhydroquinone and 4 tng UV absorbers (U-1 and U-2) were dissolved.

(3) 18B gelatin, 4 mg of silver as a green-sensitive silver halide emulsion (Em-2), 5 mg of the exemplary coupler shown in Table 5 as an M-coupler, 2 mg of antioxidant, and A layer containing 2.5 mg of dioctyl phthalate coupler solvent in which .2 mg of 2,5-di-t-octylhydroquinone was dissolved.

(4) An intermediate layer comprising the same composition as '(2).

(5) 16 mg of gelatin, 4 mg of silver, red-sensitive silver emulsion (Em-3), 3, 5 mg of silver
C-coupler and 0.1 mg of 2°5-di-t-octylhydroquinone in 2,''0mg tricresyl phosphate coupler solvent.

(6) Gelatin protective chews containing 9 mg of gelatin.

A coating aid was added to each layer from (1'')'''' to (6), and a gelatin crosslinking agent was added to layers (4) and (6).

The ultraviolet absorbers (2) and (4) include U-1 and U-
An equimolar mixture of 2 was used.

Di-t-pentylhydroquinone di-octyl ether was used as the antioxidant in (3).

U-1 After each wedge exposure of the obtained sample in the usual method,
Processing was carried out according to the following color development processing steps.

The obtained magenta dye image was measured using green light in the same manner as in Example 1, and the color development sensitivity (relative sensitivity with Sample 20 as 100) was used to calculate the display, fog, and maximum density.

In addition, the obtained sample was irradiated with a xenon fade meter for 15 days, and the residual rate of the dye image at the initial density of 1.0 (
%) to evaluate light resistance.

[Processing process] Color development, bleaching, fixing, stabilization, drying, drying [Color developer] Pure water 8
00 mAl・Reethanolamine
8g N,N-diethylhydroxylamine 5g Potassium chloride 2g 45 seconds 45 seconds 90 seconds 60 seconds 34.7±03°C 34.7±0.5°C 30°C to 34°C 60°C to 80°C Sodium tetrapolyphosphate 2g Potassium carbonate 30g Sulfite potassium
Add 0.2 g of optical brightener (4,4'-diaminostilbendisulfonic acid conductor) and 1 g of pure water to bring the total volume to 1°C, and adjust the pH to 10.2.

[Bleach-fix solution] Ammonium dihydrate, ethylenediaminetetraacetic acid, ammonium diosulfate (70% solution), ammonium sulfite (40% solution), add water to make a total volume of 1 fL, and remove potassium carbonate with glacial acetic acid.
Adjust to H5,7.

Stabilizing liquid] 0g 3g 100 mfl 27.5mJZ Lamb or 5-chloro-2-methyl-4-inthiazolin-3-one Add 1g of water to make 1fL, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to.

The M-coupler used in the (3) layer and its result in the 5th layer.
Shown in the table.

From the results shown in Table 5, Samples 11 to 18 using the magenta coupler of the present invention are different from Samples 19.2 and 19.2 using the comparative coupler.
It can be seen that compared to No. 0, it has higher color development sensitivity and maximum density, no increase in fog, and is also excellent in light resistance.

Example 5 The blue-sensitive silver halide emulsion (1) of the silver halide color photographic light-sensitive material prepared in Example 4 was used as Em-4 in Table 4, and the green-sensitive silver halide emulsion (3) was used as Em-4 in Table 4. Em- in Table 4
5, the red-sensitive silver halide emulsion of (5) was added to Em of Table 4.
Samples 21 to 3 of silver halide color photographic light-sensitive materials were prepared in the same manner as in Example 4, except that the M-couplers were replaced with M-couplers shown in Table-6.
0 was created.

The obtained sample was passed through a photosensitive needle KS-7 type (manufactured by Konica Corporation).
After wedge exposure using the same method, the same treatment as in Example 2 was carried out, and then the same measurements as in Example 4 were performed. The results are shown in Table 6.

From the results in Table 6 below, Samples 21 to 30 using the magenta coupler of the present invention have higher color development sensitivity and maximum density than Samples 29 and 30 using the comparative coupler, and there is no increase in fog. It can be seen that the film also has excellent light resistance.

[Effects of the Invention] By using a specific magenta coupler, the present invention provides high color development sensitivity and maximum density, excellent storage stability of raw samples, and improved light resistance of the resulting images. Halogen: A silveride color photographic light-sensitive material can be obtained.

Claims (1)

[Scope of Claims] A silver halide color photographic material containing a magenta dye-forming coupler represented by the general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents an aryl group, R_2 represents an anilino group, acylamino group, ureido group, or carbamoyl group, and R_3 represents a sulfonyloxy group or acyloxy group. , represents a carbamoyl group, sulfamoyl group, sulfonic acid ester group, or sulfonamide group, and R_4 is 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, or a sulfamoyl group. , represents a sulfonic acid ester group, a nitro group, or a sulfonamide group. n represents an integer from 1 to 4. ]