JPS6060645A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance the light resistance, etc., of a dye image and to reduce fog and the amt. of silver halide to be used by using a specified 2-equiv. magenta coupler to be added to a silver halide emulsion layer. CONSTITUTION:An intended silver halide photosensitive material is obtained by incorporating in a silver halide emulsion layer a magenta coupler represented by formula I in which Ar is aryl; each of R1 and R2 is alkyl or cycloalkyl; R3 is halogen, alkyl, or the like; and m is 0-4. The magenta coupler of formula I is embodied by the ones of formulae II, III, etc., and the one of formula IIis synthesized, e.g., by reacting 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxy) acetamide]-benzamido-5-pyrazolone with 2-dodecyloxyphenylmercaptan.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a novel magenta dye-forming coupler. The present invention relates to a silver halide photographic material containing an excellent novel magenta dye-forming coupler.

Prior art and its problems As is well known, subtractive color photography is based on the oxidation of an aromatic primary amine color developing agent, which is produced by reducing exposed silver halide grains. A yellow image is formed by oxidative coupling of a substance and couplers that form yellow, cyan, and magenta dyes in a silver halide emulsion layer.

In these cases, as the yellow coupler for forming the yellow dye, a compound having an open chain active methylene group is generally used, and as the magenta coupler for forming the magenta dye, pyrazolone type, pyrazolinobenzimidazole type, Compounds such as indacylon compounds are used, and compounds having phenol and naphtholic hydroxyl groups are used as the cyan turnip 2- for forming cyan dyes.

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

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

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

Various pyrazolone derivatives are known as magenta couplers, but these couplers have low coloring efficiency, and in the case of so-called four-equivalent couplers in which the coupling 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 color development efficiency, a so-called two-equivalent magenta coupler is known, in which a substituent (leaving group) capable of tin removal during color development is introduced into the active position of a pyrazolone derivative. As these two-equivalent magenta couplers, for example, couplers having an acyloxy group as a leaving group are disclosed in U.S. Pat. No. 3,311,476, and couplers having an aryloxy group are disclosed in U.S. Pat. No. 3,419,39.
No. 1, Kab 2- having a thiocyano group is disclosed in U.S. Patent No. 3.
, 214.437 and 3,253,924, 2
- A coupler having a triazolyl group is disclosed in U.S. Patent No. 3.6.
17,291, and couplers with acylthio or thioacylthio groups are described in US Pat. No. 4.032.346. However, when these two-equivalent magenta couplers are used, significant color fogging may occur, coupling activity may be low, or the couplers may be chemically unstable and turn into substances that cannot develop color over time. However, these methods were accompanied by some disadvantages, such as difficulty in synthesis and many difficulties in synthesis.

In addition, as disclosed in U.S. Patent Nos. 3,227,554 and 3,701,783, the active position 4 of pyrazolone derivatives has been substituted with an arylthio group or a heterocyclic thio group. compounds were also known.

However, many of these known thio-substituted pyrazolone compounds are so-called development inhibitor-releasing couplers (DIR).
The mercaptan produced as a result of the coupling reaction interacts with silver halide and has the function of delaying development.

For the purpose of preventing the strong photographic effect of mercaptans, thio-substituted pyrazolone couplers having a mercaptan compound with a diffusion-resistant group as a leaving group are described in Japanese Patent Publication No. 34044/1982, but these couplers have low coupling activity. However, there is a problem with the storage stability of the magenta dye produced, which makes it difficult to apply it to general color photographic materials.

Furthermore, JP-A-55-62454 describes a magenta coupler in which the 4-position of a pyrazolone derivative is substituted with R'-8- (R' represents a straight or branched alkyl or aralkyl). In these couplers, the mercaptan compound released after coupling does not have a substantial development inhibiting effect, but the couplers have drawbacks such as low coupling activity and poor image storage stability, especially light resistance. It had

Furthermore, 3-anili-5-pyrazolone magenta couplers are described in JP-A-57-35,858, but these couplers also have the drawback of low coupling activity.

■ Purpose of the Invention The present invention has been made in view of the above-mentioned circumstances, and its first object is to provide a method that has sufficient reaction activity and that can achieve high yield without causing unnecessary fog or stain. The object of the present invention is to provide a novel two-equivalent magenta coupler that forms a dye.

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

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

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

A fifth object of the present invention is to provide a new two-equivalent magenta coupler that can be obtained by a simple manufacturing method.

■Specific Structure of the Invention As a result of various studies, the present inventor has developed a silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support. It has been found that the above object can be achieved by using a silver halogenide photographic light-sensitive material, which is characterized in that the silver emulsion layer contains at least one magenta coupler represented by the following general formula CI), and the present invention I was able to complete it.

General formula [I] (wherein, Ar represents an aryl group, R1 and R2 each represent an alkyl group, a cycloalkyl group, or an aryl group, and R3 represents a halogen atom, an alkyl group, an alkoxy group, or an aryl group) , or represents a drexyl group, and m represents an integer from 0 to 4.) When represented by Ar in the general formula (I), The aryl group is, for example, a phenyl group, a naphthyl group, etc., and preferably a phenyl group, and is preferably a phenyl group. group, hydroxycarbonyl group, alkyl group (straight chain or branched alkyl group, such as methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group,
decyl group, dodecyl group, hexadecyl 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 groups (e.g. undecylcarbonylamino group, dodecylcarbonylamino group, etc.), arylcarbonylamino groups (e.g. tolylamino group, toluoylamino group, benzoylamino group, etc.), alkylsulfonamide groups (e.g. dodecylsulfone group), amide group, etc.), arylsulfonamide group (e.g., benzenesulfonamide group, etc.), alkylaminosulfonamide group (e.g., dimethylaminosulfonamide group, etc.), arylaminosulfonamide group (e.g., anilinosulfonamide group, etc.), alkylcarbamoyl group (e.g. hexadecylcarbamoyl group, etc.), 'arylcarbamoyl group (
For example, phenylcarbamoyl M, etc.), sulfonyl groups (flJ t hamethylsulfonyl group, n-dodecylsulfonyl group, etc.), alkyloxycarbonyl groups (e.g. dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, etc.), Examples thereof include alkylsulfamoyl groups (eg, methylsulfamoyl group, dimethylsulfamoyl group, etc.), and alkylsulfamoyl groups (eg, phenylsulfamoyl group, etc.).

Among these substituents, preferred are halogen atoms,
Hydroxyl group, cyan group, hydroxycarbonyl group,
These include alkyl groups, and particularly preferred are halogen atoms. Among the halogen atoms, particularly preferred are chlorine atoms; specifically, chlorine atoms are substituted at the 2nd and 3rd positions, the 2nd and 4th positions, and the 2nd and 5th positions of the phenyl group, respectively. 2,3-dichlorophenyl group, 2.4
-dichlorophenyl group, 2,5-dichlorophenyl group, and the like.

The alkyl group represented by R1 in general formula (I) is a linear or branched alkyl group, preferably having 1 carbon number.
to 22 alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), and these alkyl groups have a substituent. If you have,
Examples of this substituent include hydroxyl group, hydroxycarbonyl group, cyano group, aryl group (e.g., phenyl group, tolyl group, etc.), alkyloxycarbonyl group (e.g., ethoxycarbonyl group, hexadecyloxycarbonyl group, etc.), aryloxycarbonyl group ( (e.g., phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylsulfonamide group (e.g., methanesulfonamide group, etc.), acylamino group (e.g., acetamide group, benzamide group, etc.), alkoxy group (e.g., methoxy group, benzyl group, etc.) (oxy group, etc.), aryloxy group (eg, phenoxy group, etc.), and sulfonyl group (eg, methanesulfonyl group, etc.).

Examples of the cycloalkyl group represented by R in the general formula [■] include a cyclohexyl group, a cyclopentyl group,
Examples include 2-methyl-hexyl group and 2-ethyl-hexyl group.

Further, the aryl group represented by R□ in the general formula CI) includes, for example, a phenyl group and a naphthyl group, with a phenyl group being preferred. The aryl group may have a substituent. Examples of the substituent include the same substituents as those described for the aryl group of Ar in general formula (1) above.

In general formula CI), the alkyl group, cycloalkyl and aryl group represented by R2 can be the same groups as mentioned for R1 above.

Examples of the halogen atom represented by R3 in the general formula CI) include a chlorine atom, a bromine atom, and a fluorine atom.

The alkyl group of R8 preferably has 1 carbon number.
to 22 linear or branched alkyl groups (e.g., methyl group, ethyl group, t-butyl group, tetradecyl group, etc.), and this alkyl group may have a substituent, and the substituent Examples include the same substituents as mentioned for R1 and R2 above.

The alkoxy group for R3 is preferably one in which the alkyl moiety has 1 to 22 carbon atoms, such as a methoxy group, an ethoxy group, an octyloxy group, a dodecyloxy group, and the like. This alkyl moiety may be a linear or branched alkyl group, and may have a substituent. Examples of the substituent include the same substituents as those described for R1 and R2 above.

Furthermore, the aryl group represented by R3 in the general formula (I) is, for example, a phenyl group, α- or β-
Examples include naphthyl group and p-tolyl group. This aryl group can have a substituent, and examples of the substituent include the same substituents as those mentioned for the aryl groups R1 and R2 in the general formula CI).

Further, m in general formula CI) is from 0 to 4, preferably from θ to 2.

Specific examples of typical compounds of the magenta coupler of the present invention represented by the general formula [0 are shown below, but the present invention is not limited thereto.

(1) (5) CM.

(11) (15) (12) (16) (17) (18) (21) (22) (23) (25) (29) (30) The coupler of the present invention represented by general formula CI) It can be synthesized by a known method. In particular, the following synthetic methods are available for introducing a thio group as a leaving group into the 4-position of pi2zodine. That is, U.S. Pat. No. 3,227,554;
A method of 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 No. 701,783. , as described in JP-A-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 mercaptan, Research Disclosure.
Chem.

Pharm, Bull, 20.18621868(
1972), a method of reacting a four-equivalent pyrazolone coupler with an S-alkylthioisothiourea.

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 19 Synthesis of Exemplary Coupler 1 1-(2,4,6-)lichlorophenyl)-3-(3
-(2,4-di-tert-amylphenoxy)acetamido)benzamide-5-pyrazolone 13.42 and 2
-Dodecyloxyphenylmercaptan 5.9f was dissolved in dimethylformamide (DMF) 5(ld), and bromine 3.2F was added dropwise thereto. After the dropwise addition, it was heated to 80°C and reacted for 2 hours. The reaction solution was dissolved in ice water When poured into 〇-, a solid precipitated. This solid was filtered, washed with water, and then dried. This was recrystallized from acetonitrile to obtain the desired product in 17.
Of got it.

Yield of target product: 88%, melting point: 159-161°C, FDY
Spect kh/I/e = 964 (M”+2)
I was so excited.

Synthesis Example 20 Synthesis of Exemplary Coupler 4 1-(2-chloro-4,6-dimethylphenyl)-3-
9.52 grams of hexadecaneamide-5-pyrazolone and 6.5 grams of diphenylmercaptaf in 2-tetradecylo were dissolved in 50 grams of dimethylformamide (DMF), and 3.2 tons of bromine was added dropwise thereto. After dropping, the mixture was heated to 80°C and reacted for 2 hours. The reaction solution was poured into 500 g of ice water to precipitate a solid. This solid was treated with P, washed with water, and then dried. This was recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 12.7f of the desired product.

The yield of this target product was 80%, and the melting point was 193-19.
4℃, and FD mass spectrum M/e is 795 (M+)
Met.

As described above, the coupler of the present invention can be easily manufactured by applying conventionally known methods.

In order to produce a silver halide photographic light-sensitive material, the couplers of the present invention may be used alone or in combination of two or more. CUB 2- of the present invention can be used in both internal and external systems, but particularly good results can be obtained when it is used in a silver halide emulsion.

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

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

At least one type of coupler of the present invention is contained in the silver halide emulsion, and the content thereof is usually 90.07 to 0.7 mol, preferably 0.1 to 0.7 mol, per 1 mol of silver halide.
It is 4 moles. It can also be contained in a non-photosensitive layer adjacent to the silver halide emulsion layer.

The couplers of the present invention include dibutyl phthalate, dioctyl 7-talate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), N, N
- high-boiling water-immiscible organic solvents such as diethylcaprylamide, N,N-diethyllaurylamide, N,N-dibutyllaurylamide; low-boiling organic solvents such as ethyl butyl acetate; or methanol, ethanol;
Advantageously added to the photographic emulsion by dissolving in either a water-soluble organic solvent such as acetone, dioxane, tetrahydrofuran, or a high-boiling, water-immiscible organic solvent and/or a low-boiling and/or water-soluble organic solvent. .

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

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

Since the magenta coupler according to the present invention is used, the silver halide photographic light-sensitive material may contain other magenta couplers as necessary, specifically, pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-h-based , indacylon couplers may be used in combination.

As the colored magenta coupler, a compound in which the active site of the colorless magenta coupler is arylazo-substituted or heteroarylazo-substituted is used.

Silver halogenide photographic materials applicable to the present invention include:
Other color couplers can be contained together with the magenta coupler of the present invention to form a multicolor image. Yellow couplers that can be used in combination include benzoylacetanilide type, pivaloylacetanilide type yellow couplers, and further coupling Two-equivalent color couplers in which the carbon atom at position is substituted with a substituent that can be removed during the coupling reaction may be used in combination.

Examples of cyan couplers include phenol or naphthol derivatives, and examples of colored cyan couplers include compounds in which an arylazo-substituted phenoxy group is substituted directly or via an alkoxy group at the coupling position of a colorless cyan coupler. can.

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 dyes by reaction with oxidized developing agents are used. It is also possible to use inhibitor-releasing substances. These may be used alone or in combination of two or more.

Moreover, the magenta coupler of the present invention is disclosed in Japanese Patent Publication No. 49-265
No. 85, U.S. Patent No. 3.486.89, Research Disclosure
osure) 12044, 12840, etc. That is, by incorporating both the magenta coupler of the present invention and the aromatic primary amine developing agent into a light-sensitive material, and after imagewise exposure, processing with an alkaline bath, black and white developer, or heat treatment, It is possible to perform color development and obtain a dye image with uniform gradation.

The silver halide photographic material applied to the present invention basically consists of a support and a light-sensitive emulsion layer, but depending on the type of silver halide photographic material, it may include a subbing layer, an intermediate layer,
Generally, auxiliary layers such as a filter layer, an antihalation layer, an anticurl layer, a pack layer, and a protective layer are appropriately combined and layered. In addition, the silver halide emulsion layer itself may contain, for example, a layer containing silver halide with relatively high sensitivity and a layer containing silver halide with relatively low sensitivity, which are sensitized to the same wavelength range or different wavelength ranges. The structure may be multilayered.

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

In order to further increase the stability of the dye image formed,
Alkyl-substituted hydroxynes and their alkoxy derivatives, bishydroxynes, polymeric hydroquinones, etc. may be contained singly or in combination in the silver halide emulsion layer containing the coupler of the present invention or in a layer adjacent thereto. Furthermore, p-alkoxyphenols, 6-chromanol, 6,6'-dihydroxy-2,2'-spi-tetraroman and their alkoxy or acyloxy derivatives can be used as well.

The silver halide photographic light-sensitive material according to the present invention contains benzotriazoles, triazines, benzophenone compounds, or acrylonitrile compounds as ultraviolet absorbers in its constituent layers (e.g., protective layer, intermediate layer, emulsion layer, back layer, etc.). May contain.

In order to form a photosensitive material, silver halide is dispersed in a suitable protective colloid to constitute a photosensitive layer, and the photosensitive layer and other auxiliary layers such as an intermediate layer, a protective layer, a filter layer, etc. The commonly used retained colloids are alkali-treated gelatin, as well as acid-treated gelatin, derivative gelatin, colloidal albumin, cellulose derivatives, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, which may be used alone or in combination. It is used as

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, setting treatment, etc. processing is performed.

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

These silver halide emulsions are produced according to known and conventional methods (for example, single or double jet method, controlled double jet method, etc.). Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed.

Furthermore, even if the crystal structure of silver halide grains is uniform inside, there are also grains with a layered structure with different interior and exterior layers, so-called conversion emulsions, Lippmann emulsions, covered grain emulsions, or grains that have been optically or It may also be chemically capri-added.

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

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers include noble metal sensitizers (potassium aurithiocyanate, ammonium chloroparadate,
potassium chloroplatinate, etc.), sulfur sensitizers (allylthiocarbamide, thiourea, cystine, etc.), selenium sensitizers (active and inactive selenium compounds, etc.) and reduction sensitizers (
They are roughly divided into four types: stannous salts, polyamines, etc.). 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 light-sensitive material. Is possible.

The above-mentioned silver halide emulsion contains 1-7enyl-5-mercaptotetrazole, 3-7enyl-5-mercaptotetrazole, and 3-mercaptotetrazole in order to prevent a decrease in sensitivity and the generation of capri during the manufacturing process, storage, or processing of silver halide photographic materials. Various compounds such as heterocyclic compounds such as methylbenzothiazole, 4-hydroxy-6-methyl-1,3,3a, and 7-titrazaindene, 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 geltanaldehyde, and derivative compounds thereof such as their acetals or sodium bisulfite adducts, as well as methanesulfonic acid esters. Compounds, mucochloric acid, mucohalogenated compounds, epoxy compounds, aziridine compounds, active halogen compounds, maleic acid imide compounds, active vinyl compounds, carbonimide compounds, inoxazole compounds, N-methylol compounds , incyanate-based compounds, or inorganic hardeners such as chromium brightpan 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 used for sensitization, improvement of photographic properties, prevention of static electricity, prevention of adhesion, etc. These surfactants include natural surfactants such as saponin, alkylene oxide type, glycerin type,
Sonionic surfactants such as glycidol, higher alkylamines, quaternary ammonium salts, pyridine, other heterocycles, cationic surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acids They are divided into anionic surfactants containing acidic groups such as ester groups and phosphoric acid ester groups, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols.

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

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

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

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

Each of these basic steps may be performed independently, or two or more steps may be performed in a single treatment using a processing liquid that has these functions. For example, one-bath color processing methods containing a color developing agent, a ferric salt bleaching component and a thiosulfate fixing component, or iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate)
III) A one-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 processing such as color development, first fixing, bleaching and fixing is also possible. In addition to the above, the development process also includes a pre-hardening bath, neutralization tower, image stabilization bath,
Various processes such as washing with water are combined. Although the treatment temperature may be lower than 18°C, it is often higher than 18°C. 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 for the series of treatment steps be the same.

The color developing solution is an alkaline aqueous solution containing a developing agent and having a pH of 8 or more, preferably 9 to 12. The above-mentioned developing agent refers to a compound having a -grade amino group on an aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound. Preferred are p-phenylene diamines, such as 4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N,
N-diethylaniline, 4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline,
3-β-methanesulfonamidoethyl-4-amino-N
, N-diethylaniline, 3-methoxy-4-amino-
N-, Zf-N-β-hydroxyethylaniline, 3
-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N
, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl- N-β-[β-methoxyethoxy]ethyl-3-methyl-4-amineaniline and salts thereof, such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like.

Additives are added to the color developing solution as necessary. Main examples include alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates, phosphates, etc.), pH adjusting or buffering agents (e.g. weak acids and bases such as acetic acid and boric acid, and their salts). , development accelerators (for example, pyridinium compounds, cationic compounds, potassium sulfate, sodium sulfate, polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers,
Polymer compound with sulfide ester, So(7)
Other organic amines such as pyridine, ethanolamine, benzyl alcohol, hydrazine (JA nato), antifoggants (such as alkali bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methylbenzo)! J '7 saw #, 1
-phenyl-5-merca 7'l-f torazol, compounds for rapid processing liquids, thiosulfonyl arsenic compounds, phenazine N oxides, benzothiazolium nitrobenzoate derivatives, etc.), stain or sludge inhibitors, multilayer effects Accelerators, preservatives (eg sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfide, alkanolamine sulfide adducts, etc.), etc.

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

The silver halide photographic material according to the present invention can be subjected to a bleaching treatment in a conventional manner after the color development treatment. This treatment may be done simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary.

Various compounds are used as bleaching agents, among which red blood salts; dichromate; iron (■), cobal) (I
II), polyvalent metal compounds such as phosphorus (II), in particular complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diaminobutetrapanoltetraacetic acid, Metal complex salts such as citric acid, tartaric acid, malic acid, peracids such as alkyl peracids, persulfates, permanganates, hydrogen peroxide, etc., hypochlorites such as chlorine, bromine, and standalone powder, etc. Alternatively, a suitable combination is common. Furthermore, various additives including a bleaching accelerator can also be added to this processing solution.

After the color development process, conventional photographic processing is carried out, such as a stop solution containing an organic acid, a stop fix solution containing an organic acid and a fixing component such as hypo or ammonium thiosulfate, a fixing solution containing a fixing component such as hypo or ammonium thiosulfate, Bleach solutions containing ferric salts of aminopolycarboxylic acids and alkali halides as main components, bleach-fix solutions containing ferric salts of aminopolycarboxylic acids and fixing components such as hypo or ammonium thiosulfate, and other stabilizing solutions. It is sufficient to carry out an appropriate combination of treatments selected from treatments using treatment liquids such as the above, washing with water and drying, and the like.

The coupler according to the present invention has a low amount of silver halide, which is several to one hundredth of the amount of silver halide in the silver halide emulsion, compared to the case of ordinary silver halide light-sensitive materials. It can also be used in photographic materials.

For silver halide photographic light-sensitive materials with a reduced amount of silver halide in this way, there is a development processing method in which 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. A sufficient color image can be obtained by applying a development method using color intensification using cobalt lead salt or sodium chlorite.

The silver halide photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent precursor is a compound capable of producing a color developing agent under alkaline conditions, such as a Schiff-Pase type breaker with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a phosphoric acid precursor. Examples include amide derivative precursors, sugar amine reactant precursors, and urethane type precursors. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
No. 99, No. 2,507,114, No. 2.695,
No. 234, No. 3,719,492, British Patent No. 80
Specification No. 3,783, JP-A-53-135.628,
Publications No. 54-79,035, Research Disclosure No. 15,159, No. 12.146, No. 1
3,924 These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during development. This amount varies depending on the type of photosensitive material, but it is generally photosensitive silver halide 1
Between 0.1 and 5 mol per mole, preferably 0.5
It is used in a range of mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can be added as an emulsified dispersion using a boiling point organic solvent, or as a latex remer impregnated as described in Research Disclosure No. 14850.

(2) Specific Examples of the Invention Next, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited to these in any way.

Example 1 2 x 10-'' moles of the exemplary coupler (1) were dissolved under heating in a mixture of 15- dibutyl 7-talate and 30-'' ethyl acetate, and the solution was dissolved in Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 1. 591i gelatin aqueous solution 3 containing 5t
00ml and emulsified and dispersed using a Koniido Mill. A dispersion of this coupler was mixed with 1 mol of green-sensitive silver iodobromide (6 moles of silver iodide, 947% silver bromide) and 1 mol of a photographic emulsion containing 402 g of gelatin, and 1 mol of silver as a hardener.
2% solution of 2-bis(vinylsulfonyl)ethane 20-
was applied onto a cellulose triacetate film base and dried.

A gelatin protective layer was coated on this layer to prepare a sample (1) of a silver norogenide color photographic material. The amount of silver applied to sample (1) at this time was 2 f/n? Met.

Further, instead of exemplary coupler (1), exemplary coupler (4)
and (7) in exactly the same manner as above.
) and (3) were created.

Further, as comparative samples, comparative samples (4) and (5) were prepared in exactly the same manner as above, using the below-mentioned comparative couplers (6) in place of the exemplary coupler (1).

These samples (1), (2), (3), (4) and (
5) were each subjected to wedge exposure 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 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Constant N 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] Anhydrous sodium sulfite 4.25t Hydroxylamine + sulfate 2.01 Anhydrous potassium carbonate 37.4M Sodium bromide 1.3 Tanitrilotriacetic acid trisodium salt (monohydrate) 2.5
F potassium hydroxide 1. Of water was added to make 1 t, and potassium hydroxide was used to make pI (1 t).
Adjust to 0,0.

[Bleach solution composition]

Ethylenediaminetetraacetic acid amsonium salt 100.
0 tEthylenediaminetetraacetic acid diammonium salt
10.0y ammonium bromide 150. Of Glacial acetic acid 10.0ml [Fixer composition] [Stabilizing solution composition] Formalin (37% aqueous solution) 5.0mg Conidax (manufactured by Konishiroku Photo Industry ■) 7.5ml Add water to make 1t
shall be.

The magenta dye image obtained above was measured using a densitometer (PD-
7R Konishiroku Photo Industry ■) was used to measure the color under green light. (expressed as a relative value when the sensitivity in sample (4) K is set to 100), calculate the fog and maximum density,
The results are shown in Table 1 below. From the results shown in Table 1 above, samples (1), (2), and (3) using the coupler of the present invention are the samples using the comparative coupler. It was found that it had higher color development sensitivity and maximum density than (4) and (5), and also exhibited improved color development performance with no increase in capri.

Comparative coupler (5) (Compound described in U.S. Pat. No. 3,227,554) Comparative coupler CB) (Compound described in JP-A-55-62,454) Example 2
゜Exemplary couplers (15), (23), and (28) and comparative couplers (0 and Q)) 2 X 10''
-" moles of dibutyl phthalate) 15#+7! and 3o- of ethyl acetate were heated and dissolved, and this solution was dissolved in a 5% aqueous gelatin solution containing 1.5 F of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 300 m
1 and emulsified and dispersed using a colloid mill.

A dispersion of this coupler was mixed with a photographic emulsion containing 0-2 moles of green-sensitive silver chlorobromide (20 moles of silver chloride, 80 moles of silver bromide) and 1 ior of gelatin, and 1.2 moles of gelatin was added as a hardening agent. - 80rnt of a 2% solution of bis(vinylsulfonyl)ethane was added, coated on a polyethylene-coated paper support and dried. A gelatin protective layer was applied on this layer to prepare color photographic material samples (6) and (8) and comparative samples (9) and (lO), respectively. At this time, the amount of silver applied for samples (6) to (10) was 0.5 t.
/rr? Met. These samples (6), (7), (8
), (9), and (10) were each exposed to wedge light using a conventional method, and then processed in the following processing steps and using a developer having the following processing solution composition.

[Treatment process (33℃)] Color development 3 minutes 30 minutes Bleach fixing 1 minute 30 minutes Wash with water for 3 minutes [Color developer composition] Benzyl alcohol 10.0m mhydronulamine sulfate 2 Potassium carbonate 25. Of Potassium bromide 0.2f Anhydrous sodium sulfite 2.02 Diethylene glycol 3ml Add 1 ton of water and adjust the pH to 10.0.

[Bleach-fix solution composition]

Ethylenediaminetetraacetic acid iron sodium salt 60.0
f Ammonium thiosulfate i o o, o r Sodium bisulfite 10.0 r Sodium metabisulfite 3.02 Add water to make 1 t and adjust to pH 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 (expressed as relative sensitivity with sample (10) as 100), capri, and maximum density were calculated, and the results were used as a second image. Shown in the table.

Table 2 From the results shown in Table 2, samples (6), (7), and (8) using the magenta coupler of the present invention have a lower temperature than samples (9) and (10) using the comparative coupler. It can be seen that it is an excellent coupler with high color development sensitivity and maximum density, and no increase in fog or fog.

Comparative coupler C (compound described in JP-B-53-34,044) (compound described in JP-A-57-35,858) Example 3 Samples (1) obtained in Example 1 and Example 2 - (10
) was tested for light resistance, heat resistance, and moisture resistance.

Light resistance was determined by attaching an ultraviolet absorbing filter to each image obtained and using a xenon fade meter to express the residual density after exposure for 100 hours, with the density before exposure being 100. Moisture resistance was expressed as the residual concentration after storage for 2 hours at 50°C and relative humidity of 80°C, with the concentration before the test being 100. Furthermore, the heat resistance was expressed as the residual concentration after storage for 2 weeks at 77° C., with the concentration before the sample being 100. Table 3 shows the results.

From the results shown in Table 3, the coupler of the present invention is an excellent coupler that has excellent light resistance, moisture resistance, and heat resistance compared to comparative couplers, and is less likely to cause a decrease in image density during storage. It turns out that there is something.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural amendment (voluntary) September 16, 1982 2 Name of invention Silver halide photographic light-sensitive material 3 Relationship to the person making the amendment Patent applicant address Tokyo Shinjuku-ku Nishi-Shinjuku 1-26 Ministry No. 2 Name
(127) Konishiroku Photo Industry Co., Ltd. 4゛ Agent 〒10
2 Address: 263-9524 Matsuoka Kudan Building, No. 8 Kudanminami 2-chome, Chiyoda-ku, Tokyo (1) "Gluta/aldehyde" on page 35, lines 9-10 of the specification is corrected to "glutaraldehyde" .

(2) "Latex slimer" on page 45, line 7 of the same page is replaced with "
latex polymer”.

(3) On page 45, lines 14 and 15, "2 mols of exemplified coupler (1) 2X10'' are corrected to 15 m of dibutyl phthalate" to ``2X]0 mols of exemplified coupler (1) are 15 TILl of dibutyl phthalate.''

(4) Structural formula of comparative coupler (A) on page 49 of the same page (
5) The description regarding comparative coupler (C) and comparative coupler (D) on page 53 of the same is corrected as follows.

"Comparative coupler (C) (compound described in IJgj Publication No. 53-34,044)" (
Compound described in JP-A No. 57-35,858) (e) Amendment of the above procedure @- (spontaneous) 21 Name of invention Silver halide photographic light-sensitive material 3. Relationship with the case of the person making the amendment Patent applicant address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. Matsuoka Kudan Building Tsuge 2
63-9524 (The two lines from the bottom of the first page of the 11th written amendment are amended as follows.

(2) "Comparative coupler (C) (compound described in Japanese Patent Publication No. 53-34,044)" on page 2, line 3 of written amendment compound) l''.

(3) "Comparative coupler (D) (compound described in JP-A-57-35,858) I3" on page 2, line 6 of the written amendment is changed to "comparative coupler (D) (% JP-A-57-35-858), Compound described in No. 858).

that's all

Claims (1)

[Scope of Claims] A silver halide photographic material comprising at least one silver halide emulsion layer on a support, wherein the halogen and silver emulsion layer contain a magenta coupler represented by the following general formula CI). A silver halide photographic material containing at least one kind. General formula (I) Ar (wherein, Ar represents an aryl group, R1 and R2 each represent an alkyl group, a cycloalkyl group, or an aryl group, and R3 represents a halogen atom, an alkyl group, an alkoxy group, represents a ryl group or a hydroxyl group, and m represents an integer from 0 to 4.)