JPS61230146A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color development performance of a magenta dye, light fastness of its dye image, and the spectral absorption characteristics by incorporating a specified triazole type magenta coupler in at least one of silver halide emulsion layers formed on a support. CONSTITUTION:At least one of the silver halide emulsion layers formed on the support contains a 1H-pyrazolo[3,2-C]-s-triazole type magenta coupler substd. at the 3-position by a group represented by the formula -R1-SO2-R2 in which R1 is an >=3 C alkylene group combining -SO2-R2 with the C at the 3-position of 1H-pyrazolo[3,2-C]-s-triazole ring, and R2 is aryl; thus permitting the color developing performance of the magenta dye and light fastness of its dye image to be improved, and its spectral absorption characteristics to be enhanced.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a silver halide photographic photosensitive material containing a magenta coupler that forms a magenta dye image with high color development and improved storage stability, especially light fastness. Regarding materials. More specifically, the present invention relates to a silver halide color photographic light-sensitive material containing a novel 1H-bilane 0 [3,2-C]-s-triazole magenta coupler.

(Background of the Invention) Generally, in a silver halide color photographic light-sensitive material, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and an oxidized product of the color developing agent is generated at this time. A dye image can be obtained by coupling the dye with a coupler that forms yellow, magenta, and cyan dyes.

The coupler that has been put to practical use in the past to form the magenta dye is a pyrazolone type coupler, but this has unfavorable side absorption and is said to have poor storage stability, especially resistance to formalin gas (formalin resistance). It has its drawbacks.

In order to improve the above drawbacks, various 1H-pyrazolo[3,2-C]-8-triazole magenta couplers have been proposed. For example, U.S. Patent 3,725,0
No. 67, British Patent No. 1,252,418, British Patent No. 1.334
, No. 515. The compounds described in both patents are, of course, superior to pyrazolone magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient, and little improvement has been shown in terms of color development and light resistance of III images. Not yet.

Research Disclosure (Rθ5earchD
The compound described in No. 12443 cannot be put to practical use at all in terms of color development. Japanese Unexamined Patent Publication No. 1983-
1H-virazoO[3,2-C1-
Although 5-triazole magenta couplers have been significantly improved in terms of formalin resistance and color development, light resistance has hardly been improved.

Also, JP-A-59-99437, JP-A No. 59-125732
Although the coupler described in the issue has also been improved in color development,
There continues to be no improvement in the lightfastness of dye images based on the described couplers.

The lightfastness of the image is simply improved by the additive used. However, for the former coupler of Compound Example 19 described in the specification, although the light resistance is slightly improved, it is still not sufficient.

On the other hand, a 1H-pyrazolo[3,2-C]-s-triazole magenta coupler that improves color development and light fastness of the formed dye image is disclosed in Japanese Patent Application No. 59-243007.
No. 59-243008, No. 59-243009, No. 59-243010, No. 59-243011,
No. 59-243012, No. 59-243013,
It is disclosed in No. 59-243014 and W459-243015.

However, although the magenta couplers described in these specifications show improvements in color development and light fastness of dye images, the spectral absorption characteristics of magenta dye images are insufficient.

In other words, 1H-pyrazolo[3], which has attracted attention for its lack of side absorption and high formalin resistance,
, 2-C]-s-triazole-based magenta couplers that satisfy the following three points: color development, light fastness of dye images, and spectral absorption characteristics.

(Object of the Invention) An object of the present invention is to provide a silver halide photographic material which has good color development of a magenta dye, good light fastness of a dye image, and improved spectral absorption characteristics.

(Structure of the Invention) The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support.
This is achieved by a silver halide photographic light-sensitive material containing a 1-day-pyrazolo[3,2-C1-3-triazole magenta coupler] substituted with a group represented by the following general formula [I].

General formula [I] -R1-802-Rλ In the formula, R+ is an alkylene connecting the carbon at the 3-position of the 1H-pyrazolo[3,2-C]-s-triazole nucleus and -8O2-R) group in which the number of carbon atoms in the straight chain portion of the alkylene group is 3J:J.

and R2 represents an aryl group.

(Specific Structure of the Invention) In the group represented by the general formula [I], R1 represents an alkylene group in which the straight chain portion has 3 or more carbon atoms,
This alkylene group may be linear or branched, and the number of carbon atoms in the linear portion is 3 or more, preferably 3 or more and 6
Hereinafter, 3 or 4 alkylene groups are more preferred. The alkylene group represented by R1 may have a substituent, and examples of the substituent include an aryl group (e.g., phenyl group, etc.), a halogen atom (e.g., chlorine atom, fluorine atom, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.), cyano group, alkoxycarbonyl group (eg, methoxycarbonyl group, etc.).

Preferred alkylene groups represented by R1 below.

♂H3 In the general formula [I], R2 represents an aryl group, and specifically, this aryl group includes a phenyl group,
Examples include naphthyl group. The aryl group represented by R2 may have a substituent, such as a straight chain or branched alkyl group (for example, a methyl group,
n-butyl group, t-butyl group, t-pentyl group, t-octyl group, dodecyl group, etc.), alkoxy lI (e.g.
methoxy group, butoxy group, dodecyloxy group, etc.), halogen atom (e.g., chlorine atom, bromine atom, etc.), acylamino group (e.g., methoxyamino group, butoxyamino group, etc.), diacylamino group (e.g., methoxymethoxyamino group) , methoxyethoxyamino group, etc.), imide II (
Examples include succinimide group, etc.), sulfonamide group, alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), carbamoyl group, and acyl I group (eg, acetyl group, etc.). These substituents may have two or more, and in that case, the substituents may be the same or different.

The 1H-pyrazolo'3,2-CI-8-triazole magenta coupler of the present invention substituted with a group represented by the general formula [1] is preferably represented by the following general formula [I].

General Formula [II] In the formula, -R+-301-Rλ is a group represented by the above general formula [I]. R3 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterosm, and X represents a group that is eliminated by reaction with an oxidized product of a color developing agent, and does not contain a hydrogen atom.

In the general formula [n] above, the alkyl group represented by R3 substituted at the 6-position includes primary alkyl, secondary alkyl, and tertiary alkyl groups, and the primary alkyl group is represented by the general formula [II]. is an alkyl group in which at least two hydrogen atoms are bonded to the root carbon atom of the alkyl group bonded to the 6th-position carbon atom, such as a methyl group or an ethyl group.

As a secondary alkyl group, 11! is an alkyl group to which hydrogen atoms are bonded, for example, 1-propyl group,
5ea-butyl group, etc. The 311i alkyl group is an alkyl group in which a hydrogen atom is not bonded to the root carbon atom of the alkyl group bonded to the 6th-position carbon atom,
Examples include t-butyl group and t-pentyl group.

Examples of the cycloalkyl group represented by R3 include a cyclohexyl group.

The aryl group represented by R3 is preferably a phenyl group.

Examples of the heterocyclic group represented by R3 include a heptad ring group and a thiophene ring group.

In the general formula [I[], 111i1 is produced by reaction with an oxidized product of a color developing agent represented by
Examples of the 12-binding group include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an oxygen atom, a nitrogen atom, or a sulfur atom that is bonded to the 7-coupling position.

To explain in more detail the Ti group bonded to the 7-coupling position of the oxygen atom, nitrogen atom, or sulfur atom, 131! Examples of organic groups bonded to the coupling position of atoms include alkoxy groups, aryloxy groups,
Examples include acyloxy group, heterocyclic oxy group, etc.
Examples of the IM bonded to the coupling position of the i*i child include an acylamino group, a diacylamino group, a sulfonamide group, and a 5- or 611-membered heterocyclic group containing a nitrogen atom thereof, and furthermore, a sulfur atom. Examples of the organic group bonded to the coupling position include a thiocyano group, an alkylthio group, an arylthio group, a heterocyclic thio group, an arylsulfonyl group, and an alkylsulfonyl group.

Hereinafter, 1H-pyrazolo[3゜2-C
] Specific examples of -s-)-lyazole magenta couplers are shown below, but the present invention is not limited thereto.

Exemplary magenta coupler CsH 凰7(t) (・M17(S08山1(t) (to) This paper describes a method for synthesizing magenta couplers.

The group represented by the general formula [I] of the present invention, i.e. -R+
-8Oz-R2, is the corresponding R knee SOλ-R+-C
oo)-1, but Rz-8-R+
-COOHIIR [Obtained by oxidation with superconcentrated hydrogen according to the method of No. 47-24321 No. 1.

After obtaining Rz-3oz-R1-COOHe 17) The synthesis of IH-virazoO[3,2-C]-S-triazole was published in Research Disclosure No. 12443 and Journal of the Chemical Society, Parkin I ( J public or the Qhe+m1
calSociety, Perkin I),
1977, 2047-2052 were used as reference. 7 more
For the introduction of the leaving group at the position, reference was made to US Pat. No. 3,125,087 and JP-A-59-99437@.

A specific synthesis example will be shown below.

Synthesis S1 Synthesis of exemplary magenta coupler (1) 1) Synthesis of γ-(2-butoxy-5-t-octylphenylthio)butyric acid 2-butoxy-5-t-octyl-phenylmercaptan 29.49 and γ-butyO 8.6 g of lactone was dissolved in 100 μm of dimethylformamide, 20 μm of sodium methylate was added, and the mixture was heated and stirred at 80° C. for 2 hours.

Pour into a reaction sample and acidify with hydrochloric acid. The precipitated crystals are collected by filtration and washed with methanol to obtain the target product in almost pure form.

2) Synthesis of γ-(2-butoxy-5-t-octyl-phenylsulfonyl)butyric acid 35.6 g of γ-(2-butoxy-5-t-octyl-
Phenylthio)butyric acid to acetic acid9C)eJ! Dissolved in 50
31.8Q of 30% hydrogen peroxide is slowly added dropwise at ~60°C. Thereafter, it is heated at 100° C. for 2 hours.

After cooling, the precipitated crystals are collected by filtration. Wash thoroughly with hexane to obtain a nearly pure target product.

This was synthesized according to the method of IK, Journal of the Chemical Society, Perkin I, 1977, 2077-20521C.

Disperse the hydrazine derivatives io and ag obtained in 3) in 100■y of acetonitrile, add 6.49% of triethylamine, and dissolve the acid chloride obtained from 1121.7(+) obtained in 2) in a small amount of acetonitrile. Drip.

Then reflux for 30 minutes. The acetonitrile was distilled off, poured into water, and extracted with ethyl acetate. Distill off ethyl acetate,
The residue is purified by column chromatography.

The desired product is obtained as a light brown powder.

22. Dissolve 50-4) in toluene to obtain phosphorus oxychloride 6
．． Add 0g and boil for 2.5 hours. Thereafter, 9.8 g of triethylamine was added and boiled for an additional 15 minutes. Thereafter, toluene was distilled off, and the residue was dissolved in ethyl acetate and thoroughly washed with water.

Ethyl acetate is distilled off, and the residue is purified by column chromatography.

1.1 g of 5) in 15 m concentrated sulfur, & 35 m glacial acetic acid
Add to a mixture of 3 s of water and 3 s of water and boil for 6 hours. The acetic acid was distilled off, and the residue was poured into water and neutralized with caustic soda.

Extract with ethyl acetate and wash thoroughly with water. By distilling off the ethyl acetate, a pure target product is obtained.

7) Synthesis of 5.7 g of Exemplary Magenta Coupler (1) 6)
was dissolved in chloroform, 1.4 g of N-chloroscumimide was added thereto, and the mixture was reacted at room temperature for 1 hour. Thereafter, the reaction solution is washed with dilute alkali and then thoroughly washed with water. Chloroform is distilled off, and the residue is purified by column chromatography to obtain the desired product as a colorless powder. IR identification of the target product was performed using nuclear magnetic resonance spectroscopy.

Magenta couplers of the present invention other than the above-mentioned exemplified magenta coupler (1) can also be synthesized according to the above-mentioned synthesis example. Note that groups other than chlorine atoms as leaving groups are described in U.S. Pat.
It was introduced with reference to No. 37.

The amount of the magenta coupler according to the present invention added to the photographic light-sensitive material of the present invention is 1.5X 1G per mole of silver.
A range of mol to 7,5X 10-' mol is preferred, more preferably a range of 1X10 mol to 5x10 mol.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper, but especially when used as a color photographic paper for direct viewing, the method of the present invention can be used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which silver halide emulsion layers containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and layer order. The order may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any number used in emulsions can be used.

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

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
)H, 1)AQ may be produced by controlling and simultaneously adding them sequentially. After growth, the halogen composition of the particles may be changed using the convergence method.

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the inside of the particles and/or on the surface of the particles using iron salts or complex salts, and by placing them in an appropriate reducing atmosphere, metal ions can be added to the inside of the particles and/or on the surface of the particles. Can provide reduction-sensitized nuclei.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, the [1,0,0] plane and the [1,1,1] i
Any ratio of li can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

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

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing capri during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as anti-capri agents or stabilizers can be added before coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. The hardening agent is liI! in the processing solution. Although it is desirable to add a hardening agent to the extent that it is possible to harden the photosensitive material, it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion (latex) of a water-insoluble or nWJ synthetic polymer may be included in the photographic emulsion layer or other hydrophilic colloid layer of a photosensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. I can do it.

The emulsion layer of the silver halide color photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidized product of an aromatic 11i amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) in the color-forming ring treatment. A dye-forming coupler is used that performs the following steps to form a dye. The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming dye is formed for the blue light-sensitive emulsion layer. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.

However, depending on the purpose, a silver halide color photographic light-sensitive material may be produced by using the above-mentioned combinations in a suitable manner.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), and macenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and birazolo couplers. Examples include triazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions are reduced. Either 2-equivalence is fine.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water type emulsification dispersion method can be applied to a method of dispersing hydrophobic compounds such as couplers, and usually has a high boiling point of about 150°C or higher *i
If necessary, a low boiling point and/or water-soluble organic solvent is used in combination to dissolve the solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution to form a stirrer, homogenizer, colloid mill, flow jet mixer, ultra-low boiling point and/or water-soluble organic solvent. It may be added to the target hydrophilic colloid layer after emulsification and dispersion using a dispersing means such as a sonic device. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point oils include phenol derivatives, phthalate esters, phosphate esters, which do not react with the oxidized form of the developing agent,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
An ammonium medium having a temperature of 0° C. or higher is used.

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

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color capri-preventing agent may be used in emulsion 1 itself, or may be used in emulsion 1 itself.
A layer may be provided between adjacent emulsion layers and used as a middle dark layer.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a single filter layer, a Halley siding prevention layer and/or an irradiation prevention layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention, the gloss of the photosensitive material is reduced and the addability is increased.
A matting agent can be added for the purpose of preventing the sensitive materials from sticking to each other.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

A photographic material using the silver halide emulsion of the present invention includes a flexible reflective support such as paper or synthetic paper in which the photographic emulsion layer and other layers are laminated with a baryta layer or an α-olephne polymer, cellulose acetate, Cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
It can be applied to films made of semi-synthetic or synthetic polymers such as polycarbonate and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be used directly or (adhesiveness, antistatic property, dimensional stability, resistance It may be applied via one or more subbing layers (to improve abrasion, hardness, antihalation, frictional properties and/or other properties).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can be uniformly developed by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of from about 0.1 (J to about 309) per color developer 1!2, preferably from about 1 g to about 1.
Use at a concentration of 5g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-〇-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-diethyl-〇-phenylenediamine hydrochloride,
'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-〇-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components that are normally added to color developers, such as sodium hydroxide and carbonate. It may optionally contain alkaline agents such as sodium and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, etc. . The pH value of this color developer is usually 7 or higher, most commonly about 10 to
It is about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such a metal complex salt include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [51 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt] [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used as a sodium salt contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, the pH of borates, M salts, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, bisulfite, potassium acid, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc., boric acid, borax, sodium hydroxide, water A pH1 agent consisting of various salts such as potassium oxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be used alone or in an amount of 2 f1 or more.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach window W* (bath) may contain thiosulfate, thiocyanate, sulfite, etc. , the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleaching window i'a,
In the bleach-fix bath and in the bleach-fix replenisher storage tank, air or oxygen may optionally be bubbled, or a suitable oxidizing agent such as hydrogen peroxide, bromate, perglycide, etc. may be added as appropriate.

In the following margin [Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[Example-1] The magenta coupler of the present invention and the comparative coupler shown in Table 1 were each taken in an amount of 0.1 mol per mol of silver, and dibutyl phthalate and 3
Double amount of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with 120 s of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
Mix with 12 ooml of 5% gelatin aqueous solution containing
The mixture was emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to a green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) 4kQ, and 1,2-bis(
Samples 1 to 10 were prepared by adding 120 IF of a 2% solution of (vinylsulfonyl)ethane (water:methanol-1=1), and coating and drying it on a paper support laminated on both sides with polyethylene. (Amount of coated silver: 51 g/100 cm2) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. Table 1 shows the results.

[Development processing step: 111 degrees, time color development, 38 degrees Celsius, bleaching for 3 minutes and 30 seconds.
33℃ 1 minute 30 seconds stabilization treatment/or water washing treatment 25-30℃ 3 minutes drying
75-80°C Approximately 29 In each treatment step, the composition of the treatment liquid used was as follows.

[Color developer 1 Benzyl alcohol ethylene glycol 15 companies Potassium sulfite 2.0g Potassium bromide
0. IQ sodium chloride
0.2g potassium carbonate
30, O Q hydroxylamine sulfate 11
3, O a polyline # (TPPS)
2.5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4.4'-diaminostilbenzsulfone M derivative) 1, OQ potassium hydroxide 2. Add Oa water to bring the total volume to 11 and adjust to EIH 10.2G.

[Bleach-fixing 11 Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 Q Ethylenediaminetetraacetic acid M 3Q Ammonium thiosulfate (10% solution> 1ooml Ammonium sulfite (40% solution) 27.5 11 p@7 with potassium carbonate or glacial acetic acid. Adjust to 1 and add water to bring the total amount to 1.
Let it be Q.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 Ql-hydroxyethylidene-1,1'-diphosphone II 2 5 (+ bismuth chloride 0.29 magnesium chloride 0 .19 Ammonium hydroxide (28% aqueous solution) 2.O.

Add 1.0 g of sodium nitrilotriacetate to bring the total volume to 1F, and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

However, in Table 1, the specific sensitivity is the sensitivity of sample-1 10
0 represents the relative sensitivity of each sample, λ-aX represents the maximum spectral absorption wavelength of each sample, and D(λS) represents λ■
When the spectral reflection density at aX is 1.0, it represents the concentration at a wavelength 9On- shorter than λ-ax, while D(λ
L) represents the concentration at a wavelength 9 Qns longer than λ-ax. (See Figure 1) That is, D(λ5)-D(λ-aX
−90), D(λL)−(λ−ax+90).

The larger the value of D(λS), the larger the incorrect absorption in the blue region, and the larger the value of D(λL), the larger the incorrect absorption in the red region.

An explanatory diagram of the above D(λs) and D(λL) is shown in FIG. In addition, samples-1, 4, 5, 6, obtained in Example-1,
The absorption spectrum (wavelength-concentration curve) diagram of 9 and 10 is shown in the first
2 and 3. Here, curve 1 in FIG. 1 is the absorption spectrum curve of sample-1 (comparison), and curve 2 is the absorption spectrum curve of sample-6 (invention). Curve 3 in Figure 2 is sample-4
(Comparison) Curve 4 is the absorption spectrum curve of Sample-9 (invention). Curve 5 in FIG. 3 is the absorption spectrum curve of Sample-5 (comparison), and curve 6 is the absorption spectrum curve of Sample-10 (invention).

Light resistance was determined by exposing each sample to a xenon fade meter for 6 days and then expressing the concentration at an initial concentration of 1.0.

The structures of the comparative couplers used in Table 1 below are shown below.〇◎Comparative coupler 1 (Example C3 of 4I application No. 59-243012)) ◎Comparative coupler 2 (%Example of application No. 59-243012) 9)]◎Comparative coupler 3 ←Example 01 of Japanese Patent Application No. 59-243012)◎Comparative coupler 4 (Example (2) of Japanese Patent Application No. 59-243010)◎Comparative coupler 5 (Example 01 of Japanese Patent Application No. 59-243010) Example (5)] As is clear from the results in Table 1, the samples (Samples 6 to 10) prepared using the couplers of the present invention are different from the comparative samples (Samples 1 to 5).
), it can be seen that the color development and light resistance are excellent. Although there is not much difference in λlaX among the samples, as shown by the values of D(λS) and D(λL), the sample according to the present invention (
It can be seen that samples 6 to 10) have considerably improved irregular absorption in the blue light region and red light region compared to the comparative samples (samples 1 to 5).

As is clear from these drawings, the silver halide photographic material of the present invention has less irregular absorption in the blue light and red light regions than the comparative silver halide photographic material, and has good color reproducibility. It can be seen that

[Example 2] A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide.

The amounts added below are per 100c+e2.

(1) Gelatin of 20+eg, blue-sensitive silver chlorobromide emulsion of 5+go as the silver layer, yellow coupler of 8 quantity Q and 2.5-di-t-octylhydroquinone of 0.1 σ dissolved in 3111 di- Layer containing octyl phthalate coupler solvent.

(2) Interlayer containing 21 g of dibutyl phthalate UV absorber solvent in which 1211 J of gelatin, 0.5 mg of 2,5-di-t-octylhydroquinone, and 4 σ of UV absorber were dissolved.

(3) 18 ■ Q gelatin, 4 ■ Q green-sensitive silver chlorobromide emulsion, and 5-0 magenta coupler and 21 g.
of antioxidant and 2,5-g of dioctyl phthalate coupler solvent in which 0.21 g of 2,5-di[-octylhydroquinone was dissolved.

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

(5) 16ia of gelatin, a red-sensitive silver chlorobromide emulsion with a silver content of 4-a, and 3.519 of a cyan coupler and 0.1Q of 2.5-di-t-octylhydroquinone dissolved in 2 , a layer containing a tricresyl phosphate coupler solvent of OmQ.

(6) Gelatin protective layer containing 91G gelatin.

Coating aids are added to each layer (1) to (6), and (
A gelatin crosslinking agent was added to layers 4) and (6).

As the ultraviolet absorber (2) and (4), u with the following structure is used.
A mixture of vi and UV-2 was used. As the antioxidant (3), di-t-pentyl hydride quinone-di-octyl ether was used.

The above multilayer photosensitive material was processed in the same manner as in Example-1. Table 2 shows the yellow coupler, magenta coupler, and cyan coupler used in each layer and the results.

Each sample was measured for magenta density after exposure to white light.

Further, measurements of specific sensitivity and light resistance were carried out in the same manner as in Example 1.

From Table 2, it is clear that the light fastness of the dye ili images of the couplers of the present invention is excellent and can be further improved by using an ultraviolet absorber.

Ultraviolet absorber Y-Coupler C-Coupler CL Table 2 [Example-3] As shown in Table 3, 0.1 mole of each of the magenta coupler of the present invention and the comparative coupler were taken per mole of silver, One part of tricresyl phosphate and three parts of ethyl acetate based on the coupler weight were added and heated to 60°C to completely dissolve. This II was mixed with a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, DuPont Newsletter) 12
The mixture was mixed with tzooml of a 5% aqueous gelatin solution containing 01F, and emulsified and dispersed using an ultrasonic disperser to obtain an emulsion. Thereafter, this dispersion was added to 4 ka of green-sensitive silver iodobromide (containing 6 mol% silver iodide), and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water: methanol) was added as a hardening agent. 1
Samples 22 to 36 were prepared by adding: i) 120■1, coating and drying on a subbed transparent polyester base. (Amount of coated silver: 20 tM 100C 2) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. Table 3 shows the results.

[Development processing process] 1. Color development 38℃ 3 minutes 15 seconds 2.
White 38℃ 6 minutes 30 seconds 3, wash with water
38℃ 3 minutes 15 seconds 4, fixation 38℃
6 minutes 30 seconds 5, water washing 38°C 3 minutes 15 seconds 6, stability 38°C 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

[Color-1IfIA liquid composition] Sodium nitrilotriacetate 1.0g Sodium sulfite 4. OQ sodium carbonate
30.09 Potassium Bromide
1.5g hydroxylamine sulfate
2.5g 4-(N-ethyl-N-(3-hydroxyethylamino)-2-methyl-aniline sulfate 4.5g water added 1ρ1) 8
10.02 [1 White liquor composition] Ammonium bromide 160.0Q aqueous ammonia (28%) 25,0IJ2 ethylenediamine-tetraacetic acid sodium iron salt t3og glacial acetic acid
14-Q Add water
1Q [Fixer composition] Sodium tetrapolyphosphate 2. OQ Sodium bisulfite 4.0g Ammonium thiosulfate (70%) 1sosi) Sodium bisulfite 5.0g Add water
1! [Stabilizing liquid composition] Formalin 10. O12 water was added and the margin was 11 or less No. 3 R As is clear from the results in Table 3, samples 27 to 36 prepared using the couplers of the present invention were all superior to the comparative samples in both color development and light resistance. I know that there is.

[Brief explanation of drawings]

Figures 1, 2, and 3 are absorption spectra (wavelength-spectral reflection density curves) of the samples obtained in Example 1, respectively.
4 are explanatory diagrams of O(λS) and D(λL). Patent applicant: Roku Konishi Photo Industry Co., Ltd. Figure 1 Wavelength (ζki) Figure 2 Text & (vL kite) Figure 3 Wavelength (hemachi Figure 4 Wavelength (Maki)

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the 3-position in at least one of the silver halide emulsion layers has the following general formula [I
] 1H-pyrazolo[3,2
A silver halide photographic material containing a -C]-s-triazole magenta coupler. General formula [I] -R_1-SO_2-R_2 In the formula, R_1 is an alkylene group connecting the carbon atom at position 3 of the 1H-pyrazolo[3,2-C]-s-triazole nucleus and -SO_2-R_2. The straight chain portion of the alkylene group has 3 or more carbon atoms, and R_2 represents an aryl group.