JPS61169846A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve resistance to light and formalin and to obtain excellent colorability by incorporating a specific magenta coupler into at least one layer of a silver halide (AgX) emulsion layer on a base. CONSTITUTION:The magenta coupler expressed by the formula (R is H or substituent, n is 0-2. J is a simple coupler or divalent org. group. Z is a non-metallic atomic group which can form a nitrogenous heterocycle and does not form a condensed ring.) is incorporated into at least one layer of the AgX emulsion layer on the base. The photosensitive material incorporated therein with such magenta coupler is highly resistant to light and formalin and has the high colorability. The material is usable for color negative and positive films as well as color photographic paper, etc. and is particularly remarkable in the effect when used for the color photographic paper.

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 material containing a novel magenta coupler.

(Prior art) In conventional silver halide color photographic materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidized product of the color developing agent produced at this time and Dye images can be obtained by coupling with couplers that form 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 has poor storage stability, especially resistance to formalin gas (formalin resistance). It has the following drawbacks.

In order to improve the above-mentioned drawbacks, various 1-pyrazolo[3,2-Cose-)-lyazole magenta couplers have been proposed. For example, U.S. Patent 3,725
, No. 067, British Patent No. 1,252,418, 1.3
No. 34,515. The compounds described in both patents are, of course, superior to pyrazolone magenta couplers in terms of absorption (1), but improvements in formalin resistance are insufficient, and little improvement has been shown in terms of color development and light fastness of images. Not yet.

Research D 1 closure 1244
Compound according to 3.

This product cannot be put to practical use at all in terms of color development. Japanese Patent Application Publication No. 5
1 day-pyrazolo C3,2-CI described in 8-42045
Although the -s-triazole type magenta couplers have been significantly improved in terms of formalin resistance and color development, there has been little improvement in light resistance.

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.

As an afterthought, the light fastness of the image is simply improved by the additives used in combination. 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.

In other words, 1-day pyrazolo [3
, 2-C1-5-triazole type magenta couplers, it can be said that little improvement has been made in terms of the light resistance of dye images.

(Object of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material which has good light fastness and formalin resistance and has high color development.

(Structure of the Invention) The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula: This is achieved by a silver halide color photographic light-sensitive material containing a magenta coupler represented by [I].

General formula [I] In the formula, R represents a hydrogen atom or a substituent, and n is Oll
or 2. J represents a simple bond or a divalent organic group, and Z represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle.

(However, the nitrogen-containing heterocycle represented by 2 does not further form a condensed ring.) Below, unless otherwise specified, the group represented by in the compound represented by the general formula [I] will be simply referred to as X for convenience. represented by.

Specifically, the substituent represented by R is a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, siam L spiro compound residue, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amide L acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group , an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an aryloxy group, or a heterocyclic thio group.

Next, the magenta coupler represented by the general formula [I] of the present invention will be explained in more detail.

In the general formula [E], examples of the halogen atom represented by R include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 32 carbon atoms.
32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
Further, the alkyl group, alkenyl group or alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom, specifically, anddroxy, alkoxy, and aryloxy. , heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulf7moylamino, alkoxycarbonylamino, aryloxycarbonylamino amino, sulfonamide, imide, ureido, etc. those substituted via a nitrogen atom, those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., those substituted via a phosphorus atom such as phosphonyl, etc. It's okay.

Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a pentadecyl group, a heptadecyl group,
1-hexylnonyl group, 1.1′-dibentynonyl group, 2-chloro-t-butyl group, trifluoromethyl group,
1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-■-butanesulfonaminophenoxypropyl group , 3-4'-(α-[4" (p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl group, 3-(4'-[α-(2
",4"-di[-amylphenoxy)butanamide]
phenyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecanamidophenoxy]propyl group,
Examples include allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R is preferably a phenyl group, and this aryl group has a substituent group (for example, an alkyl group,
(alkoxy group, acylamino group, etc.).

Specifically, suenyl group, 4-t-butylphenyl group,
2.4-di-t-7milphinyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butylphenoxy)tetradecanamido]phinyl group and the like.

The heterocyclic group represented by R is preferably a 5- to 7-membered one, which may be substituted or fused. Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group,
Furkylcarbonyl groups such as phenylacetyl group, dodecanoyl group, α-2,4-di[-7milphenoxyptanoyl group, etc., arylcarbonyl group such as benzoyl group, 3-pentadecyloxybenzoyl group, p-chlorobenzoyl group, etc. Examples include groups.

Examples of the sulfonyl group represented by R include alkylsulfonyl groups such as methylsulfonyl group and dodecylsulfonyl group, and arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group, and arylsulfinyl groups such as phenylsulfinyl group and -pentadecylphenylsulfinyl group.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyl group), etc. Examples include octylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, and N-(3-(2,4-di-t-amylphenoxy)propyl)carbamoyl group.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, N, N-
Examples include diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-7enylsulfamoyl group.

Examples of the spiro compound residue represented by R include spiro[3,3]hebutan-1-yl.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3,3,1,1'']]decane-1-yl7,7-yl, Examples include dimethyl-picyclo[2°2°1]butan-1-yl.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyloxy group, and a 2-dodecyloxy group. Examples include ethoxy group and phenethyloxyethoxy group.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, pt-butylphenoxy group, -1pentadecylphenoxy group, and the like.

The heterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3.4.5.6 -tetrahydrobilanyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group, such as a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group and an arylcarbonyloxy group, which may further have a substituent, specifically an acetyloxy group, an α-chloroacetyl group, etc. Examples include oxy group and benzoyloxy group.

The carbamoyloxy group represented by R is an alkyl group,
It may be substituted with an aryl group, and examples thereof include N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N-phenylcarbamoyloxy group, and the like.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anirim L - chloroanirim L3
-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

The acylamino group represented by R includes an alkylcarbonylamino group, an arylcarbonylamino group (preferably phenylcarbonylamino group 1, etc.), and may further have a substituent, specifically an acetamido group, α-ethyl Examples include a propanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxyacetamide group, and an α-3j-butyl-4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarinide group, etc. Examples include imide groups.

The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N~methyl-N-decylureido group, an N-phenylureido group, Examples include N-p-tolylureido group.

The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group. group, N-phenylsulfamoylamino group, and the like.

The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The aryloxycarbonylamino group represented by R is
It may have a substituent, and examples thereof include phenoxylponylamino and 14-methylphenoxycarbonylamino groups.

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, etc. .

The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and a pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples thereof include an octadecylthio group, a phenethylthio group, and a 3-phenokizib avirthio group.

The arylthio group represented by R is preferably a phenylthio group, and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2
-carboxyphenylthio group, p-acetaminophenylthio group, etc.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a fused ring,
It may also have a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1.3.5-triazole-6-thio group.

Examples of the nitrogen-containing heterocycle formed by 2 include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

In addition, the substituents (for example, R to R8) on the heterocycle in general formula [I] and general formulas [1 [] to [■] described below are moieties (herein, R' and Z' are general formulas [1] to [■]). ] in R,
It has the same meaning as Z, and when X has the above-mentioned condition, it forms a so-called screw type coupler, but is of course included in the present invention.

More specifically, what is represented by the general formula [1] is represented by, for example, the following general formulas [I[] to [■1].

General formula [1r] General formula [111] General formula [rV] General formula [V] General formula [VI] General formula [■] x'' In the general formulas [n] to [■], R-R8 and X has the same meaning as R in the general formula [IF, and X is as described above.

Also, the following general formula [IF is preferred among the general formulas [IF].
■It is represented by ko.

General formula [■] In the formula, R, X and zI are the general formula [RlX in IF
and Z.

Among the magenta couplers represented by the general formulas [1[] to [■]], particularly preferred are the magenta couplers represented by the general formula [1r].

Regarding the substituents on the heterocycle in the general formulas [ff] to [■], R in the general formula [IF and R in the general formulas [II] to [■] satisfy the following condition 1. It is preferable that the following conditions are satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 3 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2i1 Only one hydrogen atom is bonded to the carbon atom, or no hydrogen atom is bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituent R on the heterocycle is one represented by the following general formula [IX].

General formula [IX] g Soy R,, -C- IO In the formula, Rq, R+. and R11 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl group, and a sulfamoyl group. group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, Represents an imido group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, Rq, Rho and RII At least two of the atoms are not hydrogen atoms.

Furthermore, two of the above Rq, Rho and RII, for example Rcl and Rho, may be combined to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle), and furthermore, in this ring, RII may be bonded to form a bridged hydrocarbon compound residue.

The group represented by R9 to R++ may further have a substituent, and specific examples of the group represented by R9 to R++ and the substituents that the group may have include the aforementioned general formula [I] Specific examples of the group and substituents represented by R are listed.

Further, specific examples of the ring formed by bonding RQ and Rho and the bridged hydrocarbon compound residue formed by R9 to Ru and the substituents thereof may include the above-mentioned general formula [1] Specific examples of cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in and their substituents are listed.

Among the general formula [IX], (i) Rq ~
If two of R++ are alkyl groups, (ii) Rq~
When one of the R's, for example R9, is a hydrogen atom and the other two, Rho and R11, combine to form a cycloalkyl group with the root carbon atom, the following holds true.

Further preferred in (1) is the case where two of RQ=R1t are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent. Specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent represented by R in the general formula [I]. Specific examples of substituents are listed.

In the general formula [I], n is represented by 0, 1 or 2.

In the general formula [I], J is a simple bond or 2
The divalent organic group represented by J includes an alkylene group, an arylene group, and a combination of an alkylene group and an arylene group. i group, and a divalent group consisting of a combination of an alkylene group, an arylene group, and an oxygen atom, and specifically, for example, an alkylene group (
(e.g., methylene group, ethylene group, etc.), arylene group (e.g., l: phosphorus group, naphthylene group, etc.), alkylenearylene group (e.g., methylenephenylene group, etc.), arylenealkylene group (e.g., phenylenemethylene group, etc.), alkylenearylenealkylene groups (e.g., methylenephenylenemethylene group, etc.), arylenealkylenearylene groups (e.g., phenylenemethylenephenylene group, etc.), alkyleneoxyalkylene groups (e.g., ethyleneoxyethylene group, etc.), alkyleneoxyphenyleneoxyalkylene groups (e.g., ethyleneoxyphenyleneoxyethylene group, etc.) ), aryleneoxyalkyleneoxyarylene groups (e.g., phenyleneoxyethyleneoxyphenylene group, etc.), and the alkylene residues and arylene groups of these groups include substituents (halogen atoms, alkyl groups, aryl groups, etc.). May have.

The magenta coupler according to the present invention preferably has a symmetrical screw body, but an asymmetrical coupler is also included in the present invention.

Specific examples of the magenta coupler of the present invention represented by the general formula [I] will be shown below, but the present invention is not limited thereto.

The couplers of the present invention can generally be synthesized by the following method.

(When n-0) To synthesize n-10-2, the compound Na of n-0
It can be synthesized by oxidation with SrO□, etc.).

Margin below Next, specific methods for synthesizing these compounds will be shown.

Journal of the Chemical 5
ociety, perkin l.

2047-(1977), U.S. Patent 3,725,067
The synthesis was carried out with reference to JP-A No. 48-30895.

Synthesis Example 1 [Exemplary Compound (2)] Reaction Scheme -→ (2) Synthesis of Compound (II) 42 g of (I) was dissolved in 2 oot/ml of chloroform,
Cool to 0°C. A solution of 12.50 N-bromosuccinimide dissolved in 5 on/ml of chloroform is added to this solution. After the dropwise addition is complete, the temperature is returned to room temperature and stirring is continued for an additional 2 hours. The solution was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane-ethyl acetate mixed solvent) to obtain 31a(i).

Synthesis of Compound (TV) 27+I tv (If) 3.10 minutes was added to 3 ounces of urea/ethanol and refluxed for 4 hours. After cooling, the solvent was concentrated to 1/3 under reduced pressure and poured into 500 μl of water.

Add 3.8g of sodium hydroxide to this and
Stir for 1 minute. Then, add concentrated sulfuric acid to neutralize.

Add 30017 ethyl acetate to this solution for extraction.

After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (acetone-toluene mixed solvent).
Obtain (IV) of Ω.

Synthesis of Exemplified Compound (2) 6.3 g of (IV) and 6.1 g of (I) are added to 200 IQ of acetonitrile, and further 2 g of triethylamine is added. After heating under reflux for 6 hours and cooling, the precipitated crystals were filtered out and recrystallized from ethanol to yield 8.5 g of the desired product (2
). The structure of the target product was confirmed by NMR, IR, and mass spectrometry.

Synthesis Example 2 [Exemplified Compound (3)] 5 g of Exemplified Compound (2) was mixed with 1 oomQ of dioxane and 5 ml of water.
Dissolve in a mixed solvent of omu and add 1.6 g of sodium bromite to this. Under M, stir for 1 hour, add 30% water
Open to 01Ω. The precipitated crystals were filtered and subjected to silica gel column chromatography (acetone-toluene mixed solvent).
Purification was performed to obtain 3.2 g of the desired product (3).

The structure of the target product was confirmed by NMR, IR, and mass spectrometry.

The amount of the magenta coupler according to the present invention added to the photographic light-sensitive material of the present invention is 1.5×10 per mole of silver.
The range is preferably from 7,5×1G moles to 7,5×1G moles, more preferably from 1×10 moles to 5×10 moles.

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. In particular, when a color photographic paper intended for direct viewing is used, 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 of those 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 methods for creating and growing 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
It may also be produced by controlling and sequentially adding H and PAg simultaneously. After growth, a conversion method may be used to change the halogen composition of the particles.

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 interior of the particles and/or on the surface of the particles using iron salts or complex salts, and can be reduced to the interior of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing 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 as they are 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 silver halide 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 grains.

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, any ratio of [1,0,01 planes to [1,1,1] planes 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 fog 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. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the 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 of a water-insoluble or sparingly soluble synthetic polymer (
latex).

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivative, 7-minophenol derivative, etc.). 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, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolo 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 need to be reduced. Either 2-equivalence may be used.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be treated with various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can apply a previously unknown method of dispersing hydrophobic additives such as couplers.1 Usually, a high boiling point organic solvent with a boiling point of about 150'C or higher is mixed with a low boiling point and /Or dissolved in combination with a water-soluble organic i-medium, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or long sonic device. After emulsification and dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic WI medium 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 organic solvent having a temperature of 0° C. or higher is used.

Anionic surfactants, nonionic surfactants, and cations can be used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. A surfactant 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 anti-capri agents are used to prevent deterioration and noticeable graininess.

The color antifoggant may be used in the emulsion layer itself, or may be used in a film intermediate layer by providing an intermediate layer between adjacent emulsion layers.

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 may have auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation 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.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, improves the ease of addition, and prevents the photosensitive materials from sticking to each other. A matting agent can be added to achieve this goal.

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).

The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, 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 The coating 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, xenon arc lamps, carbon arc lamps,
xenon flash lamp, cathode ray tube flying spot,
Various laser lights, light emitting diode lights, electron beams, X-rays, γ
Any known light source can be used, such as light emitted from a phosphor excited by rays, alpha 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 used to form an image 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 about 0.1 g to about 30 g for color developer 19;
Preferably about 1 g to about 1.5 g per color developer
Use at a concentration of

Examples of the amine phenol developer include 〇-aminophenol, p-aminophenol, 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-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino>-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline lilI acid salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p
-Toluenesulfonate and the like can be mentioned.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components normally added to color developer solutions, such as sodium hydroxide and carbonate. Alkali agents such as sodium and potassium carbonate, alkali metal sulfites, alkali metal bisulfite Il
! Salts, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The l)H value of this color developer is usually 7 or more, most commonly about 10 to 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. The bleaching agent used in the bleaching process is a metal complex salt, which 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. Its composition is aminopolycarboxylic acid or 11m! , metal ions such as iron, cobalt, copper, etc. are coordinated with organic acids such as citric acid.

The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids are alkali metal salts,
It may be an ammonium salt or a water-soluble amine salt.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] The bleaching agent used in the nitrilotriacetic acid sodium salt contains the above-mentioned metal complex salt of an organic acid 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, oxalates, 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,
Sulfites such as potassium 1lIII, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate , potassium carbonate, heavy sodium i
It may contain one or more pH buffers consisting of various salts such as sodium s, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with an electrobleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyan I salt, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

[Examples] Next, the present invention will be specifically explained using 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 tricresyl phosphate was added in an amount of 1 times the weight of the coupler and 3 times the weight of the coupler. of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
5% gelatin aqueous solution containing 011 1200IlIQ
and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to a green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide >4 ka) to give a hardening agent of 1.2
-2% solution of bis(vinylsulfonyl)ethane (water:methanol-1:1) 12om! Samples 1-1 to 1-10 were prepared by coating and drying on a subbed transparent polyester base. (Coated silver amount 20mQ/1
00 cm") The thus obtained sample was subjected to wedge exposure according to a conventional method and then subjected to the following development treatment. Table 1 shows the results.

[Development process] Color developing solution Bleaching at 38℃ for 3 minutes and 15 seconds
Liquid 4 minutes 20 seconds Water
Wash 3 minutes 15
Second fixing liquid 4
Wash with water for 20 seconds
Stable liquid for 3 minutes 15 seconds
Dry for 1 minute 30 seconds 47℃±55
℃ 16 minutes 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer composition] Potassium carbonate 30 Q Sodium bicarbonate 2.5 g Potassium sulfite 5 g Sodium bromide
1.3g potassium iodide
2 mg hydroxylamine sulfate
2.5g Sodium chloride 0.6
gSodium diethylenetriaminepentaacetate 2.5g4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8Q Potassium hydroxide 1.2g Add water and 1
9, and using potassium hydroxide or 20% sulfuric acid, p
Adjust to H10,06.

[Bleach solution composition Coethylenediaminetetraacetic acid iron ammonium salt 100 Q Ethylenediaminetetraacetic acid 10g Ammonium bromide 150g Ice vinegar H40mQ Sodium brobromine 10 (Add 1 water to make 1α, and use aqueous ammonia or glacial acetic acid to make p
Adjust to H3.5.

[Fixer composition Ammonium cothiosulfate 180 g Anhydrous sodium sulfite 12 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g Sodium carbonate 10 Q Add water to make one length.

[Stabilizing liquid composition] *A/? Li> (37% water mH) 2
mrl Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 5ml Add water and 11! shall be.

Table 1 1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of Capri density + 0.1, and sample No. 081 using comparative coupler 1) was set as 100.

2) 30'C162%RHG, :i! lI! ! After the sample was placed in a sealed container containing 6 cc of a humidity-controlled 0.9% formalin aqueous solution for 3 days, color development was performed. For comparison, a sample not treated with formalin is also developed.

In addition, formalin resistance was calculated|required according to the following formula.

3) The sample after the color development process was irradiated with a xenon fade meter for 5 days, and the percentage of dye remaining at the initial density of -1.0 was shown.

Comparison coupler 1 below; Comparison coupler 2) From table 1 below, the couplers of the present invention have color development, formalin resistance,
It is clear that it has excellent light resistance.

[Example 2 Samples 1-1 to 1-10 in Example 1 were similarly exposed to wedge light and subjected to the following development treatment.

These results are shown in Table 2. Insensitivity and light resistance were measured using the same method as in Example-1.

[Development process] Color development 38℃ 3 minutes 30 seconds Bleach fixing
33℃ 1 minute 30 seconds stabilization treatment/or water washing treatment 25-30℃ 3 minutes drying
75-80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] Benzyl alcohol 15alQ ethylene glycol 15toge potassium sulfite 2.0g potassium bromide
0.1Q sodium chloride
0.2g potassium carbonate
30.0! J Hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS)
2.5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate jl 5.5g optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1. 09 Potassium hydroxide 2.0g Add water to bring the total amount to 1 or more, p) 110.20 G-adjust.

[Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 609 Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (10% solution) 100 9 Ammonium sulfite (40
% solution) 27. Adjust to 7.1 l with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 1.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 109 or less Margin Table 2 As is clear from the results in Table 2, Sample 2 containing the coupler of the present invention It can be seen that samples from -4 to 2-10 are superior in sensitivity, color development, and light resistance compared to the comparative samples.

[Example 3] A silver halide color photographic material was prepared by sequentially coating the following layers on a polyethylene resin coated paper containing anatase type titanium oxide.

The amounts added below are based on the amount per 100012.

(1) 2Ggo of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, and 81 g of yellow coupler and 0.5 mg of silver. Layer (2) 12 m containing 3 mg of di-octyl phthalate coupler solvent in which 2.5-di-t-octylhydroquinone of leg was dissolved! I+ gelatin, 0.5 mg 2,5-
An intermediate layer comprising a 2ao dibutyl phthalate UV absorber solvent in which di-t-octylhydroquinone and a 411) UV absorber are dissolved.

(3) 18a+o gelatin, 41g of green-sensitive silver bromide emulsion as silver, and 2.5 weighs of dissolved magenta coupler of 5.9 and 0.21g of 2,5-di-t-octylhydroquinone. Layer containing dioctyl phthalate coupler solvent.

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

(5) 16 mg of gelatin, a red-sensitive silver chlorobromide emulsion with a silver content of 4 ■ O, and 3. A layer containing 2,0 mg of tricresyl phosphate coupler solvent in which Smg of cyan coupler and o, img of 2,5-di-t-octylhydroquinone were dissolved.

(6) Gelatin protective layer containing 9■O 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), L of the following structure is used.
A mixture of JV-1 and UV-2 was used.

The above multilayer photosensitive material was treated in the same manner as in Example-2. Table 3 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.

It is clear from Table 3 that the light fastness of the dye image of the coupler of the present invention is excellent, and it is also clear that it can be further improved by using an ultraviolet absorber.

Margin below UV absorber UV-1 UV-2 Y-coupler C-coupler csHst C1゜ C-3 Margin below Table 3

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I
A silver halide color photographic material containing a magenta coupler represented by the following. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a hydrogen atom or a substituent, and n is 0 or 1
or 2. J represents a simple bond or a divalent organic group. Z represents a nonmetallic atomic group capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by Z does not further form a condensed ring.)