JPS6289961A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the light resistance and to increase the sensitivity by using a specified pyrazoloazole series magenta coupler. CONSTITUTION:This silver halide color photographic sensitive material contains a pyrazoloazole type magenta coupler represented by formula I (where each of Za and Zb is =CH-, (a) or =N-, R1 is H or a substituent, R2 is a substituent and X is H or a group eliminable by a coupling reaction with the oxidized product of an aromatic primary amine developing agent). A compound represented by formula II (where each of R3 and R4 is H or halogen, one of them may be a group bonding to the pyrazoloazole ring through a secondary or tertiary C atom and one of them may be a group having one or more -NHSO2- groups) is preferably used as the coupler represented by formula I. The silver halide in the sensitive material is silver chloro(iodo)bromide or silver (iodo)bromide contg. 0-10mol% silver iodide.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material with improved color development and color image fastness to light. It is related to.

(Prior art) Pyrazoloazole couplers are conventional! - Compared to hirazolone, the spectral absorption of the dye obtained by coupling with the oxidized form of paraphenyldiamine has less unnecessary absorption around gjOnm, and various proposals have been made to improve the color reproduction of color photosensitive materials. .

In the old days, the pyrazolobenzimidazole skeleton known in U.S. Pat. The iH-pyrazolo[31"2")[',a2゜ri]triazole skeleton known from US Pat. No. 067, ! 00t30
iH-imidazo [/, J-b] pyrazole skeleton, known as No.
H-pyrazolo (/.

r-b] (/, z, sc] triazole skeleton, iH-pyrazolo (l,
t-b) A tetrazole skeleton has been proposed.

(Problem to be solved by the invention)
It is true that the azomethine dye has little unnecessary absorption in the vicinity of ≠JOnm, has a sharp edge on the long wavelength side, and is favorable for color reproduction, but the coupling rate with the oxidized form of the developing agent is slow, and the resulting color image Due to poor light fastness,
It was still unsatisfactory for use in color photographic materials.

Therefore, an object of the present invention is to combine a coupler + with an oxidized form of a developing agent.
) A silver halide color sensitizer using a pyrazoloazole coupler sound, which speeds up the processing speed, improves color development, improves the fastness of the produced color image, especially light fastness, and furthermore enables high sensitivity. We will provide all materials.

(Means to solve the problem) The above purpose? In order to achieve this, in the present invention, as a result of various studies on connection funds that connect the periphery of the pyrazoloazole skeleton and the diffusion-resistant group, the pyrazoloazole-based magenta coupler represented by the general formula [l] has been found to be suitable for these purposes. The inventors have discovered that these couplers have excellent properties, and have achieved this objective by producing silver halide color light-sensitive materials containing these couplers.

General Formula [1] The pyrazoloazole coupler represented by General Formula [1] will be explained in detail below.

In the general formula [I], the term "multimer" refers to one having one or more groups represented by the general formula [I] in the molecule, including bis-forms and polymer couplers (including two). .

Here, the polymer coupler may be a homopolymer consisting only of a monomer containing a moiety represented by the general formula [I] (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic-based monomer. Nicobolimers may also be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of amine development.

The couplers represented by the general formula [l] are each represented by the general formula (
1-/), (1-2), Cl-3), (I-'I) and (■-ta).

(I-/) (I-, z) (1-3)
(1-da) General formula (I-/) ~ (I-r
) Preferred couplers for the purpose of the present invention are those having the general formulas (1-/), (1-,2) and (1-
3), and a more preferred one is represented by the general formula (1-1).

Substituents of the general formula CI-/) to (1-3], R3,
R4 and R4 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups,
Aryloxy group, heterocyclic oxy group, acylmanxy group, carbamoyloxy group, silyloxy group, sulfonyloxytin, acylamino group, anilino group, ureido group,
Imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, hederoylamino group, alkoxy sulfonylamino group, aryloxy sulfonylamino group, sulfone gamma group, elpamoyl convex, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxysulfonyl group, and at least one of 几3, 几4 or R5 is - class tt, < means pyra through a tertiary carbon atom. zoroazole ≦ represents a group with two bonds, and at least one of R3, R, 4 or 几5 is
It is a group having one or more -NH8O2- groups, and is a general group (
I-J)'s 几4 is! It is not a substituted or unsubstituted aralkyl group.

Substituents R6 in general formulas [1-1 to [:I-'t] are:
A pyrazoloazole ring (=represents a group that is bonded) via a secondary or tertiary carbon atom.

In the general formula (1-/3 to [tod], The ring represents the group that will leave.

This also includes cases where 几3, R4, I(, 5, ordinary, or X becomes a divalent group and forms a bis body. Also, the general formula [:
I-/] to C1-t] in the vinyl monomer (-, when t3, 4, R5, or R6 represents a simple bond or linking group, through which the general A vinyl group is bonded to a moiety represented by formula CI-/1 to [I-Y].

More details: R3, R4? and R5 are hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom, etc.), argyl group (e.g. methyl group, propyl group, hexyl group, trifluoromethyl group, tridecyl Lj-(λ, di-t- amylphenoxy)propyl group, codedecyloxyethyl group, 3-phenoxypropyl group, λ-hexylsulfonyl-ethyl group, cyclopentyl group, hensyl group, etc.), aryl group (e.g. phenyl group, g-t-
i-tylphenyl ts, ti-di-t-amylphenyl group, datetradecanabadophenyl group, etc.), heterocyclic groups (e.g., caufuryl group, cochenyl group, λ-bi1
7) Dinyl group, cobenzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group,
Comethoxyethoxy group, codedecyloxyethoxy group, comethanesulfonylethoxy group, etc.>, aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, g-t-butylphenoxy, etc.), heterooxygen groups (e.g., cobenzimidazolyloxy, etc.), acyloxy groups (e.g., acetoxy, hexadecanoyloxy, etc.), carbamoyloxy groups (e.g., N-phenylene/1.zcarbamoyloxy&, N -ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.),
Acylamino group (e.g., acetamido group, benzabado group, tetradecanamide group, α-(recognized).

Darzy t-ylphenoxy)butyramide group, γ-
(3-t-butyl-q-hydroxyphenoxy)butyramide group, α-(a-(rrt-hydroyacyphenylsulfonyl)phenoxy)tecanamide group, etc.), anilino group (e.g. phenylamino group, coke chloranilino group) , coke mouth o -j-tetradecanamide anilino group %
Cochroro O-j -dodecyloxycarbonylanilino group, Heacetylani 17/M, Cochroro 5-(α
-(3-1-butyl-Hiro-hydroxyphenoxy)dodecaneabadonanilino group, etc.), ureido group (e.g.
Phenylureido group, methylureido group, N.

N-dibutylureido group, etc.), imido group (e.g.
g-<2-ethyl hedecyl ester d)) phthalimide group, etc.), sulfamoylamino group (e.g. N,N-diethylsulfamoyl group) group, N-methyl-hedecylsulfamoylamino group group, '4), alkylthio group (
For example, methylthio group, octylthio group, tetradecylthio group, λ-phenoxyenalthio group, 3-phenoxypropylthio group, J-(K-1-butylphenoxy)propylthio group, etc.), arylthio group (for example, phenylthio group, copoxy!-t, -octylphenylthio group, 3-bentatecylphenylthio group, λ-carboxyphenylthio group, -amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (for example, N
-! f /I/ sulfamoyl &, N, N-cyclovirsulfamoyl &, N-(2-dodecyl-diethyl) sulfamoyl group, heethyl-dodecyl sulfamoyl group, N, N-diethylsulfamoyl group,
etc.), sulfonyl groups (e.g. Eva, methanesulfonyl group, octane sulfonyl group, benzenesulfonyl group, toluenesulfonyl 2%, etc.), sulfinyl group (four rows are octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.) ), alkoxycarbonyl group (
For example, it represents a methoxycarbonyl group, a butyloxysulfonyl group, a dodecylcarbonyl group, an octadecylcarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenyloxycarbonyl group, a 3-pentadecyloxycarbonyl group, etc.).

at least one of R3, R4 or R5, and R6
represents a group that is bonded to the pyrazoloazole ring 1 via a co- or tertiary carbon atom.To describe these groups in detail, they are an isopropyl group, a -methyl group, a t-hexyl group, a cyclohexyl group. , adamantyl group, /-ethoxyinpropyl group, l-phenoxy-/, I-dimethylmethyl group, α.

α-dimethylbenzyl group, α, α-dimethylphenylethyl group, α-ethylbenzyl group, l-dithyl/-[gu(2-butoxy-tert-octylbenzenesulfonamide) phenylcomethyl group, l-methylthio Group CK- (g-dodecyloxybenzenesulfonate)
phenyl]ethyl group, /-methyl-2-(2-octyloxy-j-tert-octylbenzenesulfonamide) ethyl group, /, /-dimethyl=2-(2-octyloxy-!-tert-octylbenzenesulfonamide) ) ethyl group, l-methyl-J-C,! -Octyloxy 5-(Co-octyloxy-!-t er t-
octylbenzenesulfonamide) benzenesulfonade] ethyl group, /-ethyl-2-(2-dodecyloxy-!-tert-octylbenzenesulfonamide)
Ethyl &, /-(2-hydroxyethyl)-co(α-
[3-(2-octyloxy-tert-octylbenzenesulfonamido)phenoxydodecaneamido)ethyl group, etc.

To explain in detail about X,
Acetoxy group, pro/synyloxy group, benzoyloxy group, 2. Hiro-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, bilbinyloxy group, cisonamoyloxy group, phenoxy group, Hiro-cyanophenoxy group, 'dermethanesulfonabadophenoxy group, termethanesulfonylphenoxy group , α-naphthoxy group, 3-
pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethoxy group, benzyloxy group, cophenethyloxy group, cophenoxyethoxy group, terphenyltetrazolyloxy group, cobenzothiazolyloxy group, etc.), Groups linked via nitrogen atoms (for example, benzenesulfonamide M, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, co, J, t, r, pentafluorobenzaabad group, octane sulfonamide group, p-cyanophenylureido group, N,N-jethylsulfamoyla Z) group, l-pyrazolyl group,! , Tadimethyl-2. V--dioxo-3-oxazolidinyl &, /-benzyl-ethoxy-3-hydantoynyl group, 2N-/, l-dioquine-3(,2H)-oxo/, 2-benzisothiazoyl group, co-oxo 712-dihydro- 1-pyridinyl group, imidazolyl group, pyrazolyl group, 3. j-diethyl-/, 2. Gate Il Azor-il,! −
or 6-promobenzotriazol-/-yl, termethyl-/, 2. J, 91-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl MS, /-benzyl-! -hexadecyloxy-3-hydantoynyl group,! -menalu l-tetrazolyl group, l-methoxyphenyla 7'M, K-bivaloylabanophenylazo group, 2-hydroxy-l-propanoylphenylazo group, etc.) Groups linked by a sulfur atom (e.g. phenylthio group, cocarphonylazo group, etc.) xyphenyltheo group, comethoxy r-t-cutylphenylthio group, l
-methanesulfonylphenylthio group, teroctanesulfonamidophenylthio group, copoxyphenylthi-4.2-(z-hexanesulfonylethyl)-terte
rt-octylphenylthio group, benzylthio group, cocyanoethylthio group, /-ethoxycarbonyltridecylthio group,! - Phenyl 2. ．． 3. Lit, j-tetrazolylthio group, 2-penzothiazolylnao group, λ-dodecylthioterthiophenylthio group, -1phenyl-3-dotecyl-/, 2. tt-triazolyl-terthio group, etc.).

R3, B, 4. When B5 or , /, 10-decylene group, -C)12C)i2-O-C)12CH2-
1st prize),! Substituted or unsubstituted phenylene group (for example, /
, 4t-phenylene group, /, 3-) unicine group, -NHCO-R'-CONI(- group (- group (R7 represents a warrior or an unsubstituted alkylene group or a phenylene group. To R6 is a divalent The divalent group forming a bis body is a group in which the alkylene group is bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom.

HJ3.几4, or 几5 when the compound represented by the general formula CI-/) to (1,-41 is present in the vinyl monomer)
The linking group represented by is an alkylene group (arranged or unsubstituted alkylene), where the linking group is a methylene group, an ethylene group, a /-methylethylene group, /, an IO-decylene group.
5. -CH2C)-12QC)12ell. -1st class),
Phenylene group (substituted or unsubstituted) unilene group, m
l, t, / , <t-phenylene &, /.

It includes a group formed by combining a group selected from 3-phenylene group, -CONI-1-1-o-1-oco-p, and aralkylene & (for example, α, etc.). R
The alkylene linking group represented by 6 represents a group in which the above alkylene group is bonded to a pyrazoloazole ring via a λ-class or tertiary carbon atom.

The vinyl group in the vinyl monomer has the general formula CI -
/ ] to [1-r) In addition to those represented by t substituents, it is also acceptable. A preferred monomer group is a hydrogen atom, a chlorine atom, or a lower alkyl group having /-6 carbon atoms.

5% of aromatic-grade amine present IJRaku The non-chromic ethylene-like monomers that do not couple with the main product include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. actylamide, n-butylacrylamide, t-7tylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, t-
Butyl acrylate, 1so-butyl acrylate, 2
-ethylhexyl acrylate-h, n-octyl acrylate, lauryl acrylate, methyl methacrylate,
ethyl methacrylate, n-butyl acrylate 2 and β-hydroxy methacrylate), methylene dibisacrylate, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic V-vinyl Compounds (such as styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinyl-11-tene chloride, vinyl alkyl ether (example: vinyl ethyl ether), maleic acid , maleic anhydride, maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and co- and gouvinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Examples of couplers included in the present invention are shown below, but the present invention is not limited thereto.

IO L;5H17(IJ )+2 / da I C5H1, (t) , 2 no +22 +23 C4H9ft) +2 Evening +2t +27 2♂ Kota H3 3 da truth CH3 j CH3 Nawate C112NH8o2C,1-i3 CH3C00C4H.

The couplers of the present invention represented by the general formulas from Cr-/ to CI-2 can be synthesized according to the methods described in the following literatures.

Compounds of the general formula CI-/] are disclosed in JP-A-59-/1rJj
For ZF etc., compounds of the general formula [1-,
/7196, etc., the compound of general formula [1-3] is disclosed in U.S. Patent No. 91 No. 3.7 No. 062 (2).

The compound of the general formula Cl-4 is published in Japanese Patent Application Publication No. 1986-33, etc., and the compound of the general formula [Tozu] is published in the US Patent No. 1 Patent 30t/,
V-32 No. 3, 31, 9. Synthesis methods are described in J''97 and the like.

Synthesis examples of typical couplers included in the present invention are shown below.

Synthesis Example 7.7-Chloro-6-meteluko(/-methyl-j-(,,2-ocnaloxy!'-tert-octylbenzenesulfonylamide)ethyl)-/)l-pyrazolo[/,r -b] [/, 2.9] Synthesis of triazole (coupler 2).

Intermediates i, 2i, and 7y synthesized using a method similar to the method described in Patent Application No. 0-10/7.3θ were synthesized using acetonitrile-dimethylacedeamide. Mixed solvent/rOml (Mixing ratio; volume, /:/)f was dissolved in two, added with 301 trietheramine, and cooled to 10°C or higher.-1 octyl oxyether tert -Octylbenzenesulfonyl chloride g I P'lr: Gradually added dropwise, and stirred for 1 hour after dropping.Added 300ml of ethyl acetate, and diluted with 200g of saturated saline water twice.
% bicarbonate of water) once with IJum water bath solution, then 200% again
The mixture was washed with brine, and the ethyl acetate layer was dried over 20 ml of anhydrous sulfuric acid. The ethyl acetate solution was concentrated under reduced pressure to obtain oily residues (Intermediate 2).

(2) Synthesis of coupler (7) The above intermediate +179- was mixed with 300 ml of methylene chloride.
:, and while stirring at room temperature, chlorosuccinimide/21 was added in portions. After stirring at room temperature for 2 hours, the precipitated succinic acid ibide was filtered off, and the P solution was concentrated. After adding 300 g of ethyl acetate to the foil and dissolving it well, the mixture was washed twice with saturated brine.

The ethyl acetate layer was dried with anhydrous sodium sulfate (20 g) and then drawn with a chain line. The residue was crystallized from acetonitrile to give colorless crystals g9ty-, melting point i3r~7°C.

* to water ~ ? Otsu-O to 1110 〇閤 × n Meu N mo) , 2-octyloxy-〇-tert-ocnalbenzenesulfonamide) benzenesulfonamido)ethyl]- /H-pyrazoloC'=r b) ('+x, g) triazole (coupler 10).

Same as Synthesis Example 1 (intermediate of bisynthesis m+/ is used as raw material,
2-ofderoxy-5-(2-octyloxy-!-
tert-octylbenzenesulfonamide) benzenesulfonyl chloride, and then chlorinated with dichlorosuccinimide to give a melting point of /Cobb~/3100. Coupler IO was obtained as colorless crystals (hexane-ethyl acetate=Li/Eri crystallization).

・Silver halogenide does not contain silver iodide, or even if it does contain less than 10 mol of salt (iodide) ) silver bromide or (iodine) silver bromide. No. that can be used in the present invention
The silver lokenide grains may have different phases in the interior and the surface layer, may have a bonded structure or a multiphase structure, or may have a uniform phase throughout the grain except for the surface layer. Moreover, they may be mixed. For example, silver chlorobromide grains having different phases may have a core or single or multiple layers within the grain that are rich in silver eribromide of average composition. Further, the grains may have a core rich in silver chloride or a single or plural layers within the grains based on the average halogen composition. Average grain size of silver halide grains (in the case of spherical or near-spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is taken as the grain size, respectively) and the projected area (Nimotozu (average))
is preferably λμ or less θ, 7μ or more, particularly preferably lμ or less 0. /It is more than evening. Preference is given to using so-called monodisperse silver halide emulsions in the present invention. The degree of monodispersity is determined by the fluctuation rate (the standard deviation of the grain size distribution curve of silver halide divided by the average grain size): O8/! The following is preferable, and 0010 or less is more preferable. In addition, in order for the light-sensitive material to satisfy the target gradation, grain sizes are different in emulsion layers having substantially the same whiteness.

Q Monodisperse silver halide emulsions of 4i7i or more in the same order (
It is possible to mix or coat two separate layers (111 layers).Furthermore, a polydisperse silver halide emulsion of polydispersity or higher or a combination of a monodisperse emulsion and a polydisperse emulsion can be mixed or layered to form one historical T. ) is also a monkey.

The shape of the silver halide grains used in the present invention is according to the regular λ rule such as a cube, an octahedron, a dodecahedron, and a quadrupole.
ar) crystals are preferable, but ginseng with irregular crystal shapes such as spherical shapes are also preferable (and also: - those with a composite of the crystal shapes of Yokoro et al. It can also be a tabular grain, which can be crushed into a pestle.
An emulsion may be used in which tabular grains with a thickness ratio of 5 or more and two or more tabular grains occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms can also be produced.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal m1 dormer type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is P, ol afkid
ES Station “Chemistry and Physics of Photography J”
hysique l'hotographique
) (Paul Montel, 1967), C
)-F', I) uf f in "Chemistry of Photo Hole 41 J
(Photograpl+icEmulsion
Cbemistry) (Focal Press, / Ftt), V. L. Zelikman et
Preparation and Coating of Photographic Emulsions J (Making
andCoating Photographic
Emulsion ) (Focal Press
(Pub., 7961) etc. (2) It can be prepared using the described method. In other words, any of the acid method, neutral method, ammonia method, etc. may be used, and soluble silver salts and soluble silver salts can be used.
・The methods for reacting Roken salt are one-sided mixing method, simultaneous mixing method, and A! Either one combination or the like may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a form of simultaneous mixing method, the pA of /% silver halide in the liquid phase produced
It is also possible to use a method in which g is kept constant, that is, a so-called Chondral sand double jet ε. According to this method, a silver rhodanide emulsion having a regular crystal shape and grains close to uniform -f2 can be obtained.

Next (2) The additives used in the preparation of the silver halide emulsion used in the present invention (2) will be explained below.

In order to control grain growth during the formation of halogenated mFff molecules according to the present invention] Silver rhodanide solvents include, for example, ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Patent m3.27/
, / No. 17, No. 31!7 da.

No. t21, No. 3, 7C) No. t, No. 130, same beam.

297, H39, same? Bg, a7t, 37r
t), thione compounds (for example, JP-A-63-/Kg
3/Wa issue, same! 3-Otsu Z%Or No. 77737
), amine compounds (e.g. JP-A Showta%-1007
No. 17, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, thallium salts, iridium salts or chain salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present.

The photographic emulsion (=) according to the present invention may contain one of various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. , azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto Benzothiazoles, mercaptothiadiazoles, mercaptotetrazoles (f%/-phenyl-!-mercaptotetrazole), mercaptobiridines; the above-mentioned heterocough mercapto compounds having a water bathing group such as a carboxyl group or a sulfone group; Thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (Special C
Separating a number of compounds known as anti-capri agents or stabilizers such as I can do it.

The halogen imitation odor-sensitive material according to the present invention is a silicone material.

It may contain color couplers such as couplers, magenta couplers, yellow couplers, and compounds that disperse couplers.

In other words, a color-forming compound may be produced by oxidative coupling with an aromatic primary amine (for example, phenylene diamine g4 form, amine phenol derivative, etc.) during color development IW treatment. For example, yellow couplers include acylacetamide couplers (eg, bennylacetanilides, pivaloylacetanilides), etc., and uncouplers include naphthol couplers, phenol couplers, and the like. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.
It may be either one-equivalent or two-equivalent. Also, colored couplers with color correction effects or current 1"
It may also be a coupler that releases a development inhibitor along with i (so-called f) IR coupler).

Also D I 11. In addition to couplers, the products of the coupling reaction may be colorless and enriched with colorless DI LL compounds that release development inhibitors.

The photographic emulsion used in the present invention includes, for example, polyalkylene peroxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc., for the purpose of increasing sensitivity, increasing contrast, or promoting tax regulations.
It may also contain quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole visiting conductors, 3-pyrazolidones, and the like.

In the halogenated silver photographic emulsion used in the present invention, known water-bathable dyes (e.g., oquinol dyes, hemioxonol dyes, and merocyanine dyes) are used as filter dyes or for the purpose of preventing Iranation and other purposes. It's okay. In addition, known cyanine dyes, merocyanine dyes, and hemicyanine dyes may be used before, during, or after chemical sensitization as a spectral sensitizer or to control the crystal shape and size of silver rhodide. good.

The photographic emulsions used in the present invention (2) have various purposes such as coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic character improvement (for example, promotion of phenomena, high contrast, and sensitization). It may also contain a surfactant.

Regarding the light-sensitive material of the present invention (2: anti-fading agent, hardening agent, anti-color capri 4), ultraviolet gland absorber, protective colloid such as gelatin, and additives, the specific details are as follows: Disclosure vo1./74 (/ri7♂,■
) RD-/7G93 etc. (two have been described).

The finished emulsion can be prepared on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
On other plastic bases or glass plates (double coated).

The silver halide photographic light-sensitive material of the present invention can be used, for example, as a color positive film, color paper, color negative film, color reversal film, light-sensitive material for heat development, light-sensitive material for color diffusion transfer process, and the like.

Exposure to obtain a photographic image may be performed using a conventional method. That is, any of a variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, etc. The exposure time is not only 7 seconds from 171,000 seconds that is normally used in cameras, but also shorter exposure than 17iooosho.
For example, using a xenon flashlight or cathode ray tube //10'
Exposures of ~//10 seconds can be used, or exposures longer than 1 second can be used. If necessary, the original spectral composition used can be adjusted by exposure using a color filter. Laser light can also be used for exposure.

Alternatively, the pottery may be heated using light emitted from a fluorophore excited by X-rays, γ-rays, α-rays, etc.

For photographic processing of the light-sensitive material of the present invention, for example, research disclosi q-(f(, esearchDisclo
sure) / No. 74, No. ♂ ~ 30 shellfish (No. D-77b
aJ) using known methods and known treatment solutions, such as those described in ``rL''? : also applies. This photographic processing may be either photographic processing for forming an image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose f2. Is the processing temperature normal/? It can be selected between 50°C and 50°C, or even lower than 0°C or even at temperatures above 0°C.

The present invention will be explained below using actual examples, but the present invention is not limited to these two.

Actual flow example/ Exemplary compound (Coupler 2) as a coupler! .

2g of tri(2-ethylhexyl)phosphate)/7
ml, 13 ml of ethyl acetate rrm was added and dissolved under heat, and added to an aqueous gioornt containing 10 f of gelatin and 1.0 ml of sodium todecylbenzenesulfonate, and then added to a medium-high solution to form a fine emulsified dispersion of the above coupler. I got it.

The entire amount of this emulsified dispersion is F3r! In addition to 10,100 f (including R and R) of chloride and bromide containing 0 mol of chloride and 2,4-mono-dihydroxy-6-chloros-triazine sodium salt iome as a hardening agent, silver A sample was prepared by coating a paper support laminated with polyethylene on both sides so that the coating amount was 2 oomq/-ζ, and providing a gelatin layer on top of this coating layer. This person will be the sample person.

Next, coupler 7 is exemplified by compound (coupler 10)/2ψ,
Exemplary compound (coupler 2/)! , 91 (double substitution, method of preparing sample A (double substitution, preparation of samples B and C, respectively).

Furthermore, the following comparative couplers (second comparative couplers a, b and C1, respectively!, 29-).

7,! 1 and 7. Samples of gf were prepared in the same manner as described above to prepare samples E and F.

Comparative coupler a Comparative coupler b (:5H□1) These three samples were subjected to wedge exposure at 101,000 C and processed with the following processing solution to obtain a magenta colored image.

Developer solution nitrilotriacetic acid 3 to a 2. Of benzyl alcohol /! ml diethylene glycol 10rnlN a 2
S O32, Of KBr O,
Hydroxylamine [acid [j, 0'? l-amino-3-methyl-he-12-h[beta-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate, 0zNa2CO3 (/water salt)
JOy-Add water/make it a vine (pl
(10,/) Bleach-fixing solution Ammonium thiosulfate (7 elements 7wt%)/R0ralN
a2S03 /ri JN H
4CFe (EDTA))
! j! i'EDTA-, 2Na
Add af water and reduce to liter (pH 3,
9) Treatment process temperature Time +'Ji'gl 33°03 minutes 30 seconds Bleach constant Mα 33°C7 minutes 30 hours
The magenta color image of each sample obtained in this way for 3 nights and 3 minutes at 0C was clear and highly saturated. When we measured the photographic characteristics of the color images of Kohori et al., we obtained the following results.

Condolence Table 7 Photograph A characteristic value * Relative value of the reciprocal of the exposure amount that is 4 minus 1 of (fog 10, evening). The comparison sample was used as the basis ('41<100).

From this result, -NH802 in the molecule for comparative sample F.
The sensitivity, gradation, and maximum density of the comparative samples using the comparative coupler a into which the - group was introduced are somewhat the same as above, but the sensitivity of the samples A and B using the couplers 7 and IO of the present invention is dramatically higher. ,
It can be seen that the gradation and maximum density have been improved. In contrast to the comparison sample Ej2, the cutler of the present invention with the same bone structure! ,
/7a- The same can be said for Sample C, which was used for convenience. This shows that the group of couplers of the present invention is uniquely effective in terms of sensitivity, level 4, and maximum seismic intensity.

Example 3 Samples A to F prepared in Example 1 were subjected to the same processing as described in Example 1 to obtain magenta images.

For these samples, the sample was exposed to a high temperature of 000C for about 7 days, another 7 weeks at a high temperature and high humidity of 70 degrees Celsius, and another 7 days at a high temperature of 390nm. Trial 1) LIV filter that cuts UV light at side wavelengths
The fastness of the magenta dye image was tested by exposing it to a xenon fading tester (700,000 lux) for 7 days.The results are shown in Table 2. Thermal fading and wet heat fading of magenta color images are as follows:
Although there is no big difference between the comparative coupler and the sample using the coupler of the present invention, it is seen that there is a large change in photobleaching property.

Compared to the comparison sample, the sample of the present invention containing a coupler having the same skeleton as F has markedly improved color fastness. Compared to comparative sample E), which originally used a coupler with a low color fastness and a skeleton, sample C, which used the coupler of the present invention, also showed a large improvement in photobleaching property.

Example 3 As described in Table 3 below, on a paper support laminated with polyethylene on both sides (from 2M/II (bottom layer) to 7J times (top layer)), a color copying tool was prepared. A sensitive material G-J was prepared.

The composition of the coating solution containing the emulsified dispersion and emulsion of the magenta coupler used in the third layer was that of Example (double coated on A4 paper).

A three-color separation filter of G-JcB-G-L was attached to these samples, and the same exposure and color development treatments as in the actual IM example were carried out.

The obtained color image was exposed to light for one week using a hot-light fading tester (/Yuu Lux), and a fastness test of the magenta dye image was conducted. The results are shown in Table 1 (yellow stain is shown in parentheses) Table D Color image fastness () Values in parentheses are density values measured using a blow filter in the extremely colored area (Spain) */ Yellow coupler α-piparoyl −α−(,2,g-dioquine−!,j′
-dimethyloxazolidin-3-yl)-2-chloro-ter[α-(2, Hiroji-tert-pentylphenocoir)phthanide]acetanilide *2 Solvent dioctyl butyl phosphate *3 Color mixing inhibitor λ, Terdioctylhydroquinone 0 Solvent dibutyl phthalate (Coupler of the present invention, 10) χ≦solvent! +-(2-ethylhexyl) phosphate *7 Ultraviolet absorber co(2-hydroxy-J-5ec-butyl-r-te
rt-butylphenyl)penztriazole*l Cyan coupler 2-[α-<2. t-diter t-pentylphenoxy)butanamide]-y, ≦-dichloro-! -Methylphenol From the results in Table Z, it is clear that the chromogenic images obtained from the couplers of the present invention have poor fastness to the original. It was also found that the remaining coupler did not exhibit any behavior that would sensitize the color cords to light.

Patent applicant: Fuji Photo Film Co., Ltd. 1, Indication of the case: Showa to 2003, Patent Application No. 2/73/4I, 20 Title of the invention: Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship to the case: Appointment of patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, 4m ratio Showa---
We will submit a revised copy of the detailed statement (with no changes to the content), subject to amendment.

Procedural Amendment 1986//Mon/V Date Commissioner of the Patent Office, 1.
Display of incident 1985 patent application No. 3/Hiroshi No. 2,
Name of the invention No. Rodan silver color photographic light-sensitive material 3.
Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of ``Detailed explanation of the invention'' in the specification 1 Contents of the amendment Detailed explanation of the invention in the specification Correct the column as shown below.

1) Insert the text from the attached sheet after "λ-carpoxypheniυthio group," in the 7th line of the 1st J-Tei.

that's all

Claims (1)

[Scope of Claims] A silver halide color photographic material having at least one silver halide emulsion layer on a support, characterized by containing a pyrazoloazole magenta coupler represented by the following general formula [1]. A silver halide color photographic light-sensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Za and Zb are respectively =CH-, ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ or = N-, R_
1 represents a hydrogen atom or a substituent, R_2 represents a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. The case where Za=Zb is a carbon-carbon double bond includes the case where it is part of an aromatic ring. R_1, R_2 or X may form a dimer or more multimer. However, when two R^2's exist in the same molecule, they are the same or may be different. In addition, i) if R^2 is not reassigned in the same molecule, R_1, or ii) if R^2 exists in the same molecule, at least one of R_1 and R_2 is secondary or tertiary. represents a group bonded to the pyrazoloazole ring via a carbon atom. Furthermore, at least one of R_1 and R_2 is -NHS
A group having one or more O_2- groups, where Za is ▲ formula,
There are chemical formulas, tables, etc.▼, and when Zb is =N-, R_2 cannot be a substituted or unsubstituted aralkyl group. ]