JPS62253170A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproducibility, sharpness, and grainness by specify ing the proportion of colored magenta coupler in the total amount of a pyrazolotriazole type magenta coupler and the colored magenta coupler contained in a silver halide emulsion layer. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers contains the pyrazolotriazole type magenta coupler A and the colored magenta coupler B in a B/(A+B) molar ratio of >= 0.17. The coupler A is, preferably, represented by formula I or II in which each of R1 and R2 is alkyl, aryl, or heterocyclic; Z is H or a group, such as halogen, alkoxy, or the like, to be released upon the coupling reaction with the oxidation product of an aromatic primary amine color developing agent and dormation of a dye. The couplers A and B may be added to any of the emulsion layers, but generally they are used for a green-sensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material with significantly improved sharpness and graininess.

[Conventional technology]

In recent years, the image quality of silver halide color photographic materials (hereinafter referred to as color photographic materials) has improved significantly, but their sharpness and graininess are still not satisfactory.

Special +: , + W type H-Lar film small 7 Ohman) (110 film, Tisf film, etc.)
In enlarged prints from originals, the level of print quality is noticeably lowered by image granularity and poor sharpness.

This is because the graininess and sharpness of negative film are not high enough to withstand high-magnification printing.

Conventionally, various techniques for improving sharpness are known. One of them is a technology to prevent light confusion, and 1') is a technology to improve the Esso effect.

Examples of the latter technique include a method using a so-called Dllt coupler and a method using an unsharp mask. Among these, the method using unsharp mask reduces sensitivity and
This may lead to deterioration of graininess, so there is a practical limit. D
There are many ways to use Ift couplers (a known and useful old R coupler is
No. 57-93344, U.S. Patent No. 3,227,
No. 554, No. 3,615,506, No. 3.6+7.2
There are compounds described in No. 91 and No. 3,701,783.

However, when using a DIR coupler to emphasize the edge effect, the MTF (modula
Although the modulation transfer function (Lion transfer function) is improved, it is not possible to expect an improvement in MTF in the high frequency region necessary for high magnification, and undesirable side effects such as a decrease in sensitivity and a decrease in density are accompanied. Diffusivity 1) I
If you use a so-called DIR coupler such as R, timing DIR, which has an effect over a long distance, you can reduce the decrease in sensitivity and density, but the area for MTF shifts to the lower frequency side and sharpness at high magnification is reduced. I can't expect much improvement.

On the other hand, known techniques for preventing light scattering include adding a coloring substance, reducing the amount of silver halide, and making the film thinner. A large or medium reduction in the amount of coated silver reduces the number of color spots, leading to deterioration of graininess. There is also a reduction in the amount of gelatin, coupler, coupler solvent, etc. in the coating solution, but all of these methods have their limits as they result in deterioration of coating properties and reduction in color density.

Attempts have been made for a long time to add colored substances to suppress light scattering and improve sharpness, but these efforts have not achieved sufficient results due to problems such as decreased sensitivity.

In recent years, pyrazolotriazole couplers have attracted attention as magenta couplers. This coupler has little side absorption, so it is not only advantageous in terms of color reproducibility, but also has good color development, so it can be used in small amounts, which is very advantageous for thinning films, and it is effective in improving sharpness. I found out something.

However, it has been found that pyrazolotriazole couplers cannot be expected to have an effect of improving graininess.

Therefore, there is a need for IJIJ to develop a technology for improving graininess in systems using pyrazolotriazole couplers.

[Purpose of the invention]

An object of the present invention is to provide a color photosensitive material that has significantly improved not only color reproducibility and sharpness but also graininess.

a- [Structure of the Invention] An object of the present invention is to provide a light-sensitive material having a light-sensitive silver halide emulsion layer containing at least one layer of a pyrazolotriazole-based magenta coupler and a colored magenta coupler. 17 of the total coupler amount in the layer with magenta coupler
This was achieved using a light-sensitive material characterized in that more than 2 mol % of the coloring magenta coupler is a colored magenta coupler.

The pyrazolotriazole magenta coupler according to the present invention is preferably one represented by the general formula (1) or (]II.

General formula (1) General formula (n) In the above general formulas (1) and (II), R,,R.

represents an alkyl, aryl, or heterocyclic group, and the alkyl, aryl, or heterocyclic group may be bonded via an oxygen atom, nitrogen atom, or sulfur atom. Furthermore, the alkyl, aryl, and heterocyclic groups described above may be bonded via the bonding groups listed below. i.e. acylamino, carbamoyl,
The alkyl group represented by sulfonamide, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, sulfonyloxy R + , R 2 has 1 to 1 carbon atoms.
up to 20 straight-chain or branched alkyl groups (e.g. methyl, ethyl, propyl, i-propyl, sec-butyl,
(n-butyl, t-butyl, -octyl, t-octyl, dodecyl, octadecyl group, etc.). These groups further have substituents (e.g. halogen atoms and nitro, cyano, alkoxy, aryloxy, amino, acylamino, carbamoyl, sulfonamide, sulfamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl groups). Good too. Specifically, chloromethyl, bromomethyl, trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylami-7probyl, and ethylcarbamoyl. Ethyl, methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, phenylmethyl,
Examples include p-chlorophenylmethyl, naphthylethyl, ethoxycarbonylethyl, and acetylethyl groups.

Further, the aryl group may represent a phenyl or naphthyl group, and may have a substituent as shown in the section of the alkyl group above.

Further, the heterocyclic group represents a five-shell or six-shell ring group having at least one of a nitrogen atom, an oxygen atom, and a sulfur atom, and may or may not have aromaticity. For example, pyrinol, quinolyl, pyrrolyl, morpholyl, 7ranyl, tetrahydrofuranyl,
These include pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxasilyl, imidazolyl, and thiadiazolyl groups. Further, these may have the substituents shown in the section of the alkyl group.

Examples of the alkyl, aryl, and heterocyclic groups represented by R1 and R2 bonded via the above-mentioned bonding group or a nitrogen atom, oxygen atom, or sulfur atom include the following.

Here, R1 represents an alkyl, aryl, or heterocyclic group, and R2 and R3 represent a hydrogen atom, alkyl, aryl, or a heterocyclic group.

When the heterocyclic group is a pyrazolotriazolyl compound, a bis-type pyrazolotriazole compound is formed.
Of course, this is a magenta coupler included in the present invention.

In the general formulas (1) and (II), Z represents a hydrogen atom or a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, -NY (Y is a nitrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom) represents a group of atoms required to form a 5- to 6-shell ring with atoms selected from the following.

7'-ゝ＼.

゛() etc.

Specific examples of pyrazolotriazole-based magenta couplers represented by general formulas (1) and (U) are shown below in the margins, but the present invention is not limited thereto.

The rest\to, ノ = 15- C, H, 5 C6H13 (t) db C2115 7H15 CH3L; ellu (LJ Nawate C6H, 3 OCH2CON) ICH2CH20C) tg0CToC
H2SO2Ctla 2H5 Di6H13 -40= CI.

tt3 QC2H.

CH3 CH3 -ria- C.I.

Hidden CH3 Hs CH3L;81117(tJ CH3 CH4 U Shii3 C7H1! i H3CCH3 0(1;H2)20C12H25 1 ward 1 One day one N-N-N −0〇− Thatch Upper - OC'I 2 Hzs CH.

CH.

61 C8H171t) CI.

The colored magenta coupler according to the present invention is preferably represented by the following general formula.

General formula [■] Cp-N=N-R.

In the formula, Cp represents a magenta coupler residue (however, the azo group is bonded to the active site of the magenta coupler).
, R3 represents an aryl group (including one having a substituent).

The magenta coupler residue represented by Cp is preferably a 5-pyrazolone magenta coupler or a coupler residue derived from a pyrazolotriazole magenta coupler, and particularly preferred is represented by the following general formula [■].

General formula [/) R1 In the formula, R4 represents an aryl group, and R1 represents an acylamide group, an anilino group, a ureido group, or a carbamoyl group, of which an anilino group is preferred.

Each of R, , R5 includes those having a substituent.

The aryl group represented by R4 is preferably a phenyl group. Substituents for the aryl group represented by R1 include, for example, a halogen atom, alkyl, alkoxy, aryloxy, acylamihasulfonylamine 7, sulfamoyl, carbamoyl, sulfonyl, acyloxy, ester, carboxyl, sulfo, cya/, nitro group, etc. can be mentioned.

Furthermore, specific examples of R1 include phenyl, 2°4.6
-)IJ chlorphenyl, pentachlorphenyl, pentafluorophenyl, 2,4.6-)limethylphenyl, 2-chloro-4,6-nomethylphenyl, 2,6-fuchloro-4-methylphenyl, 2.4- Fukuroru 6-
Methylphenyl, 2,4-dichloro-6-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl, 2,
6-dichloro-4-[α-(2,4-not-amylphenoxy)acetamido]phenyl group and the like.

Examples of the acylamide 7 group represented by R5 include pivaloylami/, n-tetradecanamide, α-(3-pentadecylphenoxy)butyramide, 3-[α-(2
, 4-di-t-amylphenoxy)acetamide 1benzamide, benzamide, 3-acetamidobenzamide, 3(3-n-dodecylsuccinimide)benzamide, 3-(4-+tododecyloxybenzenesulfonamyl) benzamide group etc.

Examples of the anilino group represented by R3 include anilino, 2-chloroanilino, 2,4-dichloroanili/, 2
．． 4-dichloro-5-tomexyanilino, 4-cyanoanilino, 2-chloro-5-[α-(2,4-di-t-amylphenoxy)butyramide]anilino, 2-chloro-5-(3-octadecenyl succinimide) anilino, 2-chloro-5-11-tetradecanamide anilino/
, 2-chloro-5-[α-(3-t-butyl-4-hydroxy7e/xy)tetradecanamide 1 anilino, 2
-chloro-5-n-hexadecanesulfonamide aniline 7 groups and the like.

Examples of the ureido group represented by R5 include methylureido, phenylureido, 3-[a-(2,4-di-t-amylphenoxy)butyramide] phenylureido groups, and the like.

The carbamoyl group represented by R5 is, for example, n-
Tetradecylcarbamoyl, phenylcarbamoyl, 3
-[α-(2,4-note-amylphenoxy)acetamide 17yonylcarbamoyl group, etc.

The aryl group represented by R3 is preferably a phenyl group or a 7-tyl group.

Substituents for the aryl group represented by R3 include a halogen atom, alkyl, alkoxy group, aryloxy, hydroxy, acyloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, acyl, and sulfonamide. , carbamoyl, sulfamoyl group, etc.

Particularly preferred substituents are an alkyl group, a hydroxy group, an alkoxy group, and an acylamide group.

Next, specific examples of the colored magenta coupler represented by the general formula [1[1] will be described, but the invention is not limited thereto.

CM-, 2 CI M-3 CI M-4 M-5 CI M-6 CI M-7 rl) M-8 CI M-9 CI M-10 M-11 M-12 [=ρ CI M-13 rρ CM-14 rCI M-15 e I M-16 M-17 M-18 rCI M-19 M-20 rCI M-21 e I M-22 M-23 Shi I M-24 Colored according to the present invention Magenta coupler is JP-A-49
-123625, 49-131448, 52-
No. 42121, No. 52-102723, No. 54-52
No. 532, No. 58-172647, U.S. Patent No. 2,76
No. 3,552, No. 2,801.171, No. 3,519
It can be synthesized according to the method described in No. 429.

The pyrazolotriazole-based magenta coupler and colored magenta coupler of the present invention can be used in any layer of the above-mentioned Hough 4-silver halide emulsion layer, but are generally used in a green-sensitive silver halide emulsion layer. . When the green-sensitive silver halide emulsion layer consists of two or more emulsion layers, it is necessary to use it in at least one emulsion layer, and preferably in two or more emulsion layers.

Furthermore, when the emulsion layer is composed of two or more emulsion layers having different sensitivities, it is preferable to use it at least in the high-sensitivity layer.

The pyrazolotriazole magenta coupler of the present invention is usually 1X10-3 to 1 mole per 1 mole of silver halide in the light-sensitive silver halide emulsion layer, preferably 1X1
It is used in the range of 0-'' mol to 8×10-' mol, but from the viewpoint of sharpness, it is 50 mol% of the total amount of coupler in the additive layer.
It is preferable to use the following, more preferably 60 to 80
It is mole%.

Furthermore, the colored magenta coupler of the present invention is required to account for 17 mol% or more of the total amount of couplers in the additive layer, preferably 2.
It is 0 mol% or more and less than 50 mol%. Further, it is preferably 30 mol% or more and less than 50 mol%.

The magenta coupler and colored magenta coupler-containing layer of the present invention may contain magenta couplers other than the present invention. However, the content of these magenta couplers outside the present invention is less than 20 mol% of the total amount of couplers.

As magenta couplers that can be used in combination with the green-sensitive silver halide emulsion layer of the present invention, pyrazolone compounds, ingzolone compounds, cyanoacetyl compounds, pyrazoloazole compounds other than the present invention, etc. can be used, and in particular pyrazolone compounds. Compounds are advantageous.

A specific example of a magenta coupler that can be used is disclosed in JP-A-49-1
No. 11631, No. 56-29236, No. 57-947
No. 52, Special Publication No. 4B-27930, U.S. Patent No. 2,60
No. 0,788, No. 3,062゜653, No. 3,408
．． No. 194, No. 3,519,429, and Research Disclosure No. 12443.

When adding the magenta coupler of the present invention and other couplers, they can be incorporated into the green-sensitive silver halide emulsion layer by the oil-protect dispersion or latex dispersion method described below, and when the couplers are alkali-soluble, It may be added as an alkaline solution.

From the viewpoint of improving color reproducibility, sharpness, and graininess, it is preferable to use a DIR compound in combination.

Typical examples of DIR compounds that can be used in the present invention include DIR couplers in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is introduced into the active site of the coupler; 935,454
No. 3,227.554, U.S. Patent No. 4.095,9
No. 84, No. 4,149,886, JP-A-57-151
No. 944, etc. When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent,
The coupler core has the property of forming a dye while releasing a development inhibitor. In addition, in the present invention, U.S. Patent No. 3,652
, No. 345, No. 3,928,041, No. 3,958,
No. 993, No. 3,961,959, No. 4,052,2
No. 13, JP-A-53-110529, JP-A No. 54-133
It also includes compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized color developing agent, such as those described in No. 33 and No. 55-161237.

Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular water nucleus substitution reaction. Alternatively, a so-called timing DIR compound, which is a compound that releases a development inhibitor through an elimination reaction, can also be used in the present invention.

Also, JP-A-58-160954, JP-A No. 58-18294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
R compounds may also be used.

Typical specific examples of DIR compounds are described below, but the present invention is not limited thereto.

below) -,! L-;' [Exemplary compound] (D-2) ■ C11° (D-3) (D-5) rσ (D-7) (D-8) (D-9) N = N (D-11) (D-12) (D-15) (D-17) The DIR compound that can be used in combination with the present invention is preferably added to a photosensitive silver lodenide emulsion layer.

Two or more types of DIR compounds may be included in the same layer.

Also, the same DIR compound may be contained in two or more different layers.

These DIR compounds are generally preferably used in amounts of 2.times.10' to 1.times.10.sup.-' moles, more preferably 1.times.10.sup.-3 to 2.times.10-2 moles per mole of silver in the emulsion layer.

For the purpose of the present invention, which is to improve image quality, so-called timing DIR compounds or so-called diffusible DIR compounds in which the released suppressing group has high mobility are preferably used.

The silver halide emulsion used in the color light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride, etc. Any emulsion commonly used in silver halide emulsions can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion 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 created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them to I)H+9Ag in the mixing pot while controlling. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), ronium salts (including complex salts), and iron salts ( By adding metal ions using at least one metal selected from the group consisting of complex salts and containing these metal elements inside the particles and/or on the surface of the particles, by placing them in a light and suitable reducing atmosphere. , reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of 1loo1 plane to (1111 plane) can be used. Also, particles having a composite form of these crystal forms may be used, or particles of various crystal forms may be mixed.

The average grain size of silver halide grains is 0.05-
30μII+, preferably 0,1. -20 μm is used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

The silver halide emulsion is chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method or the like can be used.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex melonanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

Bingu (or protective colloid) of silver halide emulsion
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other 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 the light-sensitive material using the silver halide emulsion of the present invention contain one or more hardening agents that crosslink the baingu (or protective colloid) molecules and increase the film strength. It can be hardened by using ν).

For example, aldehydes, N-methylol compounds, nooxane derivatives, active vinyl compounds, active noxane compounds,
Mukono) can be used with rogenic acids, etc.

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

Further, for the purpose of improving dimensional stability, etc., a dispersion (latte cous) of a water-insoluble or poorly soluble synthetic polymer can be contained.

In the emulsion layer of a light-sensitive material, a dye is produced by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenenoamine derivative or an aminophenol derivative) during a color development process. A dye-forming coupler that forms is used.

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. Further, these dye-forming couplers may be either 4-equivalent or 2-equivalent. Dye-forming couplers have the effect of color correction, and by coupling with oxidized forms of developing agents, they can be used as development inhibitors, development accelerators, bleach accelerators, developing agents, silver decadenide solvents, and preparations. Compounds that release photographically useful 7-ragments such as colorants, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. Instead of a DIR coupler, a DIR compound which undergoes a force-embedding reaction with the oxidized form of a developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and IR compounds used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, which can be released by the coupling reaction. Intramolecular nucleophilic reaction at the base circle,
Included are compounds in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as an imming DIR coupler and a timing DIR compound). Moreover, the inhibitor can be either one that is diffusible after release or one that is not so diffusible. A colorless coupler that undergoes a coupling reaction with the oxidized product of an aromatic primary amine developer but does not form a dye (
Competitive couplers) can also be used in conjunction with dye-forming couplers.

As the yellow dye-forming coupler, known 7-syl acetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Pat.
, No. 057, No. 3, No. 265, No. 506, No. 3, 40
No. 8,194, No. 3,551,155, No. 3,582
No. 322, No. 3,725,072, No. 3,891,
445, West German Patent No. 1,547,868, West German Patent Application No. 2,219,917, West German Patent Application No. 2゜261.361, West German Patent No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. -10783, JP-A-47-26+33
No. 48-73147, No. 50-6341, No. 5
No. 0-87650, No. 50-123342, No. 50-
No. 130442, No. 51-21827, No. 51-10
No. 2636, No. 52-82424, No. 52-1152
No. 19, No. 513-95346, etc.

As cyan dye-forming couplers, phenol or 7-tole couplers are generally used. Specific examples of cyan color-forming couplers that can be used in addition to the couplers represented by the above-mentioned general formulas [■] to [■] are disclosed in U.S. Pat. No. 2,423, for example.
, No. 730, No. 2,801,171, No. 3,737.
No. 326, No. 3,758,308, No. 3,893,0
No. 44, JP-A-47-37425, JP-A No. 50-1013
Couplers described in No. 5, No. 50-25228, No. 50-112038, No. 50-117422, No. 50-130441, etc., and couplers described in JP-A-58-98731 are preferred. .

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent as necessary, and add a surfactant to a hydrophilic binder such as a gelatin aqueous solution using a stirrer, homogenizer, It may be emulsified and dispersed using a dispersing means such as a colloid mill, a 70-knot mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, heptata alkyl esters, phosphate esters, citric acid esters, and Rest! Organic solvents having a boiling point of 150° C. or higher, such as acid esters, alkylamides, fatty acid esters, and trimesic acid esters, are used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butyl, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

Anionic surfactants, /
It is possible to use ionic surfactants, cationic surfactants and amphoteric surfactants.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity, deterioration of sharpness, and graininess. A color antifoggant can be used to prevent the color from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

It is possible to use an image stabilizer in the photosensitive material to prevent deterioration of the dye image.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material.

The emulsion layer of a photographic light-sensitive material contains polyalkylene oxide or its derivatives, thioether compounds, thiomol 7-olins, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain quaternary ammonium compounds, urethane derivatives, urea derivatives, imiguzol derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material can be used to reduce the gloss of the light-sensitive material, improve the ease of writing,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other.

Any matting agent can be used.

The particle size of the matting agent is preferably 0.05 μW to 10 μm. The amount added is preferably 1 to 300 II1 g/ω2.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material has properties such as improved coating properties, antistatic properties, good slippage, emulsification and dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

Supports used in the photosensitive material of the present invention include paper laminated with α-olefin polymers, flexible reflective supports such as synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. , films made of polyamide, etc., flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

The surfactant is not particularly limited, and for example, natural surfactants, cationic surfactants, 7-ton surfactants, and amphoteric surfactants may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. Alternatively, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

The treatment temperature is usually selected to be in the range of 10°C to 65°C, but may also be at a temperature exceeding 65°C. Preferably, the treatment is carried out at 25°C to 45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenenoamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, ρ~toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. Compensate.

These compounds are generally about 0.0% for color developer 14.
A concentration of 1 to 30 g, more preferably color developer II!
It is then used at a concentration of about 1-15 g.

If the amount added is less than 0.18, sufficient color density cannot be obtained.

The color developing solution used in the present invention may contain an alkaline agent commonly used in developing solutions, and may further contain various additives such as pencil alcohol, alkali metal halides, development regulators, and preservatives. good. Furthermore, various antifoaming agents, surfactants, organic solvents, antioxidants, etc. can be appropriately contained.

1001 The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As the bleaching agent, a metal complex salt of an organic acid is used, and for example, one in which a metal ion such as iron, cobalt, or copper is coordinated with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, or citric acid is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches contain 5-450g/1, more preferably 20-2
Use at 50g/f.

In addition to the above-mentioned outside bleaching agent, the bleaching solution may contain a bleaching accelerator and sulfite as a preservative, if necessary.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. Typical fixing agents include compounds that react with silver halide to form water-soluble complex salts, such as thiosulfates, thiocyanates, thioureas, and thioethers, which are used in ordinary fixing processes. It is. These fixing agents are used in an amount of 5 g/Z or more, within a soluble range, but are generally used in an amount of 70 to 25 th/f. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

Incidentally, the bleaching solution and/or the fixing solution can contain various pH buffering agents. Furthermore, various optical brighteners, antifoaming agents, or surfactants may be contained.

Further, a preservative, an organic chelating agent or stabilizer such as amino/polycarboxylic acid, a hardening agent, an organic solvent, etc. can be appropriately contained.

The pH of the fixer is used at 3.0 or higher, generally from 4.5 to 10, preferably from 5 to 9.5, and most preferably from 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fix solution contains a silver halide fixing agent in addition to the above-mentioned external bleaching agent, and a preservative is also added if necessary.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

-1(II- [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In the following examples, the amount added in the photosensitive material is 1-2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic element sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) 1st layer; antihalation layer Gelatin layer containing black colloidal silver.

Second layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer average grain size (r
)0.30μ (to), Δg! 8gB containing 8mol%
Monodispersed emulsion (emulsion I) consisting of rl...silver coating amount 1.51? /m2
Sensitizing dye I... 6 x 10-5 mol per mol of silver Sensitizing dye ■... 1. OX 10-5 mol cyan coupler (C-1)...0.06 mol per mol of silver Colored cyan coupler (CC-1)...0.003 mol per mol of silver DIR compound [) -12)... 0.0015 mol per 1 mol of silver DIR compound (D-15)... 0.004 mol per 1 mol of silver 4th layer; high sensitivity red-sensitive silver halide emulsion layer average Particle size (r
) 0.65 μ ring, ^,, r containing 7.0 mol%^gB
Consists of rl.

Monodispersed emulsion (emulsion ■)...silver coating amount 1.3g/Ia2
Sensitizing dye ■... 3 x 101 moles per mole of silver Sensitizing dye ■... 1. OX 10-5 moles cyan coupler (c-i)... 0.02 mole per mole of silver Colored cyan coupler (CC-1)...0.0015 mole DIR compound (D -15)... 5th layer with o, ooi moles per mole of silver; same as the second intermediate layer, gelatin layer.

6th layer; low sensitivity green-sensitive silver halide emulsion layer pore agent-I
... Coating amount of silver 1.3 g/l 112 sensitizing dye ■... 2.5X 10-' mol sensitizing dye ■ per 1 mole of silver
... 1.2X to-5 mole magenta coupler (M-1) for 1 mole of silver... 0.9 mole power magenta coupler (CM-1) for 1 mole of silver...1 mole of silver DIR compound (D-12): 0.017 mol per mol of silver DIR compound (D-17): 0.0030 mol per mol of silver 7th layer ; High-sensitivity green-sensitive silver halide emulsion layer emulsion -■
...Amount of silver coated 1. Ig/ring 2 sensitizing dye■... 1.5X1. O-5 mole sensitizing dye ■・
... 1 mole of silver. OX 10-5 mol Magenta Kab 2-(M-1)... 0.020 mol per mol of silver Colored magenta coupler (CM-1)... 0.004 mol per mol of silver DIR compound (D-12)... 0.0010 mol per 1 mol of silver 8th layer; yellow filter gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer; low-speed blue-sensitive silver halide emulsion layer average grain size 0.
Monodisperse emulsion (emulsion ■) consisting of ^gBrI containing 6 mol% of 38μIIliAgI... Silver coating amount 0.9 g/m2 Sensitizing dye ■... 1,3X 10-' mol yellow coupler (for 1 mol of silver) y-i)... 0.29 mol per mol of silver 10th layer; high-sensitivity blue-sensitive emulsion layer average grain size 0.8μ, containing ^gB to mol %
Monodispersed emulsion (emulsion ■) consisting of rl... Silver coating amount 0.5 g/m2 Sensitizing dye V... 1.5 g/m2 per mole of silver. OX 10-' mol Yellow coupler (Y-1)... 0.08 mol per mol of silver DIR compound (D-3)... 0.002 mol per mol of silver 11th layer; 1 Protective layer - Silver iodobromide (8g 11 mol% average grain size 0.07μ)...
Trowel coating iL0.5g/so2 1os- gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer; second protective layer gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) and formalin scavenger (H8-1).

In addition to the above composition, each layer contains a gelatin hardener (H-1
) and surfactants were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye ■; Anhydro-5,5'-dichloro-9ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; Anhydro-9-ethyl-3,3'-no (3-Sulfopropyl)-4,5゜4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; anhydro-5,5'-diphenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarpocyanine hydroxide sensitizing dye ■; anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5'.

6'-nopenzooxalupocyanine hydroxide sensitizing dye ■; anhydro-3,3'-no(3-sulfopropyl)-4,5-benzo-5'-merρ V-2 Next, the 6th layer, 7 Samples 1 to 1 in which the magenta coupler and colored magenta coupler in the layer were changed as shown in Table 1.
7 was created.

After exposing each sample No. 1 to 17 thus prepared, the following development treatment was performed.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75 Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g sodium bromide
1.3g nitrilotriacetic acid, 3s1
~ Lium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to 11
and adjust the pH to 10.6 using sodium hydroxide.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 00g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
10. On+f add water 1
1 and adjust the pH to e and o using ammonia water.

[Fixer]

Ammonium thousand sulfate 175.0g Anhydrous sodium sulfite 8.5FI Sodium metasulfite 2.3g Add water to 1p
and adjust the pH to 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5J
Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5mf
Add water to make 11.

The results are shown in Table 1.

Below (Shimokin ~ ゝ-1,.

The amount of coupler added is mol% relative to 1 mol of silver halide.
, The amount in parentheses is the percentage of the total coupler in the layer.
, MTF is a relative value when sample 1 is taken as 100, RMS
is the aperture scanning area of the density point of minimum density + 0.7, 250
It is expressed as a value 1000 times the standard deviation of the variation in concentration value that occurs when scanning with a microdensitometer of 12 μm.

Therefore, the larger the MTF and the smaller the RMS, the higher the image quality.

As is clear from Table 1, in samples where the magenta coupler was a pyrazolotriazole magenta coupler and the colored magenta coupler contained 17% mole or more of the total amount of couplers in that layer, both sharpness and graininess were affected. It has improved significantly.

In particular, when applied to the ^sensitivity layer, it is further improved.

Claims (1)

[Claims] In a silver halide photographic material having a light-sensitive silver halide emulsion layer containing at least one pyrazolotriazole magenta coupler and a colored magenta coupler, all couplers in the layer containing a pyrazolotriazole magenta coupler and a colored magenta coupler quantity 17
A silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer containing colored magenta coupler in a mole % or more.