JP3165733B2 - Silver halide color photographic material containing pyrazolotriazole magenta coupler - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material containing a photographic coupler, and more particularly, to a ballasting group at a position other than the coupling position.
1H-Pyrazolo- [3,2-c] -1,2,4 with (ballastinggroup)
-Related to triazole magenta couplers.

[0002]

BACKGROUND OF THE INVENTION Color images are known to be obtained in photographic silver halide materials by the reaction between the oxidation product of an aromatic primary amine developer and a dye-forming coupler; It is known to use combinations of cyan and magenta couplers as such dye-forming couplers.

In color photographic couplers, 5-pyrazolone couplers are commonly used as magenta dye forming couplers. Dyes formed from 5-pyrazolone couplers have excellent fastness to heat and light and have nearly ideal excellent absorption. However, since they have an absorption around 430 nm in addition to their excellent absorption, the use of masking couplers or other masking techniques is required. This dye also has low resistance to the action of formaldehyde.

In order to solve these problems, as magenta dye-forming couplers, pyrazolobenzimidazole couplers described in GB 1,047,612, US Pat.
No. 725,067, more recently 1H-imidazolo- [1,2-b] -pyrazole couplers described in U.S. Pat. No. 4,500,630, and 1H-pyrazolo- [described in EP Patent No. 119860. [1,3-b] -1,2,4-triazole, Research Disclosure No. 24
No. 220, 1H-pyrazolo- [1,5-d] -tetrazole, and JP Patent Application No. 43659/85, 1H-pyrazolo- [1,
5] -Pyrazole has been proposed.

When incorporated in photographic materials, couplers are usually dispersed with the aid of high boiling solvents or adsorbed on polymer latex. The coupler is located at a position other than the coupling position.
up) makes it non-diffusible in the photographic material and is compatible with the coupler solvent or polymer latex. Pyrazolotriazole and pyrazolobenzimidazole magenta couplers having a p-hydroxyphenylsulfonyl group or a ballast group having a p-hydroxyphenylsulfinyl group as a terminal group are disclosed in EP Patent Application No.
No. 73636. Pyrazolobenzimidazole, pyrazolotriazole and imidazopyrazole magenta couplers having a substituted p-hydroxyphenylsulfonyl group or a substituted p-hydroxyphenylsulfinyl group as terminal groups are described in US Pat. No. 4,513,082. Pyrazolotriazole magenta couplers with ballast groups having aminosulfonyl or aminocarbonyl groups as terminal groups are described in U.S. Pat. Nos. 4,548,899 and 4,822,730. Pyrazolotriazole magenta couplers with a ballast group having a carboxy group are disclosed in EP Patent Application No. 284240 and U.S. Pat.
It is described in No. 4.

[0006] Although these couplers can solve the above-mentioned problems of 5-pyrazolone magenta couplers, there is a constant need for improvement or optimization of the coupler for specific applications. Many properties of the coupler and the resulting dye are improved as desired. In particular, by providing the pyrazoloazole coupler, substantially
A dye having excellent absorption at the wavelength corresponding to the 5-pyrazolone magenta coupler is obtained.

[0007]

SUMMARY OF THE INVENTION The present invention comprises a support,

[0008]

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[Wherein, L is an aralkylene divalent linking group containing a ballasting residue and is a group having an arylene group of the aralkylene group directly linked to-(NH) _n -SO _2- , Is 0 or 1, and R is a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a sulfonamide group and an acetylsulfonamide group. At least one layer containing at least one non-diffusible magenta coupler of 1H-pyrazolo [3,2-c] -1,2,4-triazole having a group having a structure represented by the following formula: And a silver halide emulsion layer.

A magenta dye is obtained by color development of the above magenta coupler. The reaction is characterized by high reactivity, high color density, low absorption in the blue and green regions, low color change regardless of storage conditions, and absorption maximum at the wavelength corresponding to the 5-pyrazolone magenta coupler.

[0011]

The magenta coupler according to the present invention has a structure represented by the following formula.

[0012]

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Wherein R ₁ is a hydrogen atom, an alkyl group or an aryl group; Z is a hydrogen atom, a halogen atom or a group which can be removed in a coupling reaction with an oxidation product of a color developer; , N and R are each as defined in formula (I).

As described above, R ₁ in the formula (II) is a hydrogen atom, an alkyl group or an aryl group. Preferred alkyl groups are those having 1 to 8 carbon atoms. More preferred alkyl groups are methyl, trifluoromethyl,
1-4 such as ethyl, ethoxyethyl and t-butyl
Having three carbon atoms. Preferred aryl groups represented by R ₁ are substituted or unsubstituted phenyl groups such as p-methoxy-phenyl, 4-t-butylphenyl or m-chloromethylphenyl.

Z is a group that can be removed in a coupling reaction with a hydrogen atom or an oxidation product of a color developer. Specific examples of such groups include a halogen atom (e.g., chlorine or fluorine), or a group bonded to a coupling position via an oxygen atom, a nitrogen atom, or a sulfur atom,
Preferably a cyclic group (e.g., an aryloxy group such as phenoxy, p-methoxyphenoxy or pt-butylcarbonamidophenoxy, an arylthio group such as phenylthio, and a heterocyclic thio group such as 1-ethyltetrazole-5-thioyl ). If the removable group is a cyclic group, it may be attached directly to the coupling position of the coupler molecule via an atom forming part of the ring (eg a nitrogen atom). Halogen atoms are preferred, and chlorine atoms are particularly preferred.

R is a halogen atom or an alkyl group (preferably an alkyl group having about 1 to 4 carbon atoms (for example, methyl, ethyl, propyl and butyl)), which is a halogen atom or an alkoxy group (preferably about 1 to 4 carbon atoms). Well-known substituents such as 4-carbon alkoxy groups (eg, methoxy, ethoxy, propoxy and butoxy) can be substituted, and these alkoxy groups can be substituted with sulfonamide or acetylsulfonamide groups.

The divalent linking group L bonded to the uncoupling position of the 1H-pyrazolo- [3,2-c] -1,2,4-triazole magenta coupler is an aralkylene group. The aralkylene group directly has an alkylene group which can be directly bonded to the arylene group, or has -O-, -S in the main chain of the aralkylene group.
-, -NHCO-, -CONH-, -NHSO ₂ -or -SO ₂ NH-.
Preferably, the arylene groups are substituted or unsubstituted phenylene groups (eg, they can be substituted with alkyl, alkoxy, halogen, or acylamino). The divalent linking group L contains a ballasting residue consisting entirely of a divalent linking group or a divalent linking group L containing a ballast residue in the form of a substituent.
Can be formed from The alkylene group can be, for example, a 1,2-alkylene group having up to 20 carbon atoms. Alternatively, the arylene group can be substituted with, for example, an alkoxy or acylamino group having up to 20 carbon atoms.

The ballasting group causes the magenta coupler according to the invention to be contained in non-diffused form in the gelatin layer used in the silver halide photographic material. These groups are generally organic groups with straight or branched chain aliphatic groups having 8 to 20 carbon atoms. These ballasting groups attach directly or indirectly to the coupler molecule. When bonding indirectly, for example, bonding is carried out via the following groups. NHCO, NHSO ₂ , NR (where R is hydrogen or alkyl), COO, O or S.

The preferred divalent linking group L has a structure represented by the following formula.

[0020]

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Wherein R ₂ is an alkyl group having 4 to 20 carbon atoms.

Examples of useful divalent linking groups are shown below.

[0023]

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Couplers particularly useful in the present invention are represented by the following formula:

[0025]

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In the formula, R, R ₁ , R ₂ and Z are as defined above.

1H-Pyrazolo- [3,2-c] -1, which can be used in the present invention
Specific examples of the 2,4-triazole coupler are shown below, but are not limited thereto.

[0028]

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The magenta coupler that can be used in the present invention can be easily synthesized using any of the known techniques. Specific examples of the coupler that can be used in the present invention are described below.

[0030]

Synthesis Example 1 Preparation of Coupler (1) 3- [1- (4-Aminophenoxy) tridecyl] -6-methyl-1H-pyrazolo- [3,2-c] -1, prepared according to EP 284,240 2,
4-Triazole (2.45 g, 0.0059 mol) was dissolved in 30 ml of tetrahydrofuran, and toluene-4-sulfonyl chloride (1.1 g, 0.00576 mol) and N, N-dimethylaniline (1.
(4 g, 0.0115 mol). After stirring at room temperature for 16 hours, the solution was poured into cold diluted hydrochloric acid and extracted with diethyl ether. The collected organic layers were washed with water, dried and concentrated. The product was recrystallized from nitromethane. The yield is 3.
3 g.

Elemental analysis results C% = 62.03 H% = 7.05 N% = 11.67 S% = 5.36 (calculated value) C% = 61.80 H% = 7.13 N% = 11.69S% = 5.41 (actual value)

NMR analysis results ¹ H NMR: δ = 0.86 (t, 3H); 1.1-1.7 (m, 2H); 2.0-2.3 (m,
2H); 2.24 (s, 3H); 2.34 (s, 3H); 5.1-5.4 (m, 1H); 6.40
(s, 1H); 6.83 (s, 4H); 7.15-7.25 (d, 2H), 7.40-7.55 (d, 2
H); 9.50 (s, 1H).

[0033]

[Synthesis Example 2] Preparation of coupler (2) 3- [1- (4-aminophenoxy) tridecyl] -6-methyl-1H-
Pyrazolo- [3,2-c] -1,2,4-triazole (8.92 g, 0.02 mol) was dissolved in 90 ml of tetrahydrofuran, and AV Kirsanov and NA Kirsanova (In
st. Org. Chem. Kiev), Zhur. Obshchei Khi
m., Vol. 29, 1802-13, 4- (aminosulfonyl) -benzenesulfonyl chloride (5.37 g, 0.021 mol) and N, N-diethylaniline (5.01) prepared according to 1959 (CA54,8693F). g, 0.042 mol). After stirring at room temperature for 6 hours, the solution was poured into cold diluted hydrochloric acid and extracted with ethyl acetate. The collected organic layer was washed with water and concentrated by drying to obtain a dark oil. The product was chromatographed on silica gel and ground with ligroin to give a solid. The yield was 10 g.

Elemental analysis result C% = 54.16 H% = 6.21 N% = 12.63 S% = 9.64 (calculated value) C% = 53.90 H% = 6.18 N% = 12.33 S% = 9.05 (actual value)

NMR analysis results ¹ H NMR: δ = 0.80 (t, 3H); 1.1-1.7 (m, 20H); 2.0-2.3
(m, 2H); 2.20 (s, 3H); 5.25 (t, 1H); 6.75 (d, 2H); 6.89 (d,
2H); 6.88 (s, 2H); 7.71 (d, 2H); 7.85 (d, 2H); 9.66 (s, 1
H); 12.59 (s, 1H).

[0035]

[Synthesis Example 3] Preparation of coupler (3) 1) Preparation of 4- (N-acetamido-sulfonyl) -benzenesulfonyl chloride

4- (Aminosulfonyl) -benzenesulfonyl chloride (10.22 g, 0.04 mol) was added to 100 ml of acetic anhydride. The solution was stirred, heated at 100 ° C. for 4 hours and poured into water. A white product was obtained, which was filtered off, washed with water and dried. The yield was 10.1 g.

Elemental analysis result C% = 32.27 H% = 2.71 N% = 4.70 S% = 21.54 (calculated value) C% = 32.15 H% = 2.64 N% = 4.77 S% = 21.44 (actual value)

NMR analysis result ¹ H NMR: δ = 1.83 (s, 3H); 7.99
(D, 2H); 8.09 (d, 2H); 11.9
(S, 1H).

2) 3- [1- (4-aminophenoxy)
Tridecyl] -6-methyl-1H-pyrazolo- [3,2-c] -1,2,4-triazole (7.87 g, 0.0176 mol) is dissolved in 100 ml of tetrahydrofuran and 4- (N-acetamidosulfonyl ) -Benzenesulfonyl chloride (5.51 g, 0.0185 mol)
And N, N-diethylaniline (4.49 g, 0.037 mol) were added. After stirring at room temperature for 16 hours, the solution was poured into cold dilute hydrochloric acid and extracted with ethyl acetate. The collected organic layers were washed with water, dried and concentrated. The product was chromatographed on silica gel. The resulting oil was dissolved in diethyl ether and precipitated in petroleum ether.
The yield was 7 g.

Elemental analysis result C% = 54.34 H% = 6.13 N% = 11.88 S% = 9.07 (calculated value) C% = 54.04 H% = 5.98 N% = 11.58 S% = 9.38 (actual value)

NMR analysis result ¹ H NMR: δ = 0.75 (t, 3H); 1.1-1.6 (m, 20H); 1.78 (s, 3
H); 2.0-2.3 (m, 2H); 2.17 (s, 3H); 5.24 (t, 1H); 6.71 (d, 2
H); 6.85 (d, 2H); 7.62 (d, 2H); 7.84 (d, 2H).

The magenta dye-forming coupler used in the present invention can be incorporated into a silver halide photographic material using any of the methods known in the art for including non-diffusible couplers. Such methods include, for example, solid dispersion methods, latex dispersion methods, and preferred oil dispersion methods. For example, in the oil dispersion method, the coupler is dissolved in a high-boiling water-insoluble solvent, and the resulting solution is, for example, described in U.S. Pat.
No. 2,322,027, etc., and emulsified in an aqueous medium. Alternatively, the hydrophobic coupler is dissolved in the high boiling organic solvent in combination with a low boiling organic solvent, and the resulting solution is, for example, U.S. Pat.
No. 2,801,171, 2,949,360, etc., the emulsion is emulsified in an aqueous medium. Typically known high boiling solvents include phthalate esters (e.g., dibutyl phthalate and dioctyl phthalate), phosphate esters (e.g., tricresyl phosphate and trioctyl phosphate) and N-substituted acid amides (e.g., N , N-diethyllauramide). Typically known low boiling solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like. Specific examples of the latex dispersion method are described in U.S. Pat. No. 4,199,363.

The pyrazolotriazole magenta coupler used in the present invention is preferably contained in a photosensitive silver halide emulsion layer. These additives are used in an amount of 0.001 mol per mol of silver halide for a color photographic light-sensitive element.
It is 3 to 1 mol, preferably 0.005 to 0.3 mol. Silver halide emulsion layers containing the pyrazolotriazole magenta couplers described above, or layers sensitive to similar regions of the visible spectrum, may be formed by conventional magenta dye-forming couplers, DIR couplers, BAR couplers, as shown below.
It may contain FAR couplers, DAR couplers and colored couplers, all of which have various effects in the processing steps.

The photographic material of the present invention preferably comprises a blue-sensitive or sensitized silver halide emulsion layer with a yellow dye-forming coupler, a green sensitized silver halide emulsion layer with a magenta dye-forming coupler and a cyan dye-forming coupler. And at least one coupler in this material is a coupler as described above. Each layer is a single emulsion layer or consists of a plurality of emulsion sub-layers sensitive to a defined region of the visible spectrum. If the multi-layer material has multiple blue, green or red subbing layers, they can in any case be relatively fast and slow subbing layers. The photographic material can have other layers such as filter layers, interlayers, overcoat layers, subbing layers, and the like.

The term "associated" is used to indicate that the coupler is present in the silver halide emulsion layer in the relationship shown below. That is, the interaction between the coupler and the layer causes a correspondence corresponding to the image between the silver image formed during development and the color image formed from the coupler. Generally, this is accomplished by adjustment of the coupler in the silver halide emulsion layer or adjustment of the coupler in an adjacent binder layer, which may be non-photosensitive. Preferred couplers for use in the present invention include those that are non-diffusible due to the presence of a hydrophobic ballast group in the molecule.

Typical examples of useful color couplers are naphthol, phenolic or pyrazoloazole cyan dye forming couplers, pyrazolone or pyrazoloazole magenta dye forming couplers and open chain or heterocyclic ketomethylene yellow dye forming couplers. is there. Cyan, magenta and yellow couplers that can be used in the present invention are described in Research Disclosure No. 17643, Chapter VII.
(December 1978) and No. 18717 (November 1979).

Typical examples of yellow dye-forming couplers that can be used in the present invention include known open-chain acylacetamide couplers such as pivaloyl acetanilide and benzoylacetanilide couplers. In the present invention, a divalent yellow coupler is preferably used. Examples of these include, for example, oxygen atom emitting yellow couplers and nitrogen atom emitting yellow couplers. Specific examples of yellow dye-forming couplers are U.S. Pat.Nos. 2,407,210, 2,875,057, 3,265,506, 3,408,194, 3,447,928,
No. 3,933,501, No. 4,022,620, No. 4,326,024 and No. 4,401,752, GB Patent No. 1,077,874 and No. 1,425,020, DE Patent Application No. 2,219,917, No. 2,261,
Nos. 361, 2,329,587 and 2,433,812, JP Patent Nos. 19031/71, 19956/70 and 10739/83
No. and JA Patent Publication (Pat. Public Disclosure) No. 1233
42/75, 87650/75, 133333/79, 6683
No. 5/73, No. 94432/73, No. 28834/75, No. 99433 /
No. 79, No. 70841/80, No. 74249/81, No. 102636/7
No. 6 and No. 87041/81.

Cyan couplers that can be used in the present invention include naphthol, phenolic and pyrazoloazole couplers. Specific examples of naphtholic couplers are described in U.S. Pat.No. 2,474,293.
And U.S. Pat.Nos. 4,052,212, 4,146,396,
Nos. 4,228,233 and 4,296,200 which are divalent naphthol couplers capable of releasing an oxygen atom. Specific examples of phenolic couplers are described in U.S. Pat.
Nos. 23,730, 2,772,162, 2,895,826 and 3,772,002. Specific examples of pyrazoloazole cyan couplers are described in EP Patent Application No. 287,265. Preferred cyan couplers for use in the present invention are U.S. Patent Nos. 2,772,162, 3,758,308,
No. 126,396, No. 4,334,011 and No. 4,327,173, D
2,5-diacylamino-substituted phenolic cyan couplers described in E Patent Application No. 3,229,729 and JA Patent Application No. 42762/83, and U.S. Patent Nos. 3,446,622 and 4,333,999.
And phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position described in JP-A Nos. 4,451,559 and 4,427,767.

The magenta dye-forming couplers defined according to the invention can be used alone or in combination. If desired, they can be used in combination with known magenta dye-forming couplers such as pyrazolone, indazolone, cyanoacetyl, pyrazoloazole and pyrazolotriazole couplers. Useful magenta dye-forming couplers include U.S. Patents 2,600,788 and 2,982.
No. 3,608, No. 3,026,653, No. 3,127,269, No. 3,3
No. 11,476, No. 3,419,391, No. 3,519,429, No. 3,
No.558,319, No.3,582,322, No.3,615,506, No.
3,384,908 and 3,891,445, DE Patent 1,810,46
No. 4, DE Patent Application No. 2,408,665, No. 2,417,945, No. 2,418,959 and No. 2,424,467, JA Patent No. 6031/6
No. 5, and JA Publication No. (Provisional Pat. Publ.) 208
26/76, 58922/77, 129538/74, 7402
7/74, 159336/75, 42121/77, 74028
/ 74, 60233/75, 26541/76 and 551
No. 22/78.

The color coupler can be a tetravalent or divalent coupler. As is known, the latter is derived from tetravalent couplers. They have, at the coupling position, a group which is released in the coupling reaction. Divalent couplers include both colorless and those which have a strong color but which replace the color of the image dye formed by fading during the coupling reaction. The latter (masking couplers) are used in conjunction with the couplers described above to modify the undesired absorption of magenta and cyan coupler image dyes in the short wavelength region.

A typical example of a masking coupler is described in US Pat.
Yellow-colored magenta couplers described in U.S. Pat.No. 4,004,929 and 4,163,670 and JA Patent 39413/82.
No. 4,138,258 and GB Patent No. 1,146,368.

Also, couplers that provide diffusible color dyes can be used with the couplers described above to increase granularity. Specific examples of such couplers are described in U.S. Pat.
Magenta couplers described in 366,237 and GB Patent No. 2,125,570, and EP Patent No. 96,873 and DE Patent Application No.
Yellow, magenta and cyan couplers described in 3,324,533.

Further, the divalent coupler has a group which is released in the color development reaction at the coupling position, and the group has a certain photographic activity (for example, development inhibition or acceleration or bleach acceleration). Provided couplers are included. These groups may exert the above-mentioned effects directly or after further removal of one or more groups. Such 2
Examples of monovalent couplers include known DIR couplers, as well as D
AR, FAR and BAR couplers are included. The couplers described in DE Patent Application Nos. 2,703,145, 2,855,697, 3,
No. 105,026, No. 3,319,428, No. 1,800,420, No.
2,015,867, 2,414,006, 2,842,063, 3,427,235, 3,209,110 and 1,547,640
No., GB Patent Nos. 953,454 and 1,591,641, and
EP Patent Application Nos. 89,843, 117,511, 118,087
Nos. 193,389 and 301,477.

This photosensitive silver halide color photographic material is disclosed, for example, in US Pat. No. 4,080,211 and EP Patent Application No. 2
7,284 and DE Patent Application Nos. 1,297,417 and 2,407,56
No. 9, No. 3,148,125, No. 3,217,200, No. 3,320,0
No. 79, No. 3,324,932, No. 3,331,743 and No. 3,
High molecular weight color couplers as described in US Pat.

The silver halide emulsion which can be used in the present invention can be a fine dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide in a hydrophilic bander. . The silver halide grains can have different phases at their interior and at their surface. The silver halide grains mainly form a surface latent image,
Or they may form latent images mainly inside them. As the hydrophilic binder, all hydrophilic polymers conventionally used in the field of photographic technology are usefully used. These include gelatin, acrylated gelatin, gelatin derivatives such as grafted gelatin,
Cellulose derivatives such as albumin, gum arabic, agar, hydroxyethyl cellulose, carboxymethyl cellulose and the like, and synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide and the like are included. Preferred silver halide grains are silver iodobromide or silver iodobromochloride containing 1 to 20 mol% of silver iodide per mol of silver halide. The silver halide grains can take any crystalline form. For example, cubic, octahedral, spherical, plate or mixed crystal forms. Silver halide grains can have a uniform grain size or a wide grain size distribution. Silver halide dimensions can range from about 0.1 to about 5 μm. The silver halide grains can have different phases between their interior and their surface. Further, the silver halide grains may be those which mainly form a latent image on the surface or those which mainly form a latent image inside them.

The total of the silver halide content in the blue-sensitive, green-sensitive and red-sensitive emulsion layers of the photographic material containing the pyrazolotriazole coupler according to the present invention is 7.5 g / g when calculated on the silver basis. m ²
That is all. The proportions in each photosensitive layer can vary as desired for a particular application. The silver halide emulsion is prepared by a single-jet method, a double-jet method or a combination of these methods, and these can be ripened using, for example, an ammonia method, a neutralization method, an acid method and the like. These are Research Disclosure 17643, I and II, December 1978.
The emulsions described in this article are optical brighteners, antifoggants, and stabilizers, antistain agents (antista
in agents) and image dye stabilizers, filters and antihalo dyes, curing agents, coating aids, plasticizers and lubricants, matting agents, development modifiers and other auxiliary substances. Such auxiliary substances are Research Disclosure 17643, V, VI, VII, VIII, XI, XIII, XVI and XX.
I, described in December 1978. The layers of the photographic material can contain various colloids. These may be used alone or in combination, such as bonding materials, as described, for example, in Research Disclosure 17643, IX, December 1978. The above layers are coated on several supporting substrates (cellulose triacetate, paper, resin-coated paper, polyester) on Research Disclosure 17643, XV and XVI, December 1978.
May be coated by various methods as described in The photosensitive silver halide contained in the photographic material of the present invention forms a visible image by being processed after exposure. This treatment is carried out by bringing the silver halide into contact with an aqueous alkaline medium in the presence of a developer contained in the medium or the material. Processing recipes and techniques are described in Research Disclosure 17643, XIX, XX and XXI, December 1978.

[0057]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Film 1 (Comparative Example) was prepared by coating the following layers in this order on a cellulose triacetate support subbed with gelatin. a) Low-sensitivity silver bromoiodide emulsion (2.5 mol% silver iodide, average grain size 0.18 μm) and medium-sensitivity silver chlorobromoiodide (silver iodide)
(7.2 mol%, silver chloride 5 mol%, average grain size 0.4 μm)
Magenta layer of green-sensitized halide salt emulsion containing a blend coated at a silver coverage and gelatin coverage of 1.8 g / m ² of 2.0 g / m ^2, and dispersed in a layer of high-boiling water-insoluble organic solvent Dye-forming coupler A was coated with a coating of 1.18 mmol / m ² .

Film 2 was prepared in the same manner as film 1 except that coupler B was used as the magenta dye-forming coupler.
(Comparative Example) was prepared.

Coupler (1) for magenta dye-forming coupler
A film 3 (product of the present invention) was prepared in the same manner as in the film 1 except for using.

Coupler (2) for magenta dye-forming coupler
Film 4 in the same manner as film 1 except that
(Product of the present invention) was prepared.

Samples of Films 1, 2, 3 and 4 were exposed through an optical step wedge to a light source having a color temperature of 5,500 ° K. and a British Journal of Photography (Briti).
sh Journal of Photography), June 12, 1974, No. 59
Standard C41 processing chemistry as described on pages 7-598 (pr.
ocessing chemistry). Table 1 shows the results of the photosensitivity measurement. In the table, speed 1 and speed 2 are -logE
Is the sensitivity expressed by E is from fog
(Exposure in meter-candle-seconds measured at densities above 0.2 and 1)
Standard 1 and Standard 2 are respectively the tip of the sensitivity curve (t
oe) and medium contrast and λ
_max is the absorption maximum wavelength (nm) of the magenta dye formed from the coupler by development in the region of the spectrum.

[0063]

[Table 1] Film fog D _max speed 1 speed 2 standard 1 standard 2 λ _max 1 0.20 2.36 1.91 1.23 1.06 0.79 554 2 0.27 2.33 1.96 1.10 0.75 0.60 546 3 0.15 2.90 1.98 1.35 1.21 0.98 554 4 0.19 2.52 1.96 1.42 1.36 0.93 556

The results shown in Table 1 show that the magenta coupler of the present invention has good fog, sensitivity and contrast values, and has an absorption maximum comparable to that of 5-pyrazolone magenta coupler A. On the other hand, the pyrazolotriazole comparative coupler B provided a photographically inferior result and the color was reddish.

[0065]

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──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Enzo Coraluppi Italy 17016 Ferrania (Savona) (address not shown) 3M Italy Richerche Societa per Acioni (72) Inventor Vinicio Busat Italy 17016 Ferrania (Savona) (without address) Inside 3M Italia Richerche Societa Pell Achioni (56) References JP-A-62-98352 (JP, A) JP-A-64-552 (JP, A) JP-A-4-242248 (JP, A) JP-A-4-289852 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 7/38

Claims (4)

(57) [Claims] 1. A support and a compound of the formula Wherein R ₁ is a hydrogen atom, an alkyl group or an aryl group, Z is a hydrogen atom, a halogen atom or a group which can be removed in a coupling reaction with an oxidation product of a color developer, and R is a hydrogen atom , An alkyl group, a sulfonamide group and an acetylsulfonamide group, n is 0 or 1, and L is an arylene group directly bonded to-(NH) _n -SO _2-. (A) a ballasting residue attached to the main chain; and (b) at least one —O—, —S—, —N in the main chain.
An aralkylene divalent bonding group containing HCO- or -CONH-. Having at least one silver halide emulsion layer containing at least one non-diffusible magenta coupler of 1H-pyrazolo (3,2-c) -1,2,4-triazole having a structure represented by the following formula: Silver halide color photographic material. 2. L is a compound of the formula Wherein R ₂ is an alkyl group of 4 to 20 carbon atoms. ]
The photographic material according to claim 1, which is a divalent group having a structure represented by the following formula: 3. The method according to claim 1, wherein said coupler is of the formula The photographic material according to claim 1, which has a structure represented by: 4. A support and a compound of the formula [Wherein, R ₁ is a hydrogen atom, an alkyl group or an aryl group, R ₂ is an alkyl group having 4 to 20 carbon atoms,
R ₃ is a hydrogen atom, an alkyl group, an alkoxy group, a sulfonamide group, or an acetylsulfonamide group;
Or Z is a hydrogen atom, a halogen atom, or a group that can be removed in a coupling reaction with an oxidation product of a color developer. Having at least one silver halide emulsion layer containing at least one non-diffusible magenta coupler of 1H-pyrazolo (3,2-c) -1,2,4-triazole having a structure represented by the following formula: Silver halide color photographic material.