JPH1172886A - Photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reactivity and raw film preservability by incorporating a specified silver halide emulsion layer. SOLUTION: A silver halide emulsion layer combined with a 1-phenyl-3- anilino-4-benzotriazolyl-5-pyrazolone type magenta dye forming DIR coupler represented by the formula is incorporated. In the formula, R1 is H, Cl, F, etc., R2 -R4 are H, halogen, alkyl, etc., R5 is H, Br, Cl, etc., R6 and R7 are H, halogen, carbonamido, etc., at least one of R6 and R7 is not H, R8 and R9 are H, halogen, alkyl, etc., at least one of R8 and R9 is not H, when R5 is H, the sum of Hammett's σ-values on the basis of the positions of the anilino nitrogen atoms of R6 and R7 is >=0.30 and R1 is also H, and when R5 is Br, Cl, etc., the sum of Hammett's σ-values on the basis of the positions of the anilino nitrogen atoms of R6 and R7 is >=0.20 and the sum of the π-values of R8 and R9 is 0.60-3.00.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic element containing a silver halide emulsion layer in which a specific magenta benzotriazole releasing DIR coupler is combined.

[0002]

BACKGROUND OF THE INVENTION Many photographic materials, especially color negative films, contain so-called DIR (development inhibitor releasing) couplers. In addition to forming image-forming dyes, DIR couplers release inhibitors that can inhibit silver development in the released layer as well as in other layers of the multilayer photographic material. DIR
Couplers help control gamma or contrast, improve sharpness or acutance, reduce graininess, and enable color correction through interlayer interimage effects. Even more effective magenta dye-forming D
There is a need for an IR coupler. For modern color negative films, magenta DIR couplers that provide advanced interimage color correction are particularly desirable. In addition, there is a need for couplers that exhibit high activity so as to maximize the release rate and release efficiency of the inhibitor and minimize the amount of coating. Further, there is a need for a magenta DIR coupler that is stable over long periods of time, especially at high temperatures. The DIR couplers of the present invention have all of these desirable properties, and in particular, are similar to the conventional similar magenta dye-forming DIRs.
Shows higher activity and stability than couplers.

[0003] Known pyrazolone couplers include those containing an unsubstituted benzotriazole coupling-off group, which fall outside the range of the substituents R ₈ and R ₉ of the present invention. U.S. Pat. No. 4,015,988 describes pyrazolone couplers (9 and 10) having a methyl or bromo substituent. However, all couplers have an o-methoxy substituent on the anilino group and thus fall outside the scope of the anilino substituents of the present invention. JP-A-60-128,444 describes a coupler having a dimethyl-substituted benzotriazole.
-Having a methoxy substituent.

[0004] Many of the prior art couplers (such as those described in GB 1,455,967) have a p-nitro substituent on the 1-phenyl group, which is also the subject of the present invention. It is out of the range of the substituent. U.S. Pat. No. 4,477,563 describes couplers having a benzotriazole releasing group (e.g., pyrazolone-based couplers), but the illustrated couplers have 2,4,6 on a 1-phenyl ring. -It contains a trichloro substitution or otherwise contains a substituent whose reactivity is not improved as desired.

[0005]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a photograph containing a silver halide emulsion layer combined with a magenta dye-forming coupler having high reactivity and good raw film preservability. Is to provide the element.

[0006]

According to the present invention, there is provided 1-phenyl-3-anilino-4- represented by the following general structural formula (I).
Provided is a photographic element comprising a silver halide emulsion layer in which a benzotriazolyl-5-pyrazolone magenta dye-forming DIR coupler is combined.

[0007]

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In the above formula, R ₁ represents a hydrogen, chlorine, fluorine or methyl group, and R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen, alkyl, phenyl, alkoxy, phenoxy, alkylthio, carboxy, Amide, sulfonamide, carbamoyl, alkoxycarbonyl and aryloxycarbonyl groups are selected from the group consisting of R ₅ represents hydrogen, bromine, chlorine, fluorine or an alkyl group; R ₆ and R ₇ are each independently hydrogen, Halogen, carbonamide, carbamoyl, sulfonamide, sulfamoyl,
Selected from the group consisting of alkylsulfonyl, arylsulfonyl, alkylsulfoxyl, arylsulfoxyl, sulfonyloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acyl, imide, trifluoromethyl and cyano groups, provided that R ₆
And at least one of R ₇ is not hydrogen, but R ₈ and R ₉
Is each independently hydrogen, halogen, alkyl, phenyl, alkoxy, phenoxy, alkoxycarbonyl,
Selected from the group consisting of aryloxycarbonyl, carbonamido, sulfonamido, carbamoyl and carbamoyloxy groups, provided that at least one of R ₈ and R ₉ is not hydrogen, and (1) when R ₅ is hydrogen Has a total Hammett sigma value of 0.30 or more based on the position of the anilino nitrogen of R ₆ and R ₇ , and R ₁ is also hydrogen; and (2) R ₅ is bromine, chlorine, fluorine Or when it is an alkyl group, the sum of Hammett sigma values of R ₆ and R _{7 based} on the position of the anilino nitrogen is 0.20 or more, and the sum of pi values of R ₈ and R ₉ is 0. It is not less than .60 and not more than 3.00.

Further, the present invention provides a magenta DIR coupler, a silver halide emulsion containing the coupler, a dye obtained by combining the coupler with a color developing solution,
It provides an image containing the dye and a method of obtaining an image by subjecting the element of the invention to imagewise exposure and then contacting it with a color developer. The elements of the present invention provide magenta dye-forming couplers that have high reactivity and good raw stock keeping.

Specific magenta dye-forming pyrazolones D
The photographic material of the present invention containing an IR coupler is as described above. It is important to note that the coupler of the present invention may
This is a point having hydrogen at the 6-position of the phenyl ring. It is important for the reactivity that C1, C
This is apparent from the results using C2 and C3.

R ₁ is a hydrogen, chlorine, fluorine or methyl group. In order to further increase the reactivity of the coupler, R ₁
Is particularly useful. Also, R ₁ , R ₂
And embodiments wherein R ₄ is hydrogen and R ₃ is hydrogen or methyl are also particularly useful. R ₂ , R ₃ and R ₄ are each independently suitably selected from hydrogen, halogen, alkyl, phenyl, alkoxy, phenoxy, alkylthio, carbonamide, sulfonamide, carbamoyl, alkoxycarbonyl or aryloxycarbonyl group Can be. Most typically, a hydrogen, fluoro, chloro, alkyl, alkoxy, carbonamido or alkoxycarbonyl group is chosen.

R ₅ is hydrogen, bromine, chlorine, fluorine or an alkyl group. A preferred example is an embodiment in which R ₅ is chlorine, fluorine or methyl, but it is convenient to use chlorine.
R ₆ and R ₇ are each independently halogen, carbonamido, carbamoyl, sulfonamido, sulfamoyl,
It is selected from the group consisting of alkylsulfonyl, arylsulfonyl, alkylsulfoxyl, arylsulfoxyl, sulfonyloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acyl, imide, trifluoromethyl and cyano groups. Generally, alkylsulfonyl, alkoxycarbonyl, carbonamido or cyano groups are useful, but usually only one of the 4- or 5-position to the anilino nitrogen is occupied by a non-hydrogen substituent. At least one of R ₆ and R ₇ is a non-hydrogen substituent.

When R ₅ is hydrogen, the sum of the Hammett sigma values of R ₆ and R _{7 based} on the position of the anilino nitrogen is greater than or equal to 0.30 and R ₁ is also hydrogen. R ₅
Is chlorine or fluorine, the sum of the Hammett sigma values of R ₆ and R _{7 based} on the position of the anilino nitrogen is 0.20 or more.

R ₈ and R ₉ are each independently hydrogen, halogen, alkyl, phenyl, alkoxy, phenoxy,
It is selected from the group consisting of alkoxycarbonyl, aryloxycarbonyl, carbonamide (eg, alkylcarbonamide, arylcarbonamide, alkoxycarbonamide, and aryloxycarbonamide), sulfonamide, carbamoyl, and carbamoyloxy group. Phenoxycarbonyl and derivatives are preferably used, including, for example, p-chlorophenoxycarbonyl, p-methylphenoxycarbonyl or p-methylthiophenoxycarbonyl, and alkoxy, carbonamide and alkoxycarbonyl substituents. Other examples include butoxycarbonylmethoxycarbonyl, 1-
Methyl-1-butoxycarbonylmethoxycarbonyl,
n-pentylcarbonylamino, 5,6-dichloro,
5,6-dipropoxy and n-butyl. R
It is necessary that at least one of ₈ and R ₉ is not hydrogen. The sum of the pie values of R ₈ and R ₉ is 0.60 or more and 3.00 or less.

R ₅ is chlorine or fluorine and the sum of the Hammett sigma values of R ₆ and R ₇ together is 0.25
In the case where the above is satisfied, the stability may be improved. R ₈
In the embodiment where the total pie value of R ₉ and R ₉ is in the range of 1.0 to 2.2, the development suppression efficiency is high, and the intermediate image of the intermediate layer tends to be good. In another embodiment, at least one of R ₈ and R ₉ is easily hydrolyzed, for example,
Phenoxycarbonyl group or -CO ₂ CH ₂ CO ₂ R ₁₀
Some groups (R ₁₀ = alkyl group or phenyl group) prevent the developer from seasoning due to a strong inhibitor. A “hydrolyzable group” refers to a compound to which the group is attached in a Kodak C-41 ™ developer solution.
It means that the half-life for hydrolysis at 0 C is within 1 hour. In addition, in order to minimize the movement of the coupler, it is desired that the total number of carbon atoms and halogen atoms contained in R _{1 to} R ₇ is 8 or more, preferably 10 or more.

The use of Hammett sigma and pi values to describe chemical properties is well established in the literature and is described, for example, in "Exploring QSAR, Fundamen.
talsand Applications in Chemistry and Biology '' (C.
Hansch and A. Leo, American Chemical Society, Was
hington, DC, 1995). There are many publications on Hammett sigma and pie values, such as "Ex
ploring QSAR, Hydrophobic, Electronic and Steric C
onstants '' (C. Hansch, A. Leo and D. Hoekman, Ameri
can Chemical Society, Washington, DC, 1995),
`` The Chemists Companion '' (AJ Gordon and RA Fo
rd, John Wiley & Sons, New York, 1972), `` Substitu
ent Constants for Correlation Analysis '' (C. Hansch
and A. Leo, John Wiley & Sons, New York, 1979) and A. Leo's `` Comprehensive Medicinal Chemistry ''
(C. Hansch, PG Sammes and JB Taylor eds., Permag
on Press, New York, 1972). In general, the pi value of a substituent increases as the hydrophobicity increases, and the sigma value increases as the electron-attracting force near the bonding point of the substituent increases. The pi and sigma values for hydrogen are zero.

Useful coverages of the magenta dye-forming pyrazolone DIR couplers of this invention range from about 0.005 to about 0.40 g / m ² , more typically from 0.01 to about 0.40 g / m ^2.
It is in the range of 0.20 g / m ² .

After dissolving the coupler of the present invention in a high boiling coupler solvent, a mixture of the organic coupler and the coupler solvent is added to an aqueous solution containing gelatin and a surfactant (by a pulverization method or a homogenization method). It is common to utilize by dispersing as small particles. In preparing such a dispersion, a removable auxiliary organic solvent such as ethyl acetate or cyclohexanone may be used to promote dissolution of the coupler in the organic phase. Useful coupler solvents in practicing the invention include aryl phosphates (eg, tolyl phosphate), alkyl phosphates (eg, trioctyl phosphate), arylalkyl mixed phosphates (eg, diphenyl 2-ethylhexyl phosphate), aryl phosphonates, alkyl Phosphonates, arylalkyl mixed phosphonates,
Phosphine oxides (eg, trioctylphosphine oxide), esters of aromatic acids (eg, dibutyl phthalate,
Octyl benzoate or benzyl salicylate), esters of aliphatic acids (eg, acetyl tributyl citrate or dibutyl sebacate), alcohols (eg, 2-hexyl-1)
-Decanol), phenol (eg, p-dodecylphenol), carbonamide (eg, N, N-dibutyldodecaneamide or N-butylacetanilide), sulfoxide (eg, bis (2-ethylhexyl) sulfoxide),
Examples include, but are not limited to, sulfonamides (eg, N, N-dibutyl-p-toluenesulfonamide) or hydrocarbons (eg, dodecylbenzene). For further coupler and co-solvents, see Research Disclosure, December 1989,
Item 308, 119, p. 993). Useful coupler: coupler solvent weight ratios are from about 1: 0.1 to 1: 8.
0, with a preferred range of 1: 0.2 to 1:
4.0.

The pyrazolone-based DIR coupler of the present invention comprises:
It can be used with various other couplers in the same or different layers of the multilayer photographic material. As a specifically conceivable embodiment, the pyrazolone DIR coupler of the present invention is
US Patent No. 5,200,309 (Merkel and Singer)
Used in green-sensitive photographic elements together with one or more 1-phenyl-3-anilino-5-pyrazolone magenta dye-forming imaging couplers defined by structural formulas I, III and IV Is mentioned. Such a dye-forming imaging coupler is represented by the following general formula.

[0020]

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In the above formula, Ar is selected from the group consisting of an unsubstituted aryl group, a substituted aryl group and a substituted pyridyl group;
The substituent is a halogen atom and cyano, alkylsulfonyl, arylsulfonyl, sulfamoyl, sulfonamide, carbamoyl, carbonamide, alkoxy, acyloxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, ureido, nitro,
Selected from the group consisting of alkyl and trifluoromethyl groups, Y is selected from the group consisting of anilino, acylamino and ureido groups; one of the substituents is a halogen atom and alkyl, aryl, alkoxy, aryloxy, carboxy Amide, carbamoyl, sulfonamide,
Sulfamoyl, alkylsulfoxyl, arylsulfoxyl, alkylsulfonyl, arylsulfonyl,
Consisting of alkoxycarbonyl, aryloxycarbonyl, acyl, acyloxy, ureido, imide, carbamate, heterocyclic, cyano, trifluoromethyl, alkylthio, nitro, carboxyl, and hydroxyl groups, and groups that form bonds to the polymer chain. Is substituted with one or more substituents selected from the group, Y further contains 6 or more carbon atoms, and X is a halogen atom and alkoxy, aryloxy, alkylthio, arylthio, acyloxy, Sulfonamide,
A coupling-off group selected from the group consisting of sulfonyloxy, carbonamido, arylazo, nitrogen-containing heterocyclic and imide groups. Y is preferably represented by the following general formula.

[0022]

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In the above formula, p is in the range of 0 to 2, and each R
_B is in the meta or para position to R _A , R _B is each independently a halogen atom and alkyl, alkoxy,
Aryloxy, carbonamide, carbamoyl, sulfonamide, sulfamoyl, alkylsulfoxyl,
Selected from the group consisting of arylsulfoxyl, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, ureido, imide, carbamate, heterocyclic, cyano, nitro, acyl, trifluoromethyl, alkylthio and carboxyl groups; And R _A is hydrogen, a halogen atom, alkyl, alkoxy, aryloxy, alkylthio, carbonamide, carbamoyl, sulfonamide,
Sulfamoyl, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, acyloxy, acyl,
It is selected from the group consisting of cyano, nitro and trifluoromethyl groups. One useful X is represented by the following general formula.

[0024]

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In the above formula, R _C and R _D are each independently hydrogen, a halogen atom, alkyl, alkoxy, aryloxy, carbonamide, ureido, carbamate,
Is selected from the group consisting of sulfonamido, carbamoyl, sulfamoyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, amino and carboxyl groups, q is 0, 1 or 2, and _RD is a meta position relative to the sulfur atom. Or para position.
In a particularly contemplated embodiment, the pyrazolone-based DIs of the present invention
Some use R couplers in combination with M-1 and M-2 (see Example 1). Hereinafter, specific examples of the pyrazolone-based DIR coupler of the present invention (A1 to A
29), but not limited thereto.

[0026]

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In the present specification, unless otherwise specified, any substituent capable of bonding to a molecule may be any substituent, whether or not substituted, as long as it does not impair the characteristics required for photographic use. included. When the term `` group '' is applied to identify a substituent containing a hydrogen that can be substituted, not only the unsubstituted form of the substituent, but also its further substituted with any of the groups described herein. It is intended to encompass shapes as well. Preferably, the group is halogen, or carbon, silicon,
It can be linked by oxygen, nitrogen, phosphorus or sulfur atoms. Substituents include, for example, halogen (eg, chlorine, bromine or fluorine), nitro, hydroxyl, cyano, carboxyl, or optionally substituted groups, eg, alkyl, including linear or branched or cyclic alkyl [Examples: methyl, trifluoromethyl, ethyl, t-butyl, 3- (2,4-di-t-
Amylphenoxy) propyl and tetradecyl], alkenyl (eg, ethylene, 2-butene), alkoxy [eg, methoxy, ethoxy, propoxy, butoxy,
-Methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy,
2- (2,4-di-t-pentylphenoxy) ethoxy and 2-dodecyloxyethoxy), aryl (eg, phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl), aryloxy (Eg, phenoxy, 2-methylphenoxy, α- or β-naphthyloxy and 4-tolyloxy), carbonamide [eg,
Acetamide, benzamide, butylamide, tetradecaneamide, α- (2,4-di-t-pentylphenoxy) acetamide, α- (2,4-di-t-pentylphenoxy) butylamide, α- (3-pentadecylphenoxy) Hexanamide, α- (4-hydroxy-3-
(t-butylphenoxy) tetradecaneamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrolin-1-yl, N-methyltetradecaneamide, N-succinimide, N-phthalimide, 2,5-
Dioxo-1-oxazolidinyl, 3-dodecyl-2,
5-dioxo-1-imidazolyl, N-acetyl-N-
Dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5- (di-t-pentylphenyl ) Carbonylamino, p-dodecylphenylcarbonylamino, p-toluylcarbonylamino, N-methylureido, N, N-dimethylureido, N-methyl-N
-Dodecyl ureide, N-hexadecyl ureide, N,
N-dioctadecylureido, N, N-dioctyl-
N'-ethylureide, N-phenylureide, N, N
-Diphenylureide, N-phenyl-Np-toluylureide, N- (m-hexadecylphenyl) ureide, N, N- (2,5-di-t-pentylphenyl)-
N′-ethylureido and t-butylcarbonamide), sulfonamides (eg, methylsulfonamide, benzenesulfonamide, p-tolylsulfonamide,
p-dodecylbenzenesulfonamide, N-methyltetradecylsulfonamide, N, N-dipropyl-sulfamoylamino and hexadecylsulfonamide), sulfamoyl {eg, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N, N-dimethylsulfamoyl, N- [3- (dodecyloxy) propyl] sulfamoyl, N- [4- (2,4-di -T-
Pentylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl and N-dodecylsulfamoyl}, carbamoyl {eg, N-methylcarbamoyl, N, N-dibutylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,4-di-t-
Pentylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl and N, N-dioctylcarbamoyl}, acyl [eg, acetyl, (2,4
-Di-t-amylphenoxy) acetyl, phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl,
Methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl and dodecyloxycarbonyl], sulfonyl (eg, methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxy) Sulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl and p-toluylsulfonyl), Sulfonyloxy (eg, dodecylsulfonyloxy and hexadecylsulfonyloxy), sulfinyl (eg, Tylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl and p-toluylsulfinyl), thio (eg, ethylthio, octylthio, benzylthio, tetradecylthio, 2- ( 2,
4-di-t-pentylphenoxy) ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio and p-tolylthio], acyloxy (eg, acetyloxy, benzoyloxy, octadecanoyloxy, p
-Dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy and cyclohexylcarbonyloxy), amines (eg, phenylanilino, 2-chloroanilino, diethylamine, dodecylamine), imino [eg, 1- (N- Phenylimido) ethyl, N-succinimide or 3-benzylhydantoinyl], phosphates (eg, dimethylphosphate and ethylbutylphosphate), phosphites (eg, diethylphosphite and dihexylphosphite), oxygen, nitrogen and sulfur A 3- to 7-membered heterocyclic ring containing at least one heteroatom selected from the group and a carbon atom, and optionally substituted heterocyclic group, heterocyclic oxy group or heterocyclic thio group; Group (eg, 2
-Furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl), quaternary ammonium (eg, triethylammonium), and silyloxy (eg, trimethylsilyloxy).

If desired, these substituents may themselves be further substituted one or more times with the aforementioned substituents. The particular substituents employed can be selected by those skilled in the art to provide the photographic properties desired for the particular application, for example, hydrophobic groups, solubilizing groups, blocking groups, releasable or releasable groups, Etc. can be included. In general, the above groups and their substituents can include those having up to 48 carbon atoms, typically 1-36, usually less than 24, but the particular substituent chosen In some cases, the number of carbon atoms may further increase.

The materials of the present invention can be used in any manner known in the art, and in any combination. Typically, the materials of this invention are included in a silver halide emulsion, and the emulsion is coated as a layer on a support to form part of a photographic element. Alternatively, unless otherwise provided, they may be incorporated adjacent to a silver halide emulsion layer that is reactively combined with a development product, such as an oxidized color developer, during development. Thus, in this specification,
The term "combined" means that the compound is in the silver halide emulsion layer or in an adjacent location where the compound can react with the silver halide development product during processing.

It may be desirable to include high molecular weight hydrophobic species or "ballast" groups in the coupler molecule to control the migration of the various components. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups containing from 8 to 48 carbon atoms. Representative substituents attached to such groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl,
It includes acyloxy, amino, anilino, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamido and sulfamoyl groups, these substituents typically containing from 1 to 42 carbon atoms. Further, such a substituent may be further substituted.

The photographic element may be a single color element or a multicolor element. Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can contain a single emulsion layer or multiple emulsion layers sensitive to a particular region of the spectrum. The layers of the photographic element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In another format, the emulsions sensitive to each of the three primary regions of the spectrum can be arranged as a single segmented layer.

A typical multicolor photographic element comprises a cyan dye image-forming unit comprising one or more red-sensitive silver halide emulsion layers in combination with at least one cyan dye-forming coupler, and at least one magenta A magenta dye image-forming unit comprising one or more green-sensitive silver halide emulsion layers in combination with a dye-forming coupler;
1 in combination with a yellow dye-forming coupler
A yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer. The element may further contain another layer such as a filter layer, an intermediate layer, an overcoat layer, a subbing layer, and the like.

If desired, a magnetic layer can be applied to the photographic element for use. For the application of the magnetic layer,
Research Disclosure (November 1992, Item 34390, Kenneth, UK)
Mason Publications (Dudley An
nex, 12a North Street, Emsworth, Hampshire, P0107D
Q)) and Hatsumei Kyokai No. 94-6023 (issued on Mar. 15, 1994), which is available from the Japan Patent Office and incorporated herein by reference. I do. If you want to use the inventive materials in a small format film, Research
Disclosure (Item, June 1994
36230) describes a suitable embodiment.

In the following description of materials suitable for use in the emulsions and elements of the invention, reference is made to the Research Disclosure (1) available above.
September 996, Item 38957). In this specification, this document is hereinafter referred to as “Research.
h Disclosure ". The contents of this Research Disclosure, including the patent specifications and publications cited therein, are hereby incorporated by reference. The section referred to hereinafter is the Research Disc.
loss section.

The silver halide emulsion-containing elements used in this invention are negative-working, as indicated by the type of processing applied to the element (ie, color negative, reversal or direct positive processing). Or a positive type. Suitable emulsions and their preparation, as well as methods of chemical and spectral sensitization, are described in Sections I-V. Various additives such as UV dyes, optical brighteners, antifoggants, stabilizers, light absorbing substances, light scattering substances, and physical property adjusting additives such as hardeners, coating aids, plasticizers,
Lubricants and matting agents are described, for example, in Sections II and VI-.
VIII. The coloring materials are described in sections X to XIII. Suitable methods for incorporating couplers and dyes, including dispersions in organic solvents, are described in Section X (E). The scan facilitation method is described in Section XIV. Supports, exposure methods, developing devices and processing methods are described in Sections XV-XX. Research Disclosure (199)
The information contained in Item 36544) in September, 2004 was published in Research Disclosure (1996).
September 38, Item 38957). Certain desirable photographic elements and processing steps, including those useful in conjunction with color reflective prints, Research
Disclosure (February 1995, Item
37038).

Coupling leaving groups are well known in the art. The group has the chemical equivalent of the coupler, ie, 2
One can determine whether it is an equivalent coupler or a four equivalent coupler, or adjust the reactivity of the coupler.
The group may be present in the layer to which the coupler is coated or another layer in the photographic recording material after dye release from the coupler, dye formation, dye hue control, development acceleration, development inhibition, bleach acceleration, bleach inhibition, electron transfer enhancement. By exerting functions such as color correction, etc., advantageous effects can be exerted.

When a hydrogen is present at the coupling site, a 4-equivalent coupler is obtained, and when another coupling-off group is present, a 2-equivalent coupler is usually obtained. Representative examples of such coupling-off groups include chloro,
Alkoxy, aryloxy, heterooxy, sulfonyloxy, acyloxy, acyl, heterocycle, sulfonamide, mercaptotetrazole, benzothiazole,
Mercaptopropionic acid, phosphonyloxy, arylthio and arylazo. These coupling-off groups are described, for example, in US Pat.
No. 5,169, No. 3,227,551, No. 3,4
No. 32,521, No. 3,476,563, No. 3,
Nos. 617,291, 3,880,661, 4,052,212 and 4,134,766 and British Patent Nos. 1,466,728 and 1,53.
Nos. 1,927, 1,533,039, UK Patent Application Publication Nos. 2,006,755A and 2,017,
No. 704A, which is incorporated herein by reference.

The photographic element includes US Pat. No. 2,367,
No. 531, No. 2,423,730, No. 2,47
No. 4,293, No. 2,772,162, No. 2,8
No. 95,826, No. 3,002,836, No. 3,
Nos. 034,892, 3,041,236, 4,333,999 and 4,883,746 and Agfa Mitteilungen's publication "Farbkuppler-
eine Literature Ubersicht '' (Band III, 156-17
(P. 5, 1961), and image dye-forming couplers such as those described in the publications which produce cyan dyes upon reaction with oxidized color developing agents. Such a coupler is preferably phenol or naphthol, which forms a cyan dye upon reaction with an oxidized color developing agent.

A coupler which forms a magenta dye upon reaction with an oxidized color developing agent is disclosed in US Pat.
No. 1,082, No. 2,343,703, No. 2,3
No. 69,489, No. 2,600,788, No. 2,
908,573, 3,062,653, 3,152,896, 3,519,429, 3,758,309 and 4,540,654 Book and the Agfa Mitteilungen publication `` Farbkupple
r-eine Literature Ubersicht '' (Band III, No. 126-1
56, 1961) and in published patents. Such a coupler is preferably a pyrazolone, a pyrazolotriazole or a pyrazolobenzimidazole which forms a magenta dye upon reaction with an oxidized color developing agent.

For a coupler which produces a yellow dye upon reaction with an oxidized color developing agent, see US Pat. No. 2,29.
No. 8,443, No. 2,407,210, No. 2,8
No. 75,057, No. 3,048,194, No. 3,
Nos. 265,506, 3,447,928, 4,022,620 and 4,443,536, and Agfa Mitteilungen's publication "Farbkuppler-
eine Literature Ubersicht '' (Band III, 112--12
6 (1961). Such a coupler is typically an open-chain ketomethylene compound.

Couplers which form colorless products upon reaction with oxidized color developing agents are described in GB 861,1.
No. 38, U.S. Pat. Nos. 3,632,345 and 3,9
Nos. 28,041, 3,958,993 and 3,961,959. Typically, such couplers are cyclic carbonyl-containing compounds that form colorless products upon reaction with oxidized color developer.

For a coupler which produces a black dye upon reaction with an oxidized color developing agent, US Pat.
No. 9,231, No. 2,181,944, No. 2,3
33,106 and 4,126,461 and German Patent Application Publication Nos. 2,644,194 and 2,650,764. . Typically, such couplers are resorcinol or m-aminophenol, which form a black or neutral product upon reaction with oxidized color developer.

In addition to the above, so-called "universal" or "washout" couplers may be used.
These couplers do not contribute to image dye formation. Thus, for example, naphthols having unsubstituted carbamoyl or carbamoyl in which the 2- or 3-position is substituted with a low molecular weight substituent can be used. For such couplers, see, for example, U.S. Pat.
No. 6,628, No. 5,151,343 and No. 5,
No. 234,800.

Known ballast groups or coupling-off groups, such as those described in US Patent Nos. 4,301,235, 4,853,319 and 4,351,897. It may be useful to use a combination of couplers that either can contain. The coupler may contain a solubilizing group as described in U.S. Pat. No. 4,482,629. The couplers may also be used in combination with "wrong" colored couplers (e.g., to adjust the interlayer correction level), and for color negative applications, EP 213,490. JP-A-58-
No. 172,647, US Pat. No. 2,983,608
No. 4,070,191 and No. 4,273,8
No. 61, German Patent Application Publication No. 2,706,117
No. 2,643,965, British Patent No. 1,
No. 530,272 and JP-A-58-11393.
A masking coupler such as that described in JP-A No. 5 can be used in combination. The masking coupler may be shifted or blocked as desired.

Improving image quality by using the materials of the present invention in combination with substances that release photographically useful groups (PUGs) that accelerate or otherwise regulate processing steps such as bleaching and fixing. be able to. European Patent Nos. 193,389 and 301,477, U.S. Patent Nos. 4,163,669 and 4,865,956
In some cases, the bleaching accelerator releasing couplers described in U.S. Pat. No. 4,923,784 and U.S. Pat. No. 4,923,784 are useful. Further, a nucleating agent, a development accelerator or a precursor thereof (British Patent No. 2,097,140; No. 2,131,18)
No. 8); electron transfer agent (US Pat. No. 4,859,5)
No. 78; 4,912,025); antifoggants and color-mixing inhibitors such as hydroquinone, aminophenol, amine, and derivatives of gallic acid; catechol; ascorbic acid; hydrazide; sulfonamide phenol; The use of compositions in combination with color-forming couplers is also conceivable.

The materials of the present invention can also be used as oil-in-water dispersions, latex dispersions or solid particle dispersions in combination with a yellow, cyan and / or magenta filter dye or a filter dye layer containing a colloidal silver sol. it can. In addition, they are "smearing"
Couplers (e.g., U.S. Pat. No. 4,366,237, EP 96,570, U.S. Pat. No. 4,420,556)
And US Pat. No. 4,543,323). Further, the composition can be coated or blocked in a protected form as described in, for example, Japanese Patent Application No. 61-258,249 or US Pat. No. 5,019,492.

The materials of the present invention can further be used with PUG-releasing image modifying compounds such as "development inhibitor releasing" (DIR) compounds. DIRs useful in combination with the compositions of the present invention are known in the art, and examples thereof are described in the following patents: U.S. Patent Nos. 3,137,578; 3,1
No. 48,022, No. 3,148,062, No. 3,
No. 227,554, No. 3,384,657, No. 3,379,529, No. 3,615,506, No. 3,617,291, No. 3,620,746,
Nos. 3,701,783 and 3,733,201
No. 4,049,455 and 4,095,98
No. 4, No. 4,126,459, No. 4,149,8
No. 86, No. 4,150,228, No. 4,211,
No. 562, No. 4,248,962, No. 4,25
No. 9,437, No. 4,362,878, No. 4,4
No. 09,323, No. 4,477,563, No. 4,
Nos. 782,012, 4,962,018, 4,500,634, 4,579,816, 4,607,004, 4,618,571,
Nos. 4,678,739 and 4,746,600
No. 4,746,601, No. 4,791,04
No. 9, No. 4,857,447, No. 4,865,9
No. 59, No. 4,880,342, No. 4,886,
Nos. 736, 4,937,179 and 4,94
No. 6,767, No. 4,948,716, No. 4,9
No. 52,485, No. 4,956,269, No. 4,
959,299, 4,996,835 and 4,985,336; British Patent 1,560,
No. 240, No. 2,007,662, No. 2,03
2,914 and 2,099,167; German Patents 2,842,063 and 2,937,12
No. 7, No. 3,636,824 and No. 3,644,
416; and EP 272,573,
Nos. 335, 319, 336, 411, and 3
No. 46,899, No. 362,870, No. 365
No. 252, No. 365, 346, No. 373, 382
Nos. 376,212, 377,463, 378,236, 384,670, and 39
Nos. 6,486, 401,612 and 401,
No. 613.

Such a compound is known as Photograph
hic science and engineinein
g (13, 174, 1969).
R. Barr, J .; R. Thirtle and P.M. W. V
Ittum's “Development Inhibitor Release Type for Color Photography (DI
R) Coupler ", which is hereby incorporated by reference. Generally, development inhibitor releasing (DIR) couplers include a coupler moiety and an inhibitor coupling off moiety (IN). Inhibitor-releasing couplers are time-delayed (DIAR couplers) that further include a timing moiety or chemical switch to delay the release of the inhibitor.
May be used. Examples of typical inhibitor moieties include oxazole, thiazole, diazole, triazole, oxadiazole, thiadiazole, oxathiazole, thitriazole, benzotriazole, tetrazole, benzimidazole, indazole, isoindazole, mercaptotetrazole, selenotetrazole, mercapto Benzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzodiazole, mercaptooxazole, mercaptothiadiazole, mercaptothiazole, mercaptotriazole, mercaptooxadiazole, mercaptodiazole, mercaptooxa Thiazole, tellurotetrazole or benz Sojiazoru and the like. In a preferred embodiment, the inhibitor moiety or group is selected from the following formula:

[0079]

Embedded image

In the above formula, R _I is a linear or branched alkyl, benzyl, phenyl or alkoxy group having 1 to about 8 carbon atoms, and such a group containing no or one or more substituents thereof. R _II is selected from R _I and -SR _I ; R _III is a linear or branched alkyl group having 1 to about 5 carbon atoms and m is 1 to 3 , And R _IV are hydrogen, halogen, alkoxy,
Phenyl group, carbonamido group, -COOR _V and -N
HCOOR _V wherein R _V is selected from substituted and unsubstituted alkyl and aryl groups.

The coupler moiety contained in the development inhibitor releasing coupler is one which typically forms an image dye corresponding to the layer in which it is located, but which is combined with another film layer As a different color. It may also be useful for the coupler moiety contained in the development inhibitor releasing coupler to form a colorless product and / or a product that is washed out of the photographic material during processing (a so-called "universal" coupler). ).

Compounds such as couplers can release PUG directly upon reaction of the compound during processing, or indirectly via a timing or linking group. The timing group delays the release of PUG, and the timing group includes a group utilizing an intramolecular nucleophilic substitution reaction (US Pat. No. 4,248,962); and utilizing an electron transfer reaction along a conjugated system. Group (US Pat. No. 4,409,3)
No. 23, No. 4,421,845, No. 4,861,
No. 701, Japanese Patent Application No. 57-188035, No. 58-98
Nos. 728, 58-209736 and 58-209
No. 738); a group which functions as a reducing agent or a coupler after a coupler reaction (US Pat. No. 4,438,193)
No. 4,618,571) and groups having a combination of the above characteristics. The timing group is typically one of the following formulas:

[0083]

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Where IN is the inhibitor moiety and Z is nitro, cyano, alkylsulfonyl, sulfamoyl (—SO ₂ NR ₂ ) and sulfonamide (—NRSO ₂
R) is selected from the group consisting of groups, n is 0 or 1, and R _VI is selected from the group consisting of substituted or unsubstituted alkyl and phenyl groups. The oxygen atom of each timing group is
The DIAR is bound to the coupling-off site of each coupler moiety.

The timing groups or linking groups can also act by electron transfer along a conjugated chain. Linking groups are known in the art under various names. They may be referred to as groups capable of utilizing a cleavage reaction by ester hydrolysis as in U.S. Patent No. 4,546,073, or groups capable of utilizing a hemiacetal or imino ketal cleavage reaction. Many. This electron transfer along the conjugated chain typically results in relatively rapid decomposition and the production of carbon dioxide, formaldehyde, and other low molecular weight by-products. Specific examples of such groups are described in European Patent Nos. 464,612 and 523,451, and US Pat. No. 4,146,396.
And JP-A-60-249148 and JP-A-60-249.
149. Suitable development inhibitor releasing couplers for use in the present invention include, but are not limited to, the following compounds.

[0086]

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[0087]

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Research Disclosure
(November 1979, Item 18716, K, UK
enth Mason Publications
(Dudley Annex, 12a North Street, Emsworth, Hamps
hire, P010 7DQ), which is incorporated herein by reference) to obtain reflective color prints utilizing the concepts of the present invention. It is possible to do something. The material of the present invention is prepared on a pH-adjusted support as described in U.S. Pat. No. 4,917,994 on European Patent No. 5,917,994.
On a low oxygen permeable support as described in US Pat. No. 53,339, together with an epoxy solvent as described in EP 164,961, for example, US Pat. No. 4,346. No. 165, No. 4,540,6
U.S. Pat. No. 4,994,359 for reducing sensitivity to multivalent cations such as calcium with a nickel complex stabilizer as described in U.S. Pat. And with a stain reducing compound as described in US Pat. No. 5,068,171. Other compounds useful in combination with the present invention are disclosed in the Japanese Patent Application Publication listed in the English abstract with the following accession number: 90
-72629, 90-72630, 90-72631,
90-72632, 90-72633, 90-7782
2, 90-78229, 90-78230, 90-79
336, 90-79337, 90-79338, 90-
79690, 90-79691, 90-80487, 9
0-80488, 90-80489, 90-8049
0, 90-80491, 90-80492, 90-80
494, 90-85928, 90-86669, 90-
86670, 90-87360, 90-87361, 9
0-87362, 90-87363, 90-8736
4, 90-88097, 90-93662, 90-93
663, 90-93664, 90-93665, 90-
93666, 90-93668, 90-94055, 9
0-94056, 90-103409, 83-6258
6 and 83-9959.

Emulsions particularly useful in this invention are tabular grain silver halide emulsions. Particularly conceivable tabular grain emulsions have a thickness of less than 0.3 .mu.m (for blue-sensitive emulsions, a thickness of 0.3 .mu.m).
Tabular grains having an average tabularity (T) of greater than 25 (preferably greater than 100) and an average tabularity (T) of greater than 25 are those emulsions that account for more than 50% of the total projected area of the emulsion grains. Here, the term “flatness” is a term recognized in the art, and is represented by the following formula: T = ECD / t ² . In the formula, ECD is the average equivalent circular diameter (μm) of the tabular grains, and t is the average thickness (μm) of the tabular grains.
m).

While the average useful ECD of a photographic emulsion can range up to about 10 μm, it is unlikely that the actual emulsion will have an ECD greater than about 4 μm. ECD
It is generally preferred to employ the smallest tabular grains ECD that do not prevent the desired speed requirements from being achieved, as both photographic speed and granularity increase with increasing.

Emulsion tabularity increases markedly with reductions in tabular grain thickness. It is generally preferred that the projected area of the intended tabular grains be occupied by thin (t <0.2 μm) tabular grains. To achieve the lowest level of granularity, it is preferred that the projected area of the targeted tabular grains be occupied by ultrathin (t <0.07 μm) tabular grains. The thickness of the tabular grains is at least about 0.0
It typically takes a range of up to 2 μm. However, thinner tabular grain thicknesses are also contemplated. For example,
U.S. Pat. No. 4,672,02 to Daubendiek et al.
No. 7 describes a tabular grain silver bromoiodide emulsion having a grain thickness of 0.017 μm (iodide content: 3 mol%). For ultrathin tabular grain high chloride emulsions,
It is described in Maskasky US Pat. No. 5,217,858.

As described above, tabular grains thinner than the specified thickness account for at least 50% of the total grain projected area of the emulsion. To maximize the benefits of high tabularity, it is generally preferred that tabular grains satisfying the above thickness criteria account for the highest conveniently achievable percentage of the total grain projected area of the emulsion. For example, in preferred emulsions, tabular grains satisfying the above thickness criteria account for 70% or more of the total grain projected area. In the tabular grain emulsion exhibiting the highest performance, tabular grains satisfying the above-mentioned thickness criterion correspond to a total grain projected area of 9%.
Accounts for 0% or more.

Suitable tabular grain emulsions can be selected from a variety of conventional teachings. Examples of such teachings include: Research Di
slosure (Section 22534, January 1983)
U.S. Pat. Nos. 4,439,520 and 4,41.
No. 4,310, No. 4,433,048, No. 4,6
No. 43,966, No. 4,647,528, No. 4,
No. 665,012, No. 4,672,027, No. 4,678,745, No. 4,693,964, No. 4,713,320, No. 4,722,886,
Nos. 4,755,456 and 4,775,617
No. 4,797,354, No. 4,801,52
No. 2, 4,806, 461, 4, 835, 0
No. 95, No. 4,853,322, No. 4,914,
No. 014, No. 4,962,015, No. 4,98
Nos. 5,350, 5,061,069 and 5,
061,616.

The emulsion may be a surface-sensitive emulsion, that is, an emulsion in which a latent image is formed mainly on the surface of silver halide grains, or an emulsion in which the emulsion is preferentially embedded inside silver halide grains. An image can also be formed. The emulsion may be a negative emulsion, for example, a surface-sensitive emulsion or an unfogged internal latent image forming emulsion, or may become a positive emulsion when subjected to uniform exposure or development in the presence of a nucleating agent. A fog internal latent image forming type direct positive emulsion may be used.

A photographic element can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image, which can then be processed to form a visible dye image. it can. Processing to form a visible dye image includes the step of contacting the photographic element with a color developer to reduce developable silver halide and oxidize the color developer. The oxidized color developer sequentially reacts with the coupler to form a dye.

When a negative-working silver halide is used, a negative image is obtained by the above processing steps. One type of such element is designed for image capture, and photographic speed (the sensitivity of the element to low light conditions) is generally important to obtain a sufficient image in such an element. Then, such an element is, for example, The Britis
h Journal of Photography
It can be processed by color negative processing such as the Kodak C-41 process described in Annual (1988, pp. 191-198). If such elements are used to obtain a cinematic observable projection print, Kodak as described in the H-24 manual available from Eastman Kodak Company
Prints can be obtained on transparent supports by employing processing methods such as the ECN-2 process. The color negative development time is typically within 3 minutes 15 seconds, desirably 90 seconds,
Furthermore, it is within 60 seconds.

The element for color reflective printing is provided on a reflective support (typically paper) and the element is passed through a color negative film treated as described above in a so-called negative / positive process. It can be optically printed by exposing to light. Then, the print is, for example, The British Journal
al of Photographic Annual
(1988, pp. 198-199), a positive reflection image can be formed by processing using the Kodak RA-4 process. Color projection prints can be processed according to the Kodak ECP-2 process described in the H-24 manual. Color print development times are typically 90
Within seconds, preferably within 45 seconds, and even within 30 seconds.

The reversal element can form a positive image without performing optical printing. Prior to the color development step, the exposed silver halide is developed without forming a dye by developing with a non-color developing agent to obtain a positive image (or a reversal image), and then the element is uniformly fogged. To make the unexposed silver halide developable. Such reversal emulsions are generally known as Kodak
Instructions for processing using a color reversal process such as the E-6 process are commercially available with accompanying instructions. Alternatively, a positive image can be obtained using a direct positive emulsion. The above emulsion is generally prepared using the above color negative (K
odak C-41), color print (Kodak)
Instructions for processing using a suitable method such as RA-4) or Reversal (Kodak E-6) are commercially available with instructions.

Preferred color developing agents include the following p-
Phenylenediamines: 4-amino-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N,
N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- (2-methanesulfonamidoethyl) aniline sesquisulfate hydrate, 4-amino-
3-methyl-N-ethyl-N- (2-hydroxyethyl) aniline sulfate, 4-amino-3- (2-methanesulfonamidoethyl) -N, N-diethylaniline hydrochloride, and 4-amino-N -Ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid.

Usually, the development step is followed by usual steps such as bleaching, fixing or bleach-fixing for removing silver and silver halide, washing steps and drying steps. The contents of patent application specifications, patent specifications and other publications referred to in this specification are incorporated herein in their entirety.

[0101]

EXAMPLES Synthesis of Couplers The magenta DIR couplers described in the present invention can be synthesized by reactions and methods well known in the field of organic chemical synthesis. The specific synthesis method of the compound (A2) of the present invention exemplifies the synthesis of these compounds. Hereinafter, Ph is phenyl, Et is ethyl, DMF is N,
N-dimethylformamide, THF represents tetrahydrofuran, tBu represents t-butyl, DCC represents dicyclohexylcarbodiimide, and DBU represents 1,8-diazobicyclo [5.4.0] undec-7-ene.

[0102]

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[0103]

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Compound 3 Compound 1 (47.8 g, 0.20 mol) under a nitrogen atmosphere
Was dissolved in dry DMF (350 mL) at room temperature.
Ethyl bromoacetate 2 (33.4 g, 0.20 mol) was added in one portion. The mixture was stirred at room temperature and triethylamine (20.2 g, 0.20 mol) was added dropwise over 20 minutes. The reaction mixture was stirred at room temperature for 2 hours. TLC (silica gel, ethyl acetate / heptane, 4
0:60), three product spots (R _f =
0.40, 0.45, 0.50). The reaction mixture was poured into a mixture of ice and water (800 mL) plus concentrated hydrochloric acid (80 mL) with stirring. The aqueous mixture was extracted three times with ethyl acetate. The extracts were combined and washed twice with saturated sodium chloride solution. The extract is dried over magnesium sulfate and
orit ™. The mixture was filtered and the solvent was removed on a rotary evaporator. The obtained residue was dissolved in hot methanol (300 mL). The hot solution was allowed to stand at room temperature overnight. The mixture was cooled in ice and filtered. The collected solid was washed with methanol at room temperature. The product was placed in a vacuum furnace (4
(0 ° C.). White plate-shaped compound 3 (melting point 1
34-137 ° C). TLC (above conditions) showed a single spot (R _f = 0.40) and the NMR spectrum was consistent with Structural Formula 3. The yield was 21.9 g (34%).

[0105]Compound 6 Compound 4 (37.0 g, 0.109 mol)
(250 mL) and dry THF (75 mL)
Was. The mixture is stirred at room temperature under a nitrogen atmosphere, and
Thiophosgene 5 (13.8 g, 9.1 mL, 0.12
Was added all at once. Stir the mixture at room temperature for 4 hours
did. TLC (silica gel, ethyl acetate / heptane, 3
0:70) indicates that part of 4 still exists.
And (R_f= 0.70). 5 (3.0m
L) is added and the mixture is stirred for a further 19 hours
did. At this point, TLC indicated that all 4 had reacted.
showed that. The reaction mixture was stirred with ice and water (10
00 mL). Add the aqueous mixture to
Extracted three times with chill. Combine these extracts and combine
Washed twice with a saturated sodium solution. The extract is sulfuric acid
Dried over magnesium and then filtered. Rotate solution
It was removed with a reevaporator. As a tan oil
Compound 6 was obtained. According to TLC (the above conditions),
Spot (R _f= 0.80) and a trace spot (R_f=
0.50). The yield is 41.0g (99%)
there were.

Compound 7 Compound 3 (9.8 g, 0.030 mol) and Compound 6
(12.2 g, 0.032 mol) in dry THF (150
mL). The mixture was stirred at room temperature under a nitrogen atmosphere to dissolve the reactants. Put the reaction flask on ice
Cool in a salt-acetone bath. When the pot temperature was 0 ° C., potassium t-butoxide (3.6 g, 0.032
Mol) was added in small portions over 5 minutes. The mixture was stirred in an ice bath for more than 30 minutes and then at room temperature for 2 hours. The reaction mixture was poured into a mixture of ice and water (600 mL) plus concentrated hydrochloric acid (50 mL). The aqueous mixture was extracted three times with ethyl acetate. The extracts were combined and washed twice with saturated sodium chloride solution. The extract was dried over magnesium sulfate and then filtered. The solvent was removed from the filtrate on a rotary evaporator to give a tan oil. TLC
(Silica gel, ethyl acetate / heptane, 40:60) showed a major spot ( _Rf = 0.25) and a minor spot ( _Rf = 0.80, 0.40). The crude product was chromatographed on a silica gel system using ethyl acetate / heptane (40:60) as eluent. R _f
Fractions containing a component of = 0.25 were combined and the solvent was removed on a rotary evaporator. Compound 7 was obtained as a tan semi-solid. The NMR spectrum was consistent with the structure of 7. The yield is 13.
6 g (64%).

Compound A2 Compound 8 (3.2 g, 0.018 mol) was dried in THF.
(75 mL). The mixture was stirred at room temperature under nitrogen and triethylamine (1.8 g, 0.01
8 mol) was added dropwise over 5 minutes. The resulting mixture was stirred at room temperature for 10 minutes. Compound 7 (13.0 g, 0.01
(8 mol) in dry THF (100 mL) was added in one portion. Then DCC (4.5 g, 0.02
(2 mol) in dry THF (20 mL) was added in one portion. The mixture was stirred at room temperature for 2 hours 30 minutes. TLC (silica gel, ethyl acetate / heptane, 4
0:60) showed a major product spot of the arylhydrazone intermediate (R _f = 0.70). DBU
(5.5 g, 0.036 mol) in dry THF (30 m
The solution dissolved in L) was added dropwise over 10 minutes. The mixture was stirred at room temperature for 2 hours. TLC (silica gel, dichloromethane / methanol, 95: 5) showed a major product spot (R _f = 0.30) (magenta bound). The reaction mixture was stirred with ice and water (60
(0 mL) and concentrated hydrochloric acid (50 mL). The aqueous mixture was extracted three times with ethyl acetate.
The extracts were combined and washed twice with saturated sodium chloride solution. The extract was dried over magnesium sulfate and then filtered. Removal of the solvent gave a tan oil which by TLC (dichloromethane / methanol, 95: 5) showed a major spot (R _f = 0.80).
(By dicyclohexylthiourea) and 0.3
0), minor spots (R _f = 0.95 and 0.50) and several small spots. The crude product was chromatographed on a silica gel system using dichloromethane / methanol (95: 5) as eluent. R _f =
Fractions containing 0.30 components were combined and the solvent was removed on a rotary evaporator. The residue obtained is taken up in methanol (75 mL) at room temperature for 1 hour 3
Stirred for 0 minutes. The mixture was filtered and the collected solid was washed with methanol at room temperature. The product was dried in a vacuum oven at room temperature. Beige powdered compound A2
Was obtained (melting point 100-102 ° C.). The NMR spectrum was consistent with the structural formula of A2. The yield is 4.
9 g (35%). Analysis result: C ₄₁ H ₄₂ Cl ₂ N
Theoretical value of ₆ O ₅ ; C = 63.98; H = 5.50; N =
10.92; Cl = 9.21, found; C = 63.3.
7; H = 5.66; N = 10.68; Cl = 8.74.
According to HPLC, the purity of A2 was 93.1%.

Photographic Example Example 1 By coating a DIR coupler with an imaging coupler in a photographic element containing silver halide,
The activity of the DIR coupler of the present invention with respect to the comparative DIR coupler can be evaluated. The photographic element can then be exposed and processed, and the amount of DIR coupler and imaging coupler remaining can be analyzed (by extraction and high performance liquid chromatography HPLC) as a function of exposure. When the logarithm of the residual amount of the DIR coupler is plotted against the logarithm of the residual amount of the image forming coupler, a straight line is obtained, and the slope corresponds to the ratio between the reactivity of the DIR coupler and the reactivity of the image forming coupler. Typically, the DIR coupler is at least twice as reactive as the imaging coupler so that the DIR coupler can effectively compete with the oxidized developer and release the inhibitor efficiently as a function of exposure. It is desirable to show the property. For comparison, the film formats shown in Table 1 were used, and M-1 represented by the following structural formula was used as an image forming coupler. A similar measurement was performed using another image forming coupler (eg, M-2 or M-
3) was also implemented. The unit of the coating amount in parentheses shown in Table 1 is g / m ² .

Table 1 Overcoat: Gelatin (5.38) bis (vinylsulfonyl) methane hardener (0.259) M-1 magenta image forming coupler (0.559) and S-1 (0.447) And ST-1 (0.112) pyrazolone DIR coupler (coating amount: 0.108 mmol / m ² ) (eg, 0.085A2) Green sensitized silver iodobromide tabular grains (1.0 × 0.09 μm) ) (1.61 Ag) gelatin (2.69) cellulose acetate support (with gel U-coat and antihalation backing layer)

Each of the DIR couplers was dispersed in tolyl phosphate (S-1, mixture of isomers) at a weight ratio of 1: 2. Typically, a DIR coupler: S-
1: An oil phase containing ethyl acetate in a weight ratio of 1: 2: 3 was mixed with gelatin and a dispersant Alkanol XC (DuPont) in a ratio of 10:
A dispersion was prepared by adding to the aqueous phase contained in a weight ratio of 1. The mixture was then passed through a colloid mill to disperse the oil phase as small particles in the aqueous phase. Ethyl acetate as an auxiliary solvent evaporates during coating. Couplers C4 and A
For 4, the solubility in ethyl acetate was limited, so that cyclohexanone was used as an auxiliary solvent. Coupler M-1 to S-1 and ST-1 (see below)
Was applied at a weight ratio of 1: 0.8: 0.2.

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Film samples were exposed and processed in a standard Kodak Flexicolor C-41 ™ process. Extracts of the M-1 and DIR couplers at various exposure stages were analyzed by HPLC as described above to determine the reactivity of the DIR coupler with coupler M-1. Table 2 shows the relative reactivity values of the comparative coupler and the DIR coupler of the present invention. From the data in Table 2, it is clear that the DIR couplers of the present invention provide the desired high reactivity.

Table 2 Reactivity to pyrazolone DIR coupler M-1 C1 (for comparison) 1.4 C2 (for comparison) 1.3 C4 (for comparison) 1.3 A1 (for the present invention) 5.7 A2 (for this example) Invention) 2.5 A5 (present invention) 2.0 A6 (present invention) 2.0 A8 (present invention) 5.0 A24 (present invention) 7.0 A25 (present invention) 2.7

Example 2 A comparative DIR coupler and a pyrazolone-based DIR coupler of the present invention were applied in the same format as in Example 1, and the stability of various DIR couplers to long-term storage or high-temperature storage, so-called raw film preservability, was evaluated. Was done.
The couplers C2 and A1 were coated in the same two-layer format as in Example 3, but the coating amounts of M-1 and DIR were the same. The film samples were fixed to remove silver halide. Place one set in a -4 ° C freezer,
The other was subjected to a 2-week incubation at 60 ° C./50% RH (accelerated test designed to mimic long-term storage). Thereafter, the film sample is removed from the remaining DI
The R coupler was analyzed by an extraction method and an HPLC method. Table 3 describes the percentage loss of each coupler in the sample after incubation, based on the control sample in the freezer. It is desired that this loss rate be less than about 15%, preferably less than 10%. All of the comparative couplers included in Table 3 show unacceptable storage stability.
The couplers of the present invention exhibit acceptable raw film storage properties. In particular, couplers A1, A5, A6 and A8 are:
It shows very good raw film stability.

Table 3 Pyrazolone-based DIR coupler Loss% of coupler after 2 weeks at 60 ° C./50% RH C2 (for comparison) 25 C3 (for comparison) 18 C4 (for comparison) 25 (hand-carried) A1 (the present invention) ) 2 A2 (present invention) 14 A4 (present invention) 12 A5 (present invention) 4 A6 (present invention) 4 A8 (present invention) 8 A24 (present invention) 7 A25 (present invention) 9

Example 3 In order to exemplify the excellent silver development suppressing effect and the interimage effect obtained by the pyrazolone-based DIR coupler of the present invention, evaluation was further made in a coser / receiver type multilayer format shown in Table 4. The structures of components not described or not described in Example 4 are listed after Table 4. The unit of the coating amount in parentheses included in Table 4 is g / m ² .

The film samples were exposed to white light (neutral) for sensitometry and subjected to standard Kodak Flexicolo.
r Processed in C-41 ™ process. Next, the status M densities of green (Coser) and red (receiver) with respect to the exposure amount were measured for the film A containing no DIR coupler, the film B containing the DIR coupler C2 for comparison and the film C containing the DIR coupler A1 of the present invention. did. Both C2 and A1 are about 1.73 micromol / m ² (0.
161 micromol / ft ² ). Green and red gamma values were then obtained from the slope of the plot of density versus log exposure. In order to enhance the interlayer interimage effect and color correction, it is desirable to substantially reduce the gamma in the receiver layer while minimizing the reduction in gamma (coser gamma) that the DIR coupler provides in its own layer. In this case, green gamma corresponds to coser gamma and red gamma corresponds to receiver gamma. For unsuppressed Film A, the green and red gammas are 1.00 and 0.99, respectively. For Film B containing the comparative coupler C2, the green and red gammas are reduced to 0.90 and 0.86, respectively. In the case of Film C containing coupler A1 of the present invention, the green and red gammas are reduced to 0.88 and 0.65, respectively. Thus, couplers C2 and A
1 slightly lowers the green coser gamma,
The amount by which coupler A1 reduces the red receiver gamma (3
4%) is much larger and more desirable than that of C2 (13%).

Table 4 Overcoat: gelatin (2.69) bis (vinylsulfonyl) methane hardener (0.227) Coser: M-1 (0.43), S-1 (0.344) and ST- 1) (0.086) A) without DIR coupler (unsuppressed control); B) for comparison of C2 (0.141) and S-1 (0.282); or C) A1 (0. 142) and S-1 (0.284) invention Green-sensitized silver iodobromide tabular grain emulsion (0.807 Ag) gelatin (2.69) interlayer: IS-1 (0.054) and S-1 (0.054) Gelatin (0.86) Receiver: CC-1 (0.753) and S-2 (0.753) B-2 (0.054) and S-3 (0.054) IR-5 (0.022) and S-5 (0.044) Red-sensitized silver iodobromide tabular grain milk (0.807Ag) Gelatin (2.69) cellulose acetate support (with gel U- coat and antihalation backing layer)

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Example 4 Table 5 schematically shows a multilayer film structure used in the present invention. The structure of the undescribed components is shown immediately after Table 5. The coating amount of the components is shown in units of g / m ² unless otherwise specified. Gelatin was used as a binder in various layers of the multilayer film. Similar compositions can be coated on a support such as polyethylene naphthalate containing a magnetic recording layer. This film can be processed by the Kodak Flexicolor C-41 ™ process to improve interimage and color.

Table 5: Multilayer film structure Overcoat layer: matte bead gelatin (0.89) UV protective layer: UV absorber UV-1 (0.111) and S-4 (0.111) UV absorber UV-2 (0.111) and S-4 (0.111) Silver bromide Lippmann emulsion ( 0.215 Ag) gelatin (0.70) High-sensitivity yellow layer: Y-1 (0.150) yellow dye-forming coupler and S-1 (0.075) IR-1 (0.032) DIR coupler and S-1 (0.016) B-1 (0 .0054) BARC and S-3 (0.0070) Blue-sensitive silver iodobromide emulsion (0.435 Ag) 4.5 mol% iodide tabular grains (2.3 × 0.13 μm) gelatin (0.753) 4. Low-sensitivity yellow layer: Y-1 (0.915) and S-1 (0.457) IR-1 (0.032) and S-1 (0.016) B-1 (0.0065) and S- 3 (0.0084) Blue-sensitive silver iodobromide emulsion (0.180 Ag) 4.5 mol% tabular grains (1.4 × 0.13 μm) Blue-sensitive silver iodobromide emulsion (0.120 Ag) 1 0.5 mol% iodide tabular grains (0.85 × 0.13 μm) Blue-sensitive silver iodobromide emulsion (0.180 Ag) 1.3 mol% iodide tabular grains (0.54 × 0.09 μm) Gelatin (1.668) bis (vinylsulfonyl) methane hardener 2.1% of total weight of gelatin 5. Yellow filter layer: R-1 (0.075), S-2 (0.121) and ST-2 (0.010) gelatin (0.861) YD-1 (0.097) and YD-2 filter dye (0.108) 6. High sensitivity magenta layer: M-1 (0.050) magenta dye-forming coupler and S-1 (0.045) ST-1 (0.005) additive MM-1 (0.025) masking coupler and S-1 (0.050) A1 (0.027) DIR coupler and S-1 (0.054) Green-sensitive silver iodobromide emulsion (0.699 Ag) 4.5 mol% iodide tabular grains (0.98 × 0 .11 μm) gelatin (1.22) Medium-sensitivity magenta layer: M-1 (0.120), S-1 (0.012) and ST-1 (0.012) MM-1 (0.030) and S-1 (0.060) A1 ( 0.031) DIR coupler and S-1 (0.062) green-sensitive silver iodobromide emulsion (0.646 Ag) 4.5 mol% iodide tabular grains (0.61 × 0.12 μm) gelatin (1. 41) 8. Low sensitivity magenta layer: M-1 (0.170), S-1 (0.153) and ST-1 (0.017) MM-1 (0.036) and S-1 (0.072) Green sensitivity Silver iodobromide emulsion (0.377 Ag) 3.3 mol% iodide cubic grains (0.275 μm) Green-sensitive silver iodobromide emulsion (0.108 Ag) 1.3 mol% iodide tabular grains (0.54 Ag) × 0.09 μm) gelatin (1.18) Interlayer: R-1 (0.075) interlayer scavenger and S-6 (0.113) gelatin (0.86) High sensitivity cyan layer: CC-1 (0.180) cyan dye-forming coupler and S-2 (0.180) CM-1 (0.032) masking coupler IR-3 (0.038) DIAR coupler and S-5 (0.076) IR-4 (0.038) DIAR coupler and S-2 (0.076) Red-sensitive silver iodobromide emulsion (0.988 Ag) 4.5 mol% iodide tabular grains (1.10. × 0.11 μm) gelatin (1.45) Medium sensitivity cyan layer: CC-1 (0.190) and S-2 (0.190) CM-1 (0.011) B-1 (0.027) and S-3 (0.035) IR-3 (0.054) and S-5 (0.108) Red-sensitive silver iodobromide emulsion (0.225 Ag) 4.5 mol% iodide tabular grains (0.98 × 0.11 μm) Red-sensitive iodobromide Silver emulsion (0.870 Ag) 3.3 mol% iodide cubic grains (0.49 μm) Gelatin (1.35) Low sensitivity cyan layer: CC-1 (0.390) and S-2 (0.390) IR-4 (0.011) and S-2 (0.022) B-1 (0.075) and S- 3 (0.098) red-sensitive silver iodobromide emulsion (0.390 Ag) 3.3 mol% iodide cubic grains (0.32 μm) gelatin (1.64) 13. Intermediate layer: R-1 (0.075) and S-6 (0.113) gelatin (0.86) Antihalation layer: Gray silver (0.15 Ag), CD-1 (0.0161), MD-1 (0.043) UV-1 (0.0753), S-4 (0.0753), S-1 Gelatin (1.61) YD-3 (0.028) and S-1 (0.056) cellulose triacetate support

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Claims (1)

[Claims] 1. 1-phenyl-3-anilino-4-benzotriazolyl-5 represented by the following general structural formula (I):
A photographic element comprising a silver halide emulsion layer in which a pyrazolone-based magenta dye-forming DIR coupler is combined. Embedded image [In the above formula, R ₁ represents hydrogen, chlorine, fluorine or a methyl group, and R ₂ , R ₃ and R ₄ each independently represent hydrogen, halogen,
Represents alkyl, phenyl, alkoxy, phenoxy, alkylthio, carbonamido, sulfonamido, carbamoyl, selected from the group consisting of alkoxycarbonyl and aryloxycarbonyl groups, R ₅ is hydrogen, bromine, chlorine, fluorine or an alkyl group, R ₆ And R ₇ are each independently hydrogen, halogen, carbonamido, carbamoyl, sulfonamido, sulfamoyl, alkylsulfonyl, arylsulfonyl, alkylsulfoxyl, arylsulfoxyl, sulfonyloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acyl , Imide, trifluoromethyl and cyano groups, provided that R
_At least one of ₆ and R ₇ is not hydrogen, and R ₈ and R ₉ are each independently hydrogen, halogen, alkyl, phenyl, alkoxy, phenoxy, alkoxycarbonyl, aryloxycarbonyl, carbonamide, sulfonamide, carbamoyl and Selected from the group consisting of carbamoyloxy groups, provided that at least one of R ₈ and R ₉ is not hydrogen, and (1) when R ₅ is hydrogen, R ₆ and R 9
Total is 0.30 or more and R ₁ of the Hammett sigma values relative to the position of the anilino nitrogen ₇ is also hydrogen, also (2) R ₅ is bromine, chlorine, if a fluorine or an alkyl group Has a sum of Hammett sigma values of 0.20 or greater relative to the position of the anilino nitrogen of R ₆ and R ₇ , and a sum of pi values of R ₈ and R ₉ of 0.6
It is 0 or more and 3.00 or less. ]