JPH04204732A - Silver halide color photographic sensitive material and silver halide color image forming method - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material superior in color development performance and hue and improved in color reproduction performance by incorporating a specified coupler. CONSTITUTION:This coupler is represented by formula I in which each of R1 and R2 is a substituent substitutable on a thiophene ring and the sum of each Hammett's substituent constant sigmap, of 0.6-1.6; and W is H atom or a group to be released by coupling with the oxidation product of an aromatic primary amine developing agent, thus permitting the obtained color photographic sensitive material to contain the coupler capable of forming a dyestuff small in side absorption and high in molecular absorption coefficient and to form a cyan dye image superior in lightfastness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material with improved color reproducibility.

[Conventional technology]

The exposed silver halide is treated with an oxidizing agent L2, and the oxidized aromatic primary amine color developing agent and the power blur react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and the like. It is well known that similar pigments are produced and color images are formed. In such photographic systems, a subtractive color process is used, in which yellow, magenta, and cyan dyes form a color image.

[Issues that Hathu tries to solve]

Conventionally, phenols or naphthols have been used as cyan couplers. However, cyan dyes formed from these couplers are insufficient in their spectral absorption characteristics, heat resistance, moisture resistance, light resistance, and the like. Various couplers have been proposed to improve these, but at present no coupler that satisfies all of these has yet been found.

A first object of the present invention is to provide a color photographic material containing a novel cyan coupler.

A second object of the present invention is to provide a color photographic material containing a novel Boo-2 uncoupler that forms a dye with little side absorption and a high molecular extinction coefficient.

A third object of the present invention is to provide a color photographic material from which a clear image with excellent image fastness can be obtained.

[Myanmar's means of solving problems]

The silver halide color photographic light-sensitive material of the present invention is characterized by containing a coupler represented by Noshiro [I] below.

General formula [1] [In the formula, R1 and R3 are substituents that can be substituted on the thiophene ring, and the sum of the values of the substituent constant σp of each Hammet) represents a substituent of 04 or more and 1.6 or less. , W represents a hydrogen atom or a leaving group that leaves when the coupler undergoes an oxidized L coupling reaction of an aromatic primary amine developing agent. ] Furthermore, the silver halide color image forming method of the present invention is characterized in that an image is formed by reacting the coupler represented by Noshiro [I] above with an oxidized product of an aromatic primary amine developing agent.

The compound represented by -Noshiro (I) above undergoes a coupling reaction with an oxidized product of an aromatic primary amine developing agent to form the following dye.

In the formula, ^r is an aromatic group, and Table 1-1R, and R2 have the same meanings as explained in -Noshiro (I).

The dye obtained from the coupler of the present invention preferably has a maximum absorption wavelength of 530 nm to 740 nm, particularly preferably.

It has a wavelength of 600 nm to 700 nm, and is effective as a cyan coupler.

The compound represented by general formula (1) will be described in detail below.

R1 and R3 are M contact layers that can be replaced with W on the thiophene ring, and the sum of their Hammett substituent constants σp is 0.
Represents 4 or more and 1.6 or less substituents (including atoms). Preferably, the total sum of substituents is 0.7 or more and 1.4 or less.

If the sum of Ro and R3 is less than 0°4, the color development will be insufficient, and if it exceeds 1°6, the coupling activity will be lost and it will no longer be useful as a coupler.

The value of Hammett's substituent constant σp here is Ha
msch, C. Leo et al. (e.g. J. Med.
, Chem16, 1207 (1973)); 1bi
It is preferable to use the values described in J.D., Animals, 304 (1977)).

In the present invention, at least one of R1 and R2 is σρ
It is preferable that the substituent has a value of 0.4 or more, R,,
It is more preferable that at least one of R2 is a substituent having a σp value of 0.4 or more, and the remaining one is a substituent having a σρ value of 0.2 or more.

Such Wt substituents of R5 and R2 include, for example, a cyano group, a carbamoyl group (for example, N-phenylcarbamoyl, N-(2-chloro-5-tetradecyloxycarbonylphenyl)carbamoyl, N,N-diethylcarbamoyl, Ni2,4-dichlorophenyl)carbamoyl or N-(2-chloro-5-hexadecanesulfonamidophenyl)carbamoyl), alkoxycarbonyl groups (e.g. ethoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl or 2-ethylhexyloxycarbonyl), aryl oxycarbonyl groups (e.g. phenoxycarbonyl or 1-naphthyloxycarbonyl), aliphatic or aromatic T-syl groups (e.g. benzoyl, acetyl, 4-chlorobenzoyl or 2.4-
dichlorobenzoyl), aliphatic or aromatic sulfonyl groups (e.g. methanesulfonyl, dodecanesulfonyl,
benzenesulfonyl, or 2-butoxy-5-t-octylphenylsulfonyl), sulfamoyl group (such as 1fN-butylsulfamoyl, N-phenylsulfamoyl or N,N-diethylsulfamoyl), nitro group, It represents a fluorinated alkyl group (eg trifluoromethyl or hebutafluoroprupyl), an aliphatic or aromatic sulfinyl group (eg tlf methanesulfinyl, benzenesulfinyl, or naphthalenesulfinyl) or a substituted aromatic group.

When either R1 or R3 represents a substituted aromatic group, examples of the substituent include a halogen atom (e.g., a chlorine atom,
bromine atom), straight or branched, dilated or cyclic, glossy or unsaturated, substituted or unsubstituted aliphatic groups, such as methyl, propyl, t-butyl, trifluoromethyl,
Tridecyl, 3-(2,4-di-t-aminophenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, cyclopentyl, benzyl, allyl, propargyl, heteroEi
M, [1eva-2-furyl, 2-thienyl, 2-pyrimidyl, 2-benzothiazolyl, sia) group, alkokene group,
For example, methoxy, ethoxy, 2-methoxyethoxy, 2
-dodecyloxyethoxy, 2-methanesulfonylethoxy, 70-loxy groups, such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, heterooxy groups, such as 2-benzimidazolyloxy, acyloxy groups, such as acetoxy, hexadecanoyloxy, carbamoyloxy groups such as N-ethylcarbamoyloxy, silyloxy groups such as trimethylsilyloxy, sulfonyloxy groups such as dodecylsulfonyloxy, acylamido groups such as acetamide, benzamide, tetradecaneamide, α-(2,4- G-t
-amylphenoxy)butyramide, 2,4-di-monoamylphenoxyacetamide, α-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide, isopentadecaneamide, anilino groups such as phenylamino, 2-chloroanilino, 2- Chloro-5-tetradecanamide ringilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-
Chloro-5-(αbe2(-butyl-4-hydroxyphenoxy)dodecanamide)Tniline, ureido groups such as phenylureido, methylureido, N,N-dibutylureido, imide groups such as N-succinimide,
3-penzylhydantoynyl, 4-(2-ethylhexanoylamino)phthalimide, sulfamoylamino groups such as N,N-dipropylsulfamoylaminodecylsulfamoylamino, alkylthio groups such as methylthio, octylthio, Tetradecylthio, 2-phenoxystiltis'', 3-phenoxypropylthio,
:3-(4(-butylphenoxy)propylthio, γ-lylthio group, e.g. phenylthio, 2-butoxy-5-
t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, peterocyclic thio group, such as 2-benzothiazolylthio, alkoxycarbonylamino group,
For example, methoxycarbonylamino, tetradecyloxycarbonylamino, aryloxycarbonylamino groups, such as phenoxycarbonylamino, 2,4-di-t
e r t. -butylphenoxycarbonylamino,
Sulfonamide groups, such as methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p
-) luenesulfonamide, octadecanesulfoninoamito'% 2-methyloxy-5-t-, butylbenzenesulfonamide, carbamoyl group, e.g.
~ Dodecyloxyethyl)carbamoyl, tomethyl-
N-dodecylcarbamoyl, ~ (3-(2,4-di-t, ert-T-milphenoxy)propyl)carbamoyl, an acyl group such as an ayathyl group, (2,4-di-te
rt-amylphenoxy>70tyl, benzoyl, sulfamoyl group, such as N-ethylsulfamoyl Jl,
N-dipropylsulfamoyl, N-(2-dodecyloxyethylsulfamoyl, N-ethyl-N-dodecylcarbamoyl, N,N-diethylsulfamoyl, sulfonyl groups, such as methanesulfonyl, octanesulfonyl , benzenesulfonyl, ), sulfonyl, sulfinyl group, such as octane sulfinyl,
dodecylsulfinyl, phenylsulfinyl, alkoxycarbonyl groups such as metquincarbonyl, butyloxycarbonyl, dodecylcarbonyl, arylo4dicarbonyl groups such as phenyloxycarbonyl, 3-bentadenyloxycarbonyl) , an aromatic group having 6 to 3 G carbon atoms, such as fucanyl,
Examples include naphthyl.

In the general formula (+), W is also a hydrogen atom! or a leaving group (hereinafter simply referred to as [leaving group j
Table 17, when W represents leaving, the leaving group is a halogen atom, an aromatic azo group, an aliphatic group, an aromatic group, a heterocyclic group, via an oxygen, nitrogen, sulfur or carbon atom.
Aliphatic/aromatic or heterocyclic sulfonyl group, aliphatic/
A group that is bonded to an aromatic or heterocyclic carbonyl group or a heterocyclic group that is bonded to a coupling position via a nitrogen atom, and the aliphatic, aromatic or heterocyclic groups included in these leaving groups are those mentioned above. The substituted aromatic group may be substituted with a substituent that is permissible in the substituted aromatic group, and when two or more of these substituents are present, they may be the same or different, and these substituents are the same as those listed above! It may have a permissible @ contact with a substituted aromatic group.

Specific examples of leaving groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g. ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group,
methanesulfonylethoxy group, etc.), diaryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyl group, etc.), acyloxy group (e.g., acetoxy group, butladecanoyloxy group, etc.), , benzoyloxy group, etc.), aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonylethoxy group, toluenesulfonyloxy group, etc.), phosphorylamino group (e.g., dichloroamothylamino group, heptafluorobutyrylamino group, etc.) , aliphatic or aromatic sulfonamide group (e.g., methanesulfonamide group, p-toluenesulfonamide group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g. phenoxycarbonyloxy group, etc.), aliphatic/aromatic or di- or heterocyclic thio group (e.g. ethylthio group, 2-carboxyethylthio group, phenylthio group, tetrazolylthio group, etc.), carbamoylamino group (e.g. N-methylcarbamoyl 5- or 6-membered nitrogen-containing heterocyclic groups (such as imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2oxo-1pyridyl) groups, etc.), imido groups (e.g., succinimide groups, hydantoynyl groups, etc.), aromatic azo groups (e.g., phenylazo groups, etc.), and these groups are further permitted as substituents for the substituted aromatic groups listed above. It may be substituted with a group. Furthermore, there are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded through a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.

- The coupler represented by Noshiro (I) can be used as a so-called internal type coupler, which is contained in a silver halide color photographic light-sensitive material, or as a so-called external type coupler, which is contained in a color developing solution. . inner coupler,
As a coupler to be used as =, in -Noshiro (I), at least one of R+ and R-5W has a total carbon number of 10 to
Preferably, it is 50.

Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

ζjunsen, senior) (+5) CtH
s(30).

(Shell F, 5-age) Each substituent R0, R3 in each coupler above
The method for synthesizing the coupler of the present invention having the Hammett substituent constant σp shown below can be performed by a known method. For example Chemische Berichte,
No. 99, page 94 (1966), and JP-A-63-3
It can be synthesized by the method described in No. 05171, the literature cited therein, or a similar method.

Next, a synthesis example will be shown.

[Synthesis example 1] Synthesis of exemplified compound (26) Exemplary compound (26) was synthesized by the following route.

Synthesis of intermediate product (51) Compound (50), 14.5 g and 9.9 g of methyl cyanoacetate
g was dissolved in 200 g of benzene, 1.54 g of ammonium acetate and 4 g of acetic acid were added thereto, and the mixture was dehydrated under reflux. After the reaction, 100% of ethyl acetate was added and washed with water. After drying, ethyl acetate was distilled off, and ethanol was added to the residue for recrystallization. By filtering off the crystals, intermediate product (51)
4.3g of was obtained.

Synthesis of Intermediate Product (52) Compound (51), 4.2 g was dissolved in ethanol 2 (7), diethylamine 1.9- was added, and while maintaining the temperature at 50°C, 190 ml of diluted alcohol was added. Reaction. After that, 10 rows of ethyl acetate was added and washed with water. After drying, ethyl acetate was distilled off and recrystallized with ethanol to obtain intermediate product (52).
0.61g of was obtained.

Synthesis of Exemplified Compound (26) 0.60 g of Compound (52) was added to 10 stf of toluene!
A solution of 0.22 g of sodium methyl chloride in 10 methanol was slowly added dropwise under a nitrogen stream while keeping the temperature at 80°C. After the reaction, the toluene was distilled off and the remaining residue contained 10m7 of methylene chloride! , 36% hydrochloric acid solution was added and extracted. After neutralization, methylene chloride is distilled off and separated by column chromatography to obtain the desired exemplary compound (26).
．． I got 2.

[Synthesis example 2] Synthesis of exemplified compound (27) Exemplary compound (27) was synthesized by the following route.

(s3) (54) Add compound (53) to 50 g of polyphosphonic acid while stirring at 90°C.
, 1.93 g was added thereto, and the mixture was heated and stirred for 4 hours. After the death,
After adding 50 g and stirring for 1 hour, the precipitated crystals were passed through a suction port to obtain 1.50 g of intermediate product (54). 1.50 g of the obtained (54) was dissolved in dimethylformamide, 3.8 g of potassium carbonate was added, and the mixture was kept at 80°C for 1
- 2.5 g of bromopentadecane were added. After the reaction, excess potassium carbonate was removed, and after neutralization, 100% of ethyl acetate was added.
was added and washed with water. By purifying the residue by column chromatography, the desired exemplary compound (27) was obtained in 2.
I got Og.

Many of the other exemplified compounds can be obtained by synthetic methods similar to those described above.

In addition, there are four methods for introducing a leaving group depending on the type of leaving group to be introduced. ■ When the leaving group is a halogen atom: The most common halogen atom is a chlorine atom, and when It is obtained by chlorinating a four-equivalent coupler, which is a hydrogen atom, with sulfuryl chloride, N-chlorosuccinimide, etc. in a halogenated hydrocarbon solvent (eg, chloroform, methylene chloride, etc.).

■ When the leaving group is a leaving group via an oxygen atom = (i) A method of halogenating the coupling position of a four-equivalent coupler and reacting it with a phenolic compound in the presence of a base;
i) There is a method in which a hydroxyl form of a four-equivalent coupler at the coupling position is reacted with an active halogenated compound in the presence of a base.

■ When the leaving group is a leaving group via a sulfur atom: (i) a method in which a four-equivalent coupler and a sulfenyl chloride serving as a leaving group are reacted in the presence of a base or in the absence of a base 7;
(11) There is a method of introducing a mercapto group into the coupling position of a four-equivalent coupler and allowing a halide to act on this mercapto group.

■ When the leaving group is a leaving group via a nitrogen atom: (i> nitrosation of the coupling position of the four-equivalent coupler with a suitable nitrosating agent j5, and reduction by an appropriate method (for example, Pc
(11) Hydrogenation using t-carbon as a catalyst, chemical reduction using dichloride, etc.) and then reacting with various halides; (iii) 6π or 10π electron system aromatics There are methods for introducing a nitrogen heterocycle into a halogenated coupler in the presence or absence of an aprotic polar solvent.

The above method of introducing a leaving group is described in U.S. Patent No. 3.894.87.
No. 5, 3.933.5 () No. 11, 4.296.19
9, 3,227, 554, 3.476, 563
No. 4.296.200, No. 4.234.678, No. 4.228.233, No. 4.351.897,
4.264.723, 4.366, 237, 3.408.194, 3.725.067, 3
．． No. 419.391, No. 3,926, 631, Japanese Patent Publication No. 56-45135, No. 57-36577, Japanese Patent Publication No. 57-3657
7-70871, 57-96343, 53-52
No. 423, 51-1058 mourning, 53-129035
No. 54-48540, etc. can be referred to.

The coupler represented by the general formula (I) of the present invention undergoes a coupling reaction with an oxidized form of a developing agent to form a dye.

When the coupler represented by the general formula (1) of the present invention is applied to a silver halide photosensitive material, it is sufficient to have at least one layer containing the coupler of the present invention on the support. The coupler-containing layer may be any hydrophilic colloid layer on the support. -Color photosensitive materials used on boats are
It can be constructed by coating at least -1 each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order on a support.
The order may be different from this. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned light-sensitive emulsion layers. These light-sensitive emulsion layers contain silver halide emulsions that are sensitive to each wavelength range and color couplers that form dyes that are complementary colors to the light to which they are exposed, thereby achieving color reproduction using the subtractive color method. be able to. However, the coloring hues of the photosensitive emulsion layer and the color coupler may not correspond as described above.

When the coupler of the present invention is applied to a color light-sensitive material, it is particularly preferable to use it in a red-sensitive silver halide emulsion layer.

The amount of the coupler of the present invention added to the light-sensitive material is 1X10-' mole per 11 moles of halogen, preferably 2X10-' mole to 3X10-' mole.

Further, when the coupler of the present invention is soluble in an alkaline aqueous solution, it can be dissolved in the alkaline aqueous solution together with a developing agent and other additives, and used for forming a dye image as so-called external mold development. In that case, the amount added is 11
．． 0.0005 to 0.05 mol, preferably 0.0005 to 0.05 mol per mol.
005 to 002 mol.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, such as dissolving it in a high-boiling organic solvent (combined with a low-boiling organic solvent if necessary) and emulsifying and dispersing it in an aqueous gelatin solution to form a silver halide emulsion. I prefer the oil droplet dispersion method in ice.
7.

Examples of high boiling point solvents used in the oil-in-ice dispersion method are described in US Pat. No. 2.322.027 and the like.

Further, the process and effects of the latex dispersion method as one of the polymer dispersion methods, and specific examples of the latex for impregnation are described in US Pat.
> No. 2.541.274, No. 2.541,230,
Special Publication No. 53-41091 and European Patent Publication No. 0291
PCT International Publication No. 1110 regarding the dispersion method using organic solvent-soluble polymers.
It is described in the specification of No. 88100723.

1. A high boiling point organic solvent that can be used in the above-mentioned oil-in-water dispersion method; phthalate esters (e.g., dibutyl phthalate, dioctyl phthalate), dicyclohexynophthalate, di-2-thylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-
amyl phenyl)iso7thaleate, bis(1,1-diethylpropyl)phthalate, esters of phosphoric or phosphonic acids (e.g., diphenyl phosphate, tri7)
ale phosphate, tricresyl phosphate, 2.
-ethylhexyl diphenyl phosphate, diocthylbutyl phosphate, tricyclohexyl phosphate, )! l-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phosphate! phosphonate), benzoic acid esters (e.g., 2-ethylhexylbenzoate, 2,4-dicUi I□1 benzoate, dodecylbenzoate, 2.-■,-fluhexyl-p-hydroxybenzoate), Tχ dos (
For example, N,N-diethyldodecanamide, N, ~.

(diethyl lauryl alcohol), alcohols or phenols (isostearyl alcohol, 2,4-di-te
rt-amylphenol, etc.), aliphatic esters (e.g., dibutoxyethyl succinate, ':] di-2 succinate,
-ethylhexyl, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-t)
ert-octylaniline, etc.), chlorinated paraffins (paraffins with a chlorine content of 10% to 80%), trimesic acid esters (e.g., tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (e.g., 2,4-di-tert-T-milphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-(4-dodecyloxyphenylsulfonyl)phenol), carboxylic acids ~tert-amylphenoxybutyric acid, 2-ethoxyoctanedenoic acid), alkyl phosphoric acids (eg, di(2-ethylhexyl) phosphoric acid, diphenyl phosphoric acid), and the like. In addition, organic solvents with a boiling point of 30°C or higher and approximately 160°C or lower (for example, ethyl acetate, butyl acetate, ethyl propionate) can be used as auxiliary solvents.
, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The high boiling point organic solvent has a weight ratio of 0 to 2.0 to the coupler.
It can be used in double amount, preferably 0 to 1.0 times amount.

The coupler of the present invention can be applied to, for example, color vapor, color reversal paper, direct positive color photosensitive material, color negative film, color positive film, color reversal film, and the like. Among these, application to color photosensitive materials having a reflective support (for example, color paper, color reversal paper) is preferred, and application to color photosensitive materials having a reflective support is particularly preferred.

The silver halide emulsion used in the present invention may be of any halogen composition such as silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide, and silver chloride.

The preferred halogen composition varies depending on the type of photosensitive material to be used, and silver chlorobromide emulsions are mainly used for color vapors, while silver iodide is preferably used for photographic photosensitive materials such as color negative films and color reversal films from 0.5 to 0.5%. 30 mol% (
Silver iodobromide emulsion containing preferably 2 to 25 mol%),
Silver bromide and silver chlorobromide emulsions are used in direct positive color light-sensitive materials. Further, so-called high silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials for color paper suitable for rapid processing. The silver chloride content of this high silver chloride emulsion is preferably 90 mol% or more, more preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is present inside and/or on the surface of the silver bromide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized phases can be located inside the grain or on the edges, corners, or surfaces of the grain surface, but one preferred example is one that is epitaxially grown on a part of the corner of the grain. .

In the present invention, it is particularly preferable to use silver chlorobromide or silver chloride which does not substantially contain silver iodide. Here, "substantially free of silver iodide" means
Silver iodide content is 1 mol% or less, preferably 0.2 mol%
Say the following.

The halogen composition of the emulsion may be different or equal among the grains, but if an emulsion having an equal /'% halogen composition is used among the grains, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (shell)〔
A particle with a so-called layered structure in which the halogen composition differs between layers or multiple layers; or a structure with a non-layered portion of different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, an edge, corner or surface of the particle); Particles having a structure in which portions of different compositions are bonded to the top thereof can be appropriately selected and used.

In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of suppressing the occurrence of pressure blur. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ, and 0.15μ to 165μ
is particularly preferred. Further, the particle size distribution thereof is preferably so-called monodisperse with a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of the silver halide grains contained in the emulsion is regular (cubic, tetradecahedral, or octahedral).
r) Those having a crystalline shape, those having an irregular m-crystalline shape such as spherical or plate-like, or those having a composite shape thereof can be used. Further, tabular grains may be used.

The silver halide emulsion used in the present invention is either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. It may be something.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No. 176.
43 (December 197B>, pp. 22-23, -1
, emulsion preparation
n and types)-, and the same magazine NO, 187
1, 6 (November 1979), 648 pages, “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell (P.
Glafkides, Che+++ie et Ph
1sique Photographique, Pa
ul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, P, Du
ffin, Photographic Bmulsi
on Chemistry (Focal Press
, 1966)), Zelikman et al. [Manufacture and Coating of Photographic Emulsions], published by Focal Press (V, L, 2eli
k+nan et al, Making ancl
Coating Photographic B+nu
lsion, Focal Press, 1964)
It can be adjusted using the method described in et al.

U.S. Patent Nos. 3.574.628 and 3.655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1.413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering),
Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4.434.226, U.S. Pat.
4.433.048, 4.439.520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a silk-like structure. Further, silver halides having different compositions may be bonded by the epitaxial bond 1, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening. Examples of the compounds used include salts of cadmium, zinc, button, copper, thallium, etc., or salts or complex salts of Group I elements such as iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc. can.

The additives used in the physical ripening, chemical ripening, and spectral sensitization steps of the silver halide emulsion used in the present invention are listed in Research Disclosure No. 17643, Research Disclosure No. 17643,
It is described in IB716b and No. 307105, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the two Research Disclosures in section 1-1, and the relevant descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4.411.987 and US Pat.
Compounds that can be immobilized by reacting with formaldehyde as described in No. 435.503 can also be added to the photosensitive material.

Various color couplers can be used in combination with the present invention, and specific examples thereof include the above-mentioned Research Disclosure?
-(RD) No, 17643, ■-C-G and same N
o, 307105, ■-1'' to 6.

Yellow coupler and 12, e.g. US patent boxes 3, 9
33.501, 4.022.620, 4.32
No. 6.024, No. 4.401.752, No. 4.248
．． No. 961, Special Publication No. 58-10739, British Patent No. 1
゜425.020, 1゜476, 760, U.S. Patent Box 3.973.968, 4.314.023,
4゜511.649, European Patent No. 249.473A
Preferably, those described in No.

In the coupler of the present invention, from the viewpoint of color reproducibility, the maximum absorption wavelength of the coloring dye formed is located on the short wavelength side, and
It is preferable to use an Ikaro coupler which sharply reduces absorption in a long wavelength region exceeding nm. As such a yellow coupler, for example, Japanese Patent Application Laid-Open No. 63423047
No. and Japanese Patent Application Laid-open No. 1-173499.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Patent Box 4.3
10.619, 4.351.897, European Patent No. 73.636, US Patent Box 3.061.432, 3.725°067, RD Magazine No. 24220 (1
June 984), JP-A No. 60-33552, RD Magazine N
o, 24230 (June 1984), Japanese Patent Application Publication No. 1983-
No. 43659, No. 61-72238, No. 60-357
No. 30, No. 55-118034, No. 60-18595
1, U.S. Patent Box 4.500゜630, U.S. Patent Box 4.540
．． No. 654, No. 4.556.630, International Publication WO3
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Box 4.052.212.
No. 4.146.396, No. 4.228.233, No. 4, 296,200, No. 2.369.929,
2.801.171, 2.772.162, 2.895.826, 3.772.002, 3
．． No. 758.308, No. 4.334.0], No. 1, No. 4
, 327, 173, West German Patent Publication No. 3.329.72
No. 9, European Patent No. 121.365A, European Patent No. 249°45
No. 3^, U.S. Patent Box 3,446, No. 622, U.S. Patent Box 4.33
No. 3.999, No. 4.775.616, No. 4, 451
．． No. 559, No. 4.427.767, No. 4.690.
No. 889, No. 4.254.212, No. 4.296.1
99, JP-A No. 61-42658, etc. are preferred.

In addition, colored dyes are used to correct unnecessary absorption of coloring pigments.
A coupler may also be used, as disclosed in Research Ice Closure No. 17643, Section 6, U.S. Patent Box 4, 16.
Preferred are those described in Japanese Patent Publication No. 3.670, Japanese Patent Publication No. 57-39413, U.S. Pat.

In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in U.S. Patent Box 4.774.181, and U.S. Patent Box 4.777, 12.
It is also preferable to use a coupler having a dye precursor group as a leaving group which reacts with a developing agent to form a dye as described in No. 0.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.366, 237 and British Patent No. 2,125.
, No. 570, European Patent No. 96.570, and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
．． No. 576,910, British Patent No. 2.102.173, etc.

Couplers that release photographically useful residues upon coupling can also be used in the present invention. The old R coupler that releases a development inhibitor is published in the aforementioned RD Magazine No. 17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4.248.962
No. 4.782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097.1.40, British Patent No. 2.131.188, and JP-A-59-157638.
No. 59-170840 is preferred.

Other couplers that can be used in combination with the photosensitive material of the present invention include competitive couplers described in U.S. Patent No. 4.130.427, U.S. Pat.
8.393, 4.310.618, etc., JP-A-60-185950, JP-A-62-2
DIR redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds as described in EP 173.3028, etc.; couplers that release dyes that fade after separation as described in EP 173.3028; , RD Magazine No.
No. 11449, same magazine No. 24241, Japanese Unexamined Patent Publication No. 6
Bleach accelerator releasing couplers described in US Pat. No. 1-201247 etc., ligand releasing couplers described in US Pat. No. 4.774.1
Examples include couplers that emit fluorescent dyes as described in No. 81.

The standard usage amount of color couplers that can be used in combination is in the range of 0.001 to 1 mol per 1 mol of photosensitive silver halide, preferably 0.01 to 0 for yellow couplers.
．． 5 mol, for magenta coupler 0°003 to 0.3
mole, and for cyan coupler, it is 0.002 to 0.3 mole.

These couplers that can be used in combination can be introduced into the light-sensitive material by the various known dispersion methods mentioned above.

The light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. Organic anti-fading agents for cyan, magenta and/or yellow images include /%4 droquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols. Typical examples include hindered phenols, gallic acid derivatives, methane dioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds.

Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-diγlkyldithiorubamato)nickel complex can also be used.

Specific examples of organic anti-fading agents include U.S. Pat.
No. 0.290, No. 2.418.613, No. 2.7D0
．． No. 453, No. 2.701.197, No. 2.728.
No. 659, No. 2.732.300, No. 2.735.7
No. 65, No. 3.982.944, No. 4゜430, 42
No. 5, British Patent No. 1.363.921, U.S. Patent No. 2
, 710.801, 2.816.028, etc.; U.S. Patent Nos. 3.432.300, 3.573°050, 3.574.627;
6-hydroxychromans, 5-hydroxychromans, and subicromans described in U.S. Pat. Spiroindanes described in US Pat. No. 2.735.765, British Patent No. 2.066,975, JP-A-59-0539, and p-alkoxyphenols described in JP-A-57-19765, etc.; Patent No. 3.700.455, Patent No. 4.22
No. 8.235, JP-A-52-72224, JP-A-52
-Hindered phenols described in US Pat. No. 3,457,079; gallic acid derivatives described in US Pat.
Methylenedioxybenzenes described in U.S. Patent No. 4.332゜886; Aminophenols described in Japanese Patent Publication No. 56-21144; U.S. Patent Nos. 3.336.135 and 4.268.593, British Patent No. 1.326.889
No. 1.354.313, No. 1.410.846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983-1140
Hindered amines described in US Pat. No. 36, No. 59-53846, No. 59-78344, etc.; US Pat. No. 4.050.
No. 938, No. 4.241.155, British Patent No. 2.0
Examples include metal complexes described in 27.731(A) and the like. These compounds can achieve this purpose by co-emulsifying the couplers (usually 5 to 100% by weight with respect to their respective color couplers) and adding them to the photosensitive layer. In order to prevent the deterioration caused by UV rays, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As the ultraviolet absorber, a benzo)U azole compound substituted with W at an aryl group (for example, US Pat. No. 3,533.7)
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3.314.794 and U.S. Pat. No. 3.352.6)
81), benzophenone compounds (e.g., those described in JP-A No. 4Er2784), cinnamate ester compounds (e.g., U.S. Pat. No. 3.705.805,
3.707.395), butadiene compounds (as described in U.S. Pat. No. 4.045.229)
Alternatively, benzoxazole compounds (eg, those described in US Pat. No. 3,406,070 and US Pat. No. 4,271,307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by R. Weiss (Academic Press, published in 1964).

The photosensitive materials of the present invention include JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941.
1,2-benzisothiazolin-3-one described in No.
n-butyl p-hydroxybenzoate, phenol,
It is preferable to add various preservatives or antifungal agents such as 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl>benzimidazole).

When the photosensitive material of the present invention is a direct positive color photosensitive material, research disclosure magazine No. 0122534 (
It is possible to use nucleating agents such as hydrazine compounds and quaternary complex compounds as described in J.D., January 1983), and nucleating accelerators that enhance the effects of these nucleating agents.

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" that can be preferably used in the present invention refers to one that has high reflectivity and makes the dye image formed in the silver halide emulsion layer clear, and such a reflective support For example, a support is coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., or a support using a hydrophobic resin containing dispersed light-reflecting substances. Includes those used. For example, baryta paper; polyethylene-coated paper; polypropylene synthetic paper; transparent support with a reflective layer or a reflective material (e.g. glass plate, polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, etc.).

The photosensitive material according to the present invention has the above-mentioned RD No. 1764.
3, pages 28-29, and same No. 18716, 61
5. Development processing can be carried out by the usual methods described in the left column to right column. For example, the color development process includes a color development process, a desilvering process, and a water washing process. When performing reversal development processing, black and white development processing
A washing or rinsing process, a reversal process, and a color development process are performed. In the desilvering process, instead of the bleaching process using a bleaching solution and the fixing process using a fixing solution, a bleach-fixing process using a bleach-fixing solution can be performed,
The bleaching process, fixing process, and bleach-fixing process may be combined in any order. A stabilization step may be performed instead of the water washing step, or a stabilization step may be performed after the water washing step. It is also possible to carry out a monobath processing step using a one-bath development, bleaching and fixing treatment solution in which color development, bleaching and fixing are carried out in one bath. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process,
A postdural treatment process, a preparation process, a supplementary process, etc. may also be performed. An intermediate water washing step may be optionally provided between the above steps.

In these treatments, a so-called activator treatment step may be performed instead of the color development treatment step.

The color developing solution used in the development of the light-sensitive material of the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-Ryominor N, N-diethylRyoniline, 3-Methyl-4=amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfone Tmidoethylaniline, 3-methyl-4-amino-N-ethyl-β
-methoxyethylaniline and their sulfates, hydrochlorides, and 1)-1 luenesulfonates. These compounds can also be used in combination depending on the purpose.

The color developer contains p)I buffers such as alkali metal carbonates, borates or phosphates; chloride, bromide, iodide salts, benzimidazoles, penzotiTzoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant such as. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl yamitribazide,
various preservatives such as triethanolamine, catechol sulfonic acids; organic solvents such as ethylene glycol, diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers; competitive couplers. 1 = Auxiliary developing agents such as phenyl-3-pyrazolidone; Nucleating agents such as sodium chloride, boron hydride and hydrazine compounds; Viscosifying agents niaminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphono Various acid salts represented by carboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, Nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,
(N, N-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid) and salts thereof); 4.Fluorescent brighteners such as 4'-diamino-2,2'-disulfostilbene-based compounds; Various surfactants such as alkylsulfonic acids, arylsulfonic acids, fatty carboxylic acids, and aromatic carboxylic acids can be added.

Preferably, the color developing solution in the present invention does not substantially contain benzyl alcohol. Substantially not containing benzyl alcohol means preferably not more than 2 ml/l, preferably not more than 0.5 d/β, and most preferably not.

It is preferable that the color developing solution in the present invention does not substantially contain sulfite ions. "Substantially no sulfite ions are contained" preferably means not more than 3,0 x 10-'' mol/β, more preferably not containing sulfite ions.

Preferably, the color developing solution in the present invention does not substantially contain hydroxylamine. Substantially hydroxylamine-free preferably means 5. OX], 0
3 mol/l or less, more preferably not. The color developing solution of the present invention preferably contains an organic preservative other than hydroxylamine (for example, a hydroxylamine derivative or a hydrazine derivative).

The pH of these color developing solutions is generally 9 to 12.

Further, as the color reversal development process, a black and white development process, a water washing or rinsing process, a reversal process, and a color development process are performed. As the reversal process,
A reversal bath containing a fogging agent or a light reversal treatment may be used. Alternatively, the above-mentioned fogging agent may be included in the color developing solution and the reversal process step may be omitted.

The black-and-white developer used in black-and-white development processing is one that is commonly used in processing known black-and-white photographic materials.
It can contain various additives that are generally added to black and white developers.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, N-methyl-P-T minophenol and hydroquinone; preservatives such as sulfites; water-soluble agents such as acetic acid and boric acid. pH buffering agents consisting of neutral acids; pH buffering agents or development accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate; inorganic agents such as potassium bromide, 2-methylbenzimidazole, and methylbenzdeazole water softeners such as ethylenediaminetetraacetic acid and polyphosphate; antioxidants such as ascorbic acid and jetanolamine; organic solvents such as triethylene glycol and cellosolve; Examples include surface overdevelopment inhibitors such as iodides and mercapto compounds.

In addition, when reducing the amount of replenishment of these developing solutions, it is preferable to prevent evaporation of the solution and air oxidation by reducing the area of contact with the air in the processing tank. The method of reducing the contact area with the air in the processing tank as described above and 1. Then, a method of providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank can be mentioned. This technique is preferably applied not only to both color development and black and white development steps, but also to all subsequent steps. Furthermore, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developer, such as a regenerating means.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion bath is subjected to desilvering treatment.

In the desilvering process, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. further processing in two consecutive bleach-fixing baths, a fixing treatment before the bleach-fixing treatment;
Alternatively, bleaching treatment may be carried out after bleach-fixing treatment depending on the purpose. In the present invention, bleach-fixing treatment immediately after color development is effective in achieving the effects of the present invention.

Examples of bleaching agents used in bleaching solutions and bleach-fixing solutions include compounds of polyvalent metals such as iron (II); peracids; quinones; iron salts, and the like. Typical bleaching agents include:
Iron chloride; ferricyanide; dichromate; iron (III
) (for example, metal anchor rings of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-diaminopropanetetraacetic acid)-persulfates. Among these, aminopolycarboxylic acid iron (I[[) complex salts are preferred from the viewpoint of effectively exerting the effects of the present invention. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. Bleach solutions or bleach-fix solutions using these aminopolycarboxylic acid iron(III) complexes are used with a PI of 3.5 to 8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; and metal corrosion inhibitors such as ammonium sulfate can be added to the bleach and bleach-fix solutions. .

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
~5°5, specifically acetic acid, propionic acid, etc. are preferred.

The fixing agent used in fixing solutions and bleach-fixing solutions can include thiosulfates, thiocyanates, thioether compounds, thioureas, large amounts of iodide salts, etc., but thiosulfates are generally used. ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred.

As the preservative for the fixing solution and bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294769 are preferred. Furthermore, for the purpose of stabilizing the fixing solution and bleach-fixing solution, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-7 hydroxyethylidene-1,1-diphosphonic acid, N, N, N', Preference is given to adding N'-ethylenediaminetetraphosphonic acid).

The fixer and bleach-fixer may further contain various fluorescent brighteners; antifoaming agents; surfactants; polyvinylpyrrolidone; methanol and the like.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators include U.S. Pat.
93.858, West German Patent No. 1.290.812, West German Patent No. 2,059, 988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-534
No. 2623, No. 53-95630, No. 53-9563
No. 1, No. 53 (No. 04232, No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure?-No. 17129 (1)
Compounds having a mercapto group or disulfide group as described in JP-A No. 1978-140129; thiapridine derivatives described in JP-A No. 45-8506, JP-A No. 52-20832, 5:3 -32735, thiourea derivatives described in U.S. Patent No. 3.706.561;
16.235; West German Patent No. 966.
Polyoxyethylene compounds described in Japanese Patent Publication No. 410 and 2.748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434 and Japanese Patent Publication No. 49-42434.
No. 9-59644, No. 53-94927, No. 54-3
No. 5727, No. 55-26506, No. 58-1639
Compounds described in No. 40; bromide ions and the like. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Patent No. 3.893.858 and West German Patent No. 1.290.812.
The compounds described in JP-A No. 53-95.630 are preferred. Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes. Furthermore, the treatment temperature is 25°C to 50°C, preferably 35°C to 4°C.
The temperature is 5°C.

In the desilvering step, it is preferable that stirring be as strong as possible. A specific method for strengthening the agitation includes the method described in JP-A-62-183460 in which a jet of a processing liquid impinges on the emulsion surface of a photosensitive material. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions.

The light-sensitive material of the present invention is generally subjected to a water washing step after desilvering treatment. A stabilization step may be performed instead of the water washing step. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57J
No. 543, No. 5B-14834, No. 60-20345
All known methods described in this issue can be used. Further, a washing step-stabilizing step may be carried out using a stabilizing bath containing a dye stabilizer and a surfactant as the final bath, as typified by the processing of color light-sensitive materials for photography.

The washing solution and stabilizing solution include water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid, and organic aminophosphonic acid; chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate; 1 salt,
Metal salts such as ^1 salt and B1 salt; surfactants; hardeners;
It can contain a bactericide and the like.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Get seven settings extensively. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Te1evis
ion Bngineers, Volume 64, P, 24
8-253 (May 1955 issue). Furthermore, the method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively.

The pH of the washing water is 4-9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 15 to 45°C.
10 minutes, preferably 30 seconds to 5 minutes at 25 to 40°C.

Dye stabilizers that can be used in the stabilizing solution include:
aldehydes such as formalin and glutaraldehyde,
Examples include N-methylol compounds such as dimethylol urea, hexamethylenetetramine, and aldehyde sulfite adducts.

In addition, the stabilizing liquid may include other buffers such as boric acid and sodium hydroxide; chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid; and sulfuric agents such as T-kanolamine. It may contain an inhibitor; a fluorescent whitening agent; an antifungal agent, etc.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing, and it is preferable to use various precursors of the color developing agent. For example, indoaniline compounds described in U.S. Patent No. 3.342.597, U.S. Patent No. 3.342.599, RD Magazine No.
Ship base type compounds described in No. 14.850 and No. 15.159 of the same magazine, aldol compounds described in No. 13.924 of the same magazine, metal salt complexes described in U.S. Pat. Examples include urethane compounds described in No.-135628.

The light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development. A typical compound is disclosed in JP-A-56-643.
No. 39, No. 57-144547, and No. 58-11
It is described in No. 5438, etc.

Various processing solutions in the present invention are used at 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but 1. It is possible to accelerate the processing and shorten the processing time, or conversely, lower the temperature to improve image quality and stability of the processing solution.

Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

[Example 1] In order to investigate the basic hue of the dye obtained from the coupler of the present invention, dye (61) of exemplified compound (26) was synthesized by a conventional method, and its absorption wavelength was measured.

Figure 1 shows the absorption waveform of (61) in ethyl acetate. A conventionally known phenolic cyan dye (62) was used as a comparative compound.

As is clear from FIG. 1, it can be seen that the short-wave side edge breakage is better than that of comparative compound (62).

[Example 2] [Preparation of Sample 101] Sample 101 having the layer structure shown below was prepared on a cellulose triacetate film base. The first layer coating solution was prepared as follows.

(Preparation of first layer coating solution) Cyan coupler (^-I>1.01 g and 0.8 g of dibutyl phthalate were added to 10.0 cc of ethyl acetate and completely dissolved. A solution of this coupler in ethyl acetate was added to 42 g of ethyl acetate. It was added to a 10% aqueous gelatin solution (containing 5 g/j! of sodium dodecylbenzene sulfonate) and emulsified and dispersed using a homogenizer. After emulsifying and dispersing, distilled water was added to make the total amount 100 g. This emulsified dispersion 100g
and 8.2 g of a high silver chloride emulsion (silver bromide content: 0.5 mol %) were mixed and dissolved to prepare a first layer coating solution having the composition shown below. As a gelatin hardener, 1-oxy-
3,5-dichloro-5-triazine sodium salt was used.

(Layer structure I&) The layer structure of each layer is shown below.

Support cellulose triacetate film 1st layer (emulsion layer) High silver chloride emulsion 0.29 g/m in terms of silver
Gelatin 2.50g/m' Cyan coupler (^-”) 0.49g
/m'dibutyl phthalate 0.39
g/Go second layer (protection N) Gelatin 1.60g/m' [
Preparation of samples 102 to 1120 In sample 101, the coupler shown in Table 1 was used instead of the cyan coupler (^-■).
Sample 101 was prepared in the same manner as Sample 101, except that the same molar amount was replaced.

Shinkabu − ＾−■ （、） 吋Processing process Temperature Time Color development
Bleach fixing at 38℃ for 45 seconds
35℃ 45 seconds rinse ■ 35℃
Rinse for 30 seconds■ 35℃
Rinse for 30 seconds 0 35℃ 3
Drying for 0 seconds 80℃ 60 seconds (
A 3-tank countercurrent flow system was used for rinsing ■-■. ) The composition of each treatment liquid is as follows.

Color developer water B
ODm! Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0g Triethanolamine 8.0g Potassium chloride
3.1g potassium bromide
0.015g potassium carbonate
25.0g hydrazinoniacetic acid
5.0g N-ethyl-N-(β-methanesulponamide ether)-3-methyl-4 = Ryomino Tniline sulfate 5.0g, i-light whitening agent (11111TBX-4 manufactured by Sumitomo Chemical) 2.0g Add water to 10100O! .

pH (with potassium hydroxide) 10.05 Bleach-fix water 40
0ml ammonium osulfate solution (700g#) 1
00 Ammonium Sulfite 45.0g
EthylenediTminetetraacetic acid iron(III) 55.0g
Ammonium ethylenediaminetetraacetic acid 3.0g Ammonium bromide 30.0g Nitric acid (67%
) Add 27.0g water
Sample 201-412 prepared as above at 1,000 dpl (5,8 rinsing liquid ion-exchanged water (calcium, magnesium is 3 ppm or less) or more) was subjected to continuous wedge exposure using internal light, and then developed using the processing steps shown below. I did it.

After development, the density was measured and a characteristic curve (
log8 vs Schiff? /@ degrees) was calculated. On this characteristic curve, the sensitivity was evaluated by the value of the logarithm (LogB) of the exposure amount that gives a density value of (fog density +0.5).

Next, on this specific curve, the gradation was evaluated by the value of the slope of the straight line connecting the point giving the density value of (fog density + 0.5) and the point giving the density value of (fog density + 1.5). .

Further, spectral absorption measurements were performed at the highest density portion, and the hue was evaluated based on the magnitude of sub-absorption given by the following equation.

The results of absorption concentration at the magnitude of sub-absorption - 420 nm/absorption concentration at the maximum absorption wavelength are summarized in Table 1.

*Represented as a relative value to sample 101.

From Table 1, it is clear that the coupler of the present invention has excellent absorption characteristics with small secondary absorption on the short wavelength side of the spectral absorption characteristics, and exhibits good coloring properties that provide high sensitivity and high gradation. .

[Example 3] As a silver halide color photosensitive material, the European patent [iPO
, No. 355,660^2 (corresponding to: Unexamined Japanese Patent Publication No. 2439544
Sample N described in Example 2 of the Publication No. 1SS, N, 07/393.747).

, 214 (multilayer color paper) was used. however,
Ill-10 was used instead of ■-23 described in the publication as a bisphenol compound, and yellow coupler (Bx
Y), image stabilizer (Cpd-8), solvent (Sol
v-5), the oxonol dyes were changed to the following compounds, and the following compounds were used as preservatives (antibacterial and antifungal agents), and as the cyan coupler for the fifth layer, example couplers (1), (3), (4), (9),
(10), (12), (14), (17), (1
9), (22), and (24) in equimolar amounts.

(Left below) (Exy) Yellow coupler (Cpd-8) Color image stabilizer OHOH 1:1 (Mole ratio) 1111 compound (Cpd-10) Preservative (cpd-xi) 1
9 + l (fffffl ratio) mixture with 7iW agent (Sol v-6) solvent So,N
a (4υ/l+1) This color photosensitive material was also subjected to a color development process according to the method described in Example 2.

The results showed good color reproducibility (especially green).

[Example 4] In Example 2, silver iodobromide (
A sample was prepared in the same manner as in Example 2 except that an emulsion containing 8.0 mol % of silver iodide was used. These samples are 201-212
shall be. The thus prepared sample was developed by the following processing steps and evaluated in the same manner as in Example 2.

The results are the same as in Example 2, and the obtained color image shows excellent spectral absorption characteristics with small secondary absorption on the short wavelength side, and the photographic properties are also good, with higher sensitivity and higher gradation than the comparative sample. It was confirmed that this coupler exhibits excellent color development.

Processing method Processing time Processing temperature Color development @
3 minutes 15 seconds 38℃ bleaching 1 minute 00
38℃ bleach fixing 3 minutes 15 seconds
38℃ water washing (1) 40 seconds 35℃
Water washing (2) 1 minute 00 seconds Stable at 35℃ 40 seconds Dry at 38℃
Drying 1 minute 15 seconds at 55°C Next, the composition of the treatment solution will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.01-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate
30.0 Potassium Bromide
1.4 Potassium iodide 1.
5 ■ Hydroxylamine sulfate 2.44-[N
-ethyl-N-β- hydroxyethylamino] -2-methylaniline sulfate 4.5 Add water
1.0pP)I
10.05 (bleaching solution)
(Unit g) Ethyndiaminetetraacetic acid ferric ammonium trihydrate 120.0 Ethylenediγ
Minetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate
10.0 bleach accelerator
0.005M ammonia water (27%)
15.0ffL+! add water
1.0j! pH 6.3 (Bleach-fix solution) (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g/l) 24 (1 , (] d! Ammonia water (27%) 6. Add Od water 1.0! PH7,2 (Washing liquid) Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) ) and DH type ring basic anion exchange resin T Amberlite IR^-4
Water was passed through a mixed-bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 31 TIg/i, followed by sodium isocyanurate dichloride 20
■/l and 0.15 g/β of sodium sulfate were added. The roll of this liquid is in the range of 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2. Omf polyoxyethylene-p-0,3 Monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Add disodium salt water 1.01p H5,
0-11,0 [Example 5] The 3rd to 5th layers BX-2, EX-4, and EX-10 in photosensitive material 1 of Example 1 of JP-A No. 2-93641 were used as examples of cuffler (1), etc. A sample was prepared in the same manner except that the moles were replaced, and the treatment was carried out in the same manner. As a result, color tubes with excellent color reproduction were obtained.

[Example 6] Samples 201 to 212 prepared in Example 4 were subjected to wedge exposure using internal light, and then developed using the processing steps shown below.

After the development process, the sample was left at 80° C. for two weeks to perform a color fading test. The cyan density (DI) after the fading test was measured when the cyan density before the fading test was 1.0, and the image fastness of each sample was calculated using the following formula (this was taken as the dye residual rate). was evaluated.

Dye residual rate - ((Di) / 1.0) xlOO
In addition, samples that had been separately subjected to the same treatment were irradiated for 3 days using a xenon fading tester, and the light fastness of the image of each sample was evaluated in the same manner as above.

The results are shown in Table 2 for Mato Island.

In addition, when the photographic properties were investigated from the characteristic curve of the sample processed by the above-mentioned method, as in Example 4, both the sensitivity and gradation of the coupler of the present invention were higher than that of the comparative coupler.
It was confirmed that good color development was exhibited.

Processing process Time Temperature first phenomenon 6 minutes 38℃ Water washing 2 minutes 38℃ Inversion 2 minutes 38℃ Color development 6 minutes 38℃ Preparation 2 minutes 38℃ bleaching
6 minutes 38℃ fixation 4 minutes
Wash with water at 38°C for 4 minutes. Cool at 38°C.
Dry at room temperature for 1 minute. The composition of the processing solution used is as follows.

No.-Developer water 7D
Omf! Nitrilo N, N, N-trimethylenephosphonic acid pentasodium salt 2g Sodium sulfite
20g Hydroquinone monosulfonate 30g Sodium carbonate (-hydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2g potassium bromide
2.5g potassium thiocyanate
1.2g potassium iodide (0.1% solution) 2
-Add water to 10100O'!
pH9,60 Inverted liquid water 700
ml! Nitrilo-N,N,N-)limethylenephosphonic acid pentasodium salt 3g stannous chloride (
trihydrate) Igp-aminophenol
0.1g sodium hydroxide
Add 8g of glacial acetic acid and 15 drops of water to make 10 mouthfuls! p++
6.00 Color developer water 700
dNitrilo-N,N,N-)limethylenephosphonic acid pentasodium salt 3g Sodium sulfite 7g Sodium tertiary phosphate (12
water salt) 36g potassium bromide 1
g Potassium iodide (0.1% solution) 90 Sodium hydroxide 3 g Citrazic acid 1.5 g N-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl-4-aminotriline sulfate 11g3.6-cythiaoctane-1.8. -Diol, add 1g water
1000dpt+
11.80 Adjustment liquid water 700
m! ! Sodium sulfite 12g Lithium ethylene diamine acetate (trihydrate) 8g Thioglycerin 0.4-glacial acetic acid
3- Add water
10100O! p1
6.60 bleach solution water 800
ffLf! Sodium ethylenediaminetetraacetate (trihydrate) 2g Ethylenediaminetetraternate iron III) ammonium (trihydrate) 120g Potassium bromide 100g Add water
1000dpH5,70 Fixer water 800
Add sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Water
1000100O6,60 Stable liquid water 80
〇-Formalin (37% by weight) 5.0-
Fuji Drywell (surfactant manufactured by Fuji Film ■) 5. 1000m with added water! ! pH 7.0 Table 2 As is clear from Table 2, the color images obtained from the couplers of the present invention are superior in fastness to high temperatures and light compared to the comparative samples.

〔Effect of the invention〕

The coupler represented by the general formula (1) of the present invention has high sensitivity and gradation, exhibits good photographic properties, and exhibits excellent spectral absorption characteristics with little sub-absorption on the short wavelength side. Therefore, use of the coupler represented by -Noshiro (1) above can provide a silver halide color photographic light-sensitive material that has excellent color development and hue, and improves color reproducibility.

[Brief explanation of the drawing]

FIG. 1 shows the exemplary compound (2) of the present invention described in Example 1.
6) and the conventionally known phenolic cyan dye (62) in ethyl acetate solvent, the vertical axis is the absorption concentration (normalized to 1). , and the horizontal axis represents wavelength (nm>).

Claims (2)

[Claims] (1) A silver halide color photographic material containing a coupler represented by the following general formula [I]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 are substituents that can be substituted on the thiophene ring, and the sum of the values of each Hammett's substituent constant σ_p is 0.4 or more It represents a substituent of 1.6 or less, and W represents a hydrogen atom or a leaving group that leaves when the coupler undergoes a coupling reaction with an oxidized product of an aromatic primary amine developing agent. ] (2) A method for forming a silver halide color image, which comprises forming an image by reacting a coupler represented by the following general formula [I] with an oxidized product of an aromatic primary amine developing agent. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 are substituents that can be substituted on the thiophene ring, and the sum of the values of each Hammett's substituent constant σ_p is 0.4 or more It represents a substituent of 1.6 or less, and W represents a hydrogen atom or a leaving group that leaves when the coupler undergoes a coupling reaction with an oxidized product of an aromatic primary amine developing agent. ]