JPH04184437A - Color image forming method and silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a dye image having a fine hue and superior fastness to heat by bringing a specified cyan coupler and the oxidized body of a developing agent into a coupling reaction. CONSTITUTION:A cyan coupler represented by formula I and the oxidized body of a developing agent are brought into a coupling reaction. In the formula I, X is H or a group releasable by a coupling reaction with the oxidized body of a developing agent, R<1> is H or a substituent and R<2> is an electron withdrawing group having >=0.10 Hammett's substituent constant sigmap but R<2> is not carboxyl, alkoxycarbonyl or carbamoyl. A dye forming reaction by the coupling reaction is represented by formula II (where Ar is not arom. group). A dye image having a fine hue and superior fastness to heat is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming a color image using a novel dye-forming coupler and a silver halide color photographic light-sensitive material.

(Prior art) After exposing a silver halide color photographic material to light,
By color development processing, a developing agent such as an aromatic primary amine oxidized by silver halide reacts with a dye-forming coupler to form a color image. Generally, in this method, a subtractive color reproduction method is often used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.

Phenols or naphthols are often used as cyan image forming couplers.

However, conventionally used cyan dyes obtained from phenols and naphthols have sub-absorption in the blue and green regions, which is particularly unfavorable in terms of green color reproduction (improvement is desired).

On the other hand, a coupler in which a petero atom is introduced into a ring with a dissociable group is disclosed in U.S. Patent No. 2,293.004 with N-substituted 2.6
-cyhydroxypyridine is only disclosed.

However, the N-7 conversion 2 described in this US patent specification,
The absorption wavelength of the dye obtained from 6-cyhydroquinepyridine is on the very short wavelength side, and the absorption peak is also broad.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to improve the absorption characteristics of coloring pigments (
That is, the present invention provides a method for forming a color image using a novel dye-forming coupler that has a sharp absorption waveform with no sub-absorption in the blue and green regions and excellent color reproducibility, and a silver halide color photographic light-sensitive material. There is a particular thing.

(Means for Solving the Problems) An object of the present invention is to produce a color image using silver halide, which is characterized in that a Noan coupler represented by the general formula C12 and an oxidized form of a developing agent are subjected to a force-pulling reaction. This was achieved by a method of forming or a silver halide color photographic light-sensitive material characterized by containing the coupler.

General formula (1) (wherein, X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a developing agent, R1 represents a hydrogen atom or a substituent, and R2 is Hammett's substituent constant σ
The value of 2 represents an electron-withdrawing group of 0.10 or more. However, Rz is not a carboxyl group, an alkoxycarbonyl group, or a carbamoyl group. ) Hereinafter, the present invention will be explained in more detail.

1 In formula (1), R1 represents a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an aliphatic group (preferably having 1 to 36 carbon atoms), and an aromatic group (preferably having 6 to 36 carbon atoms). , e.g. phenyl, naphthyl), heterocyclic groups (e.g. 3-pyridyl, 2-furyl), alkoxy groups (e.g. methoxy, 2-methoxyethoxy), aryloxy groups (e.g. 2,4-di-tert-amylphenoxy,
2-chlorophenoxy, 4-anophenoxy), alkenyloxy groups (e.g. 2-propenyloxy), amino groups (e.g. butylamino, dimethylamino, anilino, N-methylanilino), acyl groups (e.g. acetyl,
benzoyl), aliphatic or aromatic oxycarbonyl groups (e.g. butoxycarbonyl, phenoxycarbonyl), acyloxy groups (e.g. acetoxy, benzoyloxy), aliphatic or aromatic oxysulfonyl groups (e.g. butoxycarbonyl), sulfonyloxy groups (e.g. toluene). sulfonyloquino), acylamino groups (e.g. acetylamino, penduylamino), sulfonamide groups (e.g. methanesulfonamide, henzenesulfonamide, dipropylsulfamoylamino), carbamoyl groups (e.g. dimethylcarbamoyl, phenylcarbamoyl), sulfamoyl groups (e.g. diethylsulfamoyl, phenylsulfamoyl), imide groups (e.g. succinimide, hydantoinyl), ureido groups (e.g.
e.g. phenylureido, dimethylureido), aliphatic or aromatic sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (e.g. ethylthio, phenylthio), hydroxy groups,
Represents a cyano group, carboxyne group, nitro group, sulfo group, electron-withdrawing group, etc.

In this specification, the term "aliphatic group" refers to a linear, branched, or cyclic aliphatic hydrocarbon, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups.Representatives thereof Examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group, 1so-propyl group, tert-butyl group, tert-butyl group,
t-octyl group, tert-dodecyl group, cyclohexyl group, nclopentyl group, allyl group, vinyl group, 2
-Hexadecenyl group, propargyl group, etc.

-S In formula (1), R1 is more preferably an acylamino group, a sulfonamide group, a ureido group, or an electron-withdrawing group (preferably, the value of the substituent constant σ of /% me/nod is 0.10 Hammett's substituent constant herein, which represents a substituent (more preferably a substituent whose value of σ is 0.35 or more, still more preferably a substituent whose value of σ is 0.60 or more) As the value of σ9, Hansch, C
, reports by Leo et al. (e.g. J, Med, Che-, ■,
1207 (1973) Kuchi bid, Zen, 304 (197
It is preferable to use the values described in 7)).

Electron-withdrawing groups (including atoms) with a value of σ of 0.10 or more
) include chlorine atom, bromine atom, iodine atom, cyano group, aliphatic/aromatic acyl group (e.g. formyl, acetyl, benzoyl), carboxyl group, carbamoyl group (
(e.g. carbamoyl, methylcarbamoyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, diphenylmethyloxycarbonyl), nitro groups, alkylsulfonyloxy groups (e.g. methanesulfonyloxy), aliphatic/aromatic acyloxy groups (e.g. acetyloxy, hezoyloxy), arylsulfonyloxy groups (e.g. Hensensulfonyloxy), phosphono groups, phosphoryl groups (e.g. dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl groups, aliphatic/aromatic sulfonyl groups (e.g. trifluoromethanesulfonyl, difluoromethanesulfonyl) , methanesulfonyl, benzenesulfonyl), alkyl groups substituted with other electron-withdrawing groups (e.g. trichloromethyl, trifluoromethyl, chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), other electron-withdrawing groups Aryl groups substituted with attractive groups (e.g. pentachlorophenyl, pentafluorophenyl), heterocyclic residues (e.g. 2-benzoxasilyl,
2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), amino groups substituted with other electron-withdrawing groups (e.g. ditrifluoromethylamino), alkoxy substituted with other electron-withdrawing groups groups (eg, trifluoromethoxy), and the like.

That is, by using the coupler represented by the formula (1) of the present invention, the absorption of the coloring dye is sharp, and moreover,
Images with excellent color reproducibility can be formed.

Examples of electron-withdrawing groups with a value of σ of 0.35 or more include cyano groups, nitro groups, aliphatic/aromatic acyl groups, carbamoyl groups, alkoxycarbonyl groups, Phosphono group, phosphoryl group, heterocyclic residue (e.g. 1-tetrazolyl), sulfamoyl group, aliphatic/aromatic sulfonyl group, or alkyl group, aryl group, amino group or alkoxy group substituted with other electron-withdrawing group Examples include bases.

Examples of the electron-withdrawing group having a value of σ of 0.60 or more include a cyano group, a nitro group, and an aliphatic/aromatic sulfonyl group.

In the general formula (1), R2 represents an electron-withdrawing group having a Nomet substituent constant σ of 0.10 or more,
It cannot be a carboxyl group, an alkoxycarbonyl group, or a carbamoyl group.

More preferably, the value of Hammett's substituent constant σ is 0.
Represents an electron-withdrawing group of 35 or more. More preferably σ,
represents an electron-withdrawing group with a value of 0.60 or more. The specific electron-withdrawing groups for each are as explained for R1. Further, R1 and R2 may be the same or different.

In the general formula (1), X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent (hereinafter referred to as a leaving group).

Specific examples of leaving groups include halogen atoms (e.g. fluorine, chlorine, bromine), alkoxy groups (e.g. ethoxy, dodecyloxy, methoxyethyl, nivamoylmethoxy,
carboxypropyloxy, methylsulfonylethquine), aryloxy groups (e.g. 4-chlorophenoxy,
4-methoxyphenoxy, 4-carboxyphenoxy)
, acyloxy groups (e.g. acetoxy, tetradecanoyloxo, henzyl oxo), aliphatic or aromatic sulfonyloquine groups (e.g. methanesulfonyloquine,
toluenesulfonyluoquine), ananolamino groups (e.g. dichloroacetylamino, 5-butafluorobutyrylamino), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamide, p-toluenesulfonamide)
, alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, henzyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic/aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio), carbamoyl Amino group (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino), 5
or 6-membered nitrogen-containing heterocyclic group (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1.2
-dihydro-2-oxo-1-pyridyl), imide group (
Examples include succinimide, hydantoinyl), and aromatic azo groups (eg, phenylazo).

Furthermore, there are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.

In general formula (1), the leaving group represented by X is preferably chlorine, an alkoxy group, an aliphatic thio group, or an aromatic thio group.

The coupler represented by the general formula N) 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. The coupler to be used as the internal coupler has a general formula (1) in which at least one of R1, R2, and X has a total carbon number of 10 to
Preferably, it is 50.

The coupler of the present invention is effective as a cyan coupler.

Next, specific examples of the coupler of the present invention will be shown, but the present invention is not limited thereto.

(5) -N) ICONMCI-37CN
Cf floor R'
R2X(7) -NH5OzC+bH3s
CF+ C1 (8)
-N)IsOJH(CHz)sOc+2Hzs
CN C1(9) CN
CFn H(
12) -CONH(CH2)30C12I2S
CF3 C1(14) -C
OzC+Jsi CN
C1l110. R'
R” XC5H++(t) N[l R'
R”XF Floor R' R
'XC1tHts Synthesis examples of representative compounds of the couplers of the present invention are shown below.

Mu Kapoo 3 Å It was synthesized using the following route.

■ Coupler (3) Disperse 24.0 g of 4-cyano-2,6-cyhydroxy-3-phenylazopyridine (1) in 300 d of methanol, add 41.4 g of potassium carbonate, and further add 52.2 g of hydrosulfide soda. An aqueous solution of was added little by little. After heating under reflux for 30 minutes, the mixture was returned to room temperature, saturated brine was added, and the mixture was extracted three times with ethyl acetate.

The extract was condensed 4 times, and dimethylacetamide 200% was added to this.
m, add pyridine 8.1d, 2-(2,4-dit
ert-amylphenoquino)butanoyl chloride 33.
8 g was added dropwise. After stirring at room temperature for 1 hour, the mixture was poured into water and extracted with ethyl acetate. After distilling off the solvent, the residue was purified by column chromatography to obtain 20.3 g of coupler (3) as amorphous.

Mu 2 Kapoo 9 ethyl trifluoroacetylacetate 3.0jli! , α−
Disperse 1.70 g of ananoacetamide in 20 ml of ethanol, and add 2.0 g of piperidine to this. Od was added and the mixture was heated under reflux for 3 hours. After distilling off the solvent, silica gel column chromatography (CH2C1z/CHzOH=10/1~5/
1) to obtain 1.0 g of coupler 9. The structure was confirmed by mass spectra (M'' = 204) and 'H-NMR.

Other couplers were also synthesized using the same method.

Other dye-forming couplers of the present invention represented by general formula (1) (where X is a hydrogen atom, hereinafter referred to as "four-equivalent coupler") can also be synthesized by the same synthesis method as above.

A dye-forming coupler in which X is a leaving group in the general formula (H) can be synthesized by introducing M leaving group into the thus obtained four-equivalent coupler using the method described below.

The method of introducing a leaving group depends on the type of leaving group to be introduced.
The following method 4) can be mentioned.

■When the leaving group is a halogen atom: The most common halogen atom is a chlorine atom, and the general
It can be obtained by chlorinating a four-equivalent coupler in which X is a hydrogen atom in 1) 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: (1) A method of halogenating the coupling position of a four-equivalent coupler and reacting it with a phenol compound in the presence of a base; (2)
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: (]) 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, and (2)
There is a method of introducing a mercapto group into the pulling position of a four-equivalent coupler and causing a halide to act on this mercapto group.

■When the leaving group is a leaving group via a nitrogen atom: (1) The coupling position of the four-equivalent coupler is nitrosated with an appropriate nitrosating agent, and then reduced by an appropriate method (for example, Pd-
Hydrogenation using carbon as a catalyst, chemical reduction using stannous chloride, etc.) and then reacting with various halides; (2) changing the coupling position of the four-equivalent coupler to an appropriate halogen on the other side; (3) 6π or 10π electron system aromatic nitrogen There is a method of introducing a 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. 3.894.8.
No. 75, No. 3,933,501, No. 4.296.19
No. 9, No. 3,221.554, No. 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
．． 419,391, 3,926.631, JP 56-45135, JP 57-36577, JP 57-70871, JP 57-96343, JP 53-
No. 52423, No. 51-105820, No. 53-12
No. 9035, No. 54-48540, etc. can be referred to.

The dye-forming reaction by the coupling reaction between the cyan coupler represented by the general formula (1) of the present invention and the oxidized product of the developing agent is shown below.

Pigment formation scheme: (The above R', R2 and X are the same as shown in the above general formula (1), and Ar represents an aromatic machine,
, ) (Hereinafter in the margin) When the coupler represented by the general formula (1) of the present invention is applied to a silver halide photosensitive material, if the support has at least one layer containing the coupler of the present invention. often,
The layer containing the coupler of the present invention may be any hydrophilic colloid layer on the support. In general color light-sensitive materials, a blue-sensitive silver halide emulsion layer, a green malignant silver halide emulsion layer, and a green malignant silver halide emulsion layer are provided on the support. It can be constructed by coating at least one emulsion layer and one red-sensitive silver halide emulsion layer in this order, but it is also possible to coat the infrared-sensitive silver halide emulsion layer in a different order. It can be used in place of at least one of the photosensitive emulsion layers described above. 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 preferably used 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-' mol-1 mol per 1 mol of silver halide, preferably 2.times.10-' mol to 3.times.10-' mol.

Further, when the coupler of the present invention is soluble in an alkaline aqueous solution, it can be dissolved in an 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 color developer II
0.0005 to 0.05 mol per liter, preferably o, o
os~0.02 mole.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, and can be dissolved in a high-boiling organic solvent (combined with a low-boiling Il solvent if necessary) and emulsified and dispersed in an aqueous gelatin solution to form a silver halide emulsion. The oil-in-water dispersion method is preferred.

Examples of high boiling point solvents used in the oil-in-water 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 latex for impregnation are disclosed in U.S. Patent No. 4,199,363 and West German Patent Application No. (OLS).
No. 2,541.274, No. 2,541.230, Japanese Patent Publication No. 53-41091 and European Patent Publication No. 029104
It is listed in the issue, etc., and there is also @f! Regarding the dispersion method using a-medium soluble polymer, PCT International Publication No. 1108
It is described in the specification of B100723.

Examples of high-boiling organic solvents that can be used in the above-mentioned oil-in-water dispersion method include phthalate esters (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis( Esters of phosphoric acid or phosphonic acid I! (For example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate) ), benzoic acid esters (e.g., 2-ethylhexylbenzoate-2+4-dichlorobenzoate, dodecylhenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, N,N-diethyl laurylamide)
, alcohols (such as isostearyl alcohol), aliphatic esters (such as dibutoxyethyl succinate,
Di-2-ethylhexyl succinate, 2-tetradecanoate
hexyldecyl, tributyl citrate, diethyl azelate, instearyl lactate, trioctyl citrate), aniline derivatives (N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins (chlorine paraffins with a content of 10% to 80%), trimesic acid esters (e.g., tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenol M (e.g., 2,4-di-ter
t-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-(
4-dodecyl quinphenylsulfonyl)phenol)
, carboxylic acids (e.g. 2-(2,4-ter
Examples include t-amylphenoquine butyric acid, 2-ethoxyoctandecane #i), alkyl phosphoric acids (eg, di(2-ethylhexyl) phosphoric acid, diphenyl phosphoric acid), and the like. It can also be used as an auxiliary container with a boiling point of 30°C or higher, approximately 16
0°C or less @78 agents (for example, ethyl acetate, butyl acetate, ethyl propionate, 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 twice the amount, preferably in an amount of 0 to 1.0 times.

The coupler of the present invention can be applied to, for example, color paper, color reversal paper, direct positive color brightening material, color 7 Ga film, color positive film, color reversal film, and the like. Among these, application to color photosensitive materials having a reflective support (eg, color paper, color reversal paper) is 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 emulsion is mainly used for color papers, and 0.5 to 0.5 to 0.5 to silver iodide is used for photographic photosensitive materials such as color negative films and color reversal films. 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 localized silver bromide phase is present inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described below.The halogen composition of the localized phase is The silver oxide content is preferably at least 10 mol%, more preferably more than 20 mol%.

These localized phases can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

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 the same among the grains, but if an emulsion having the same halogen composition among the grains is used, 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) [-layer or multiple layers] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) 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 fog. 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 0.1 μ to 2 μ, and 0.15 μ to 1.5 μ
μ 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).
) crystal shapes, irregular crystal shapes such as spherical, plate-like, etc., or composite shapes 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) Nch17643
(December 1978), pp. 22-23, “1. Emulsion preparation and
d types)”, and the same magazine floor 18716 (197
November 9), 64B pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P.

Glafkides, Chi+eie et Ph1
sique Photographique.

Paul Montel, 1967), Duffin, “
Photographic Emulsion Chemistry”.

Published by Focal Press (G, F, Duffir++Ph
otographicEmulsion Chemi
try (Focal Press, 1966)
), "Manufacture and Coating of Photographic Emulsions" by Ze1tsukman et al.
Published by Focal Press (V, L, Zelikman e
t a+,, Making and Coating
Photographic Esulsion, Foc
al Press.

(1964) and others.

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 Particles, by Gutoff, Photographic Science and Engineering
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,
434.226, 4,414゜310, 4,4
33.048, British Patent No. 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, it may have a silk-like structure, or silver halides of different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

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 compounds to be used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group I elements such as iron, ruthenium, rhodium, palladium, 7-osmium, iridium, and platinum. 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 Nα17643 Nct18.
716 and 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 three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

(Left below) Type of additive RD17643 RD18716
RD3071051, chemical sensitizer J page 23
Page 648 right column Page 866 2, Sensitivity increase side 6
Page 48 right column 3, Spectral sensitizers, pages 23-24 Page 648 right 1 IA Pages 366-868 Supersensitizers - 64
Page 9, right column 4, brightener page 24, page 647, right column
868 page 9, hardening agent page 26 page 651 left column
874-875 pages 10, binder 26 pages 65
Page 1 left 1ill Pages 873-874 14, Mantle agent
Pages 878-879 In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4.41L9B7 and US Pat.
It is also possible to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 03.

Various color couplers can be used in combination with the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) N1117643, ■-C-C and the same Nc
It is described in the patent described in i307105, ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4.4OL No. 752, No. 4,248,9
No. 61, Special Publication No. 58-10739, British Patent Nos. 1 and 4
No. 25,020, US Pat. No. 1, US Pat. No. 476,760, US Pat. No. 3,973,968, US Pat. Preferably.

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 a yellow coupler that sharply reduces absorption in a long wavelength region exceeding Fll+. As such a yellow coupler, for example, JP-A-63-12
It is described in No. 3047 and Japanese Patent Application Laid-open No. 1-173499.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
10,619, 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, 3,725,067, RD Blockage 24220 (1984
(June), JP-A No. 60-33552, RD Magazine Tanane 242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
No. 5-118034, No. 60-185951, U.S. Patent No. 4,500,630, U.S. Patent No. 4,540,654,
No. 4,556,630, International Publication WO3B10479
Special numbers such as those described in No. 5 are preferred.

Examples of cyan couplers that can be used in combination in the present invention include phenolic and naphthol couplers, and U.S. Pat. , No. 200,
2,369゜929, 2,801,171, 2,772,162, 2゜895, 826, 3
, No. 772,002, No. 3,758,308, No. 4,
No. 334,011, No. 4,327,173, West German Patent Publication No. 3.329,729, European Patent No. 121,36
No. 58, No. 249°453A, U.S. Patent No. 3.446
．． No. 622, No. 4,333,999, No. 4,775,
No. 616, No. 4,451,559, No. 4, 427
.

No. 767, No. 4,690,889, No. 4,254,2
No. 12, No. 4.296.199, JP-A-61-426
Those described in No. 58 and the like are preferred.

In addition, colored dyes are used to correct unnecessary absorption of coloring pigments.
Coupler may be used, Section 1-G of Research Disclosure Nn17643, U.S. Patent No. 4,163,
No. 670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4.
No. 004,929, No. 4,138,258, GB 1,146.368 are preferred, and the fluorescence emitted upon coupling as described in U.S. Pat. No. 4,774.181 It is also preferable to use a coupler that corrects unnecessary absorption of a coloring dye by a dye, or a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. .

Couplers whose coloring dyes have appropriate diffusivity include U.S. Pat. No. 4,366.237 and British Patent Department 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. 4,576.910, British Patent No. 2.102.173
It is stated in the number etc.

Couplers that release photographically useful residues upon coupling can also be used in the present invention. A DIR coupler releasing a development inhibitor is described in the aforementioned RD magazine Nct17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57451944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
No. 4.782°012 is preferred.

Couplers that imagewise release a nucleating side or a development accelerator during development include British Patent Department No. 2.097.140;
Those described in JP-A No. 2,331,188, JP-A No. 59-157638, and JP-A No. 59-170840 are preferred.

Other couplers that can be used in combination with the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc., U.S. Pat.
8.393, multi-equivalent couplers described in JP-A Nos. 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, such as those described in EP 173,302A; RD magazine floor 11
No. 449, same magazine No. 124241, JP-A-61-20
Bleach accelerator releasing couplers described in US Pat. No. 1247, etc., ligand releasing couplers described in US Pat. , 774.181, etc., which emit a fluorescent dye.

The standard usage amount of the color coupler that can be used in combination is in the range of 0.001 to 1 mol per 1 mol of photosensitive silver halide, and preferably 0.01 to 0.01 mol for yellow couplers.
5 mol, for magenta couplers 0.003 to 0.3 mol, and for cyan couplers 0.002 to 0.3 mol.

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 anti-capri agent.

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 hindered phenols, mainly hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols. Representative examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, gold acid complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

As a specific example of anti-fading method, U.S. Patent No. 2.3
No. 60,290, No. 2,418,613, No. 2,70
No. 0,453, No. 2,701.197, No. 2.728
．． No. 659, No. 2.732.300, No. 2,735,
No. 765, No. 3,982,944, No. 4,430゜4
Hydroquinones described in British Patent Box No. 25, British Patent Box No. 1.363,921, U.S. Patent Box No. 2, 710.801, British Patent Box No. 2,816,028, etc.; U.S. Patent Box No. 3,432,300
No. 3,573°050, No. 3,574.627, No. 3,698,909, No. 3.764,337,
6-hydroxychromans, 5-hydroxychromans, and spirochromans described in JP-A-52-152225, etc.; spiroindanes described in U.S. Patent No. 4,360,589; U.S. Patent No. 2,735°765 , P-alkoxyphenols described in British Patent Box No. 2,066.975, JP-A No. 59-10539, Japanese Patent Publication No. 5749765, etc.;
Hindered phenols described in JP-A No. 228, 235, JP-A-52-72224, JP-B-Sho 52-6623, etc.;
Gallic acid derivatives described in U.S. Patent No. 3,457,079; methylenedioxybenzenes described in U.S. Patent No. 4,332,886; aminophenol derivatives described in Japanese Patent Publication No. 56-21144; U.S. Patent No. 3 , No. 336,135, No. 4.268.593, British Patent Box 1,326,8
No. 89, No. L354.313, No. 1.410,846
No., JP 51-1420, JP 58-11403
Hindered amines described in US Pat. No. 6, No. 59-53846, No. 59-5846;
No. 938, No. 4,24L155, British Patent Box 2,02
Examples include metal complexes described in No. 7,731 (A) and the like. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

As ultraviolet absorbers, hensitriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533.7
94), 4-thiazuridone compounds (for example, those described in 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-46-2784), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705.805,
No. 3,707,395), butadiene compounds (as described in U.S. Patent No. 4,045,229)
Alternatively, benzoxazole compounds (for example, those described in US Pat. No. 3,406,070 and US Pat. No. 4,271,307) can be used. Ultraviolet absorbing couplers (for example, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, and the like may be used, and 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. Details of the method for producing gelatin are described in The Macromolecular Chemistry on Gelatin, written by Arthur Ice (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.
L2-benzisothiazolin-3-one described in No.
-Butyl P-hydroxybenzoate, phenol, 4
It is preferable to add various preservatives or antifungal agents such as -chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole.

When the light-sensitive material of the present invention is a direct positive color light-sensitive material, Research Disclosure Magazine-22534 (19
A nucleating agent such as a hydrazine compound or a quaternary heterocyclic compound as described in 1983 (January 1983), or a nucleating accelerator that enhances the effect of these nucleating agents can be used.

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.

“Reflective support” that can be preferably used in the present invention
This refers to a substance that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer.Such reflective supports include titanium oxide, zinc oxide, calcium carbonate, and sulfuric acid on the support. Examples include 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 is the above-mentioned RDIkt1764.
3, pages 28-29, and N1118716, 615
Development processing can be carried out by the usual methods described in the left column to right column. For example, when performing a 0 reversal development process in which a color development process, a desilvering process, and a water washing process are performed as a color development process, a black and white development process, a water washing or rinsing process, a reversal process, and a color development process are performed. A processing step is 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, or a bleaching process, a fixing process, The bleach-fixing steps may be combined in any order, the stabilization step may be performed instead of the washing step, or the stabilization step may be performed after the washing step. It is also possible to carry out a monobath processing step using a one-bath development, bleach-fixing processing solution in which color development, bleaching and fixing are carried out in one bath. In combination with these processing steps,
A pre-hardening process, a neutralization process, a stop-fixing process, a post-hardening process, an adjustment process, a supplementary process, etc. may 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 photosensitive material of the present invention is as follows:1.
It is an alkaline aqueous solution whose main component is an aromatic primary amine color developing agent. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, and typical examples include 3-methyl-4-amino-N,N-diethylaniline, -Methyl-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and P-)luenesulfonates. Two or more of these compounds can also be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates; chloride salts, bromide salts,
It is common to include development inhibitors or anticapri agents such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids; ethylene glycol, organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers; competitive couplers;
Auxiliary developing agents such as enyl-3-pyrazolidone; nucleating agents such as sodium boron hydride and hydrazine compounds; viscosity imparting agents; Various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N, N~trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-tetramethylenephosphonic acid, ethylene diamine di(
0-hydroxyphenyl acid #) and salts thereof); 4,
Fluorescent brighteners such as 4'-diamino-2,2'-disulfostilbene compounds; various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids are added. can do.

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 M1/f, more preferably not more than 0.5 m/f, 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 3.0 x 101 mol/l or less, more preferably no sulfite ions.

It is preferable that the color developing solution in the present invention does not substantially contain hydroquinolamine. Substantially not containing hydroquinolamine preferably means 5. OX10
-"mol/! or less, more preferably it is not contained. The color developing solution in 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, -S-like, a black 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 caprase agent or a light reversal treatment may be used. Alternatively, the reversal process step may be omitted by incorporating the capulase agent into the color developing solution.

The black-and-white developer used in the black-and-white development process is one used in the processing of commonly 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-virazolidone, N-methyl-p-aminophenol and hydroquinone; preservatives such as sulfites; and water-soluble agents such as acetic acid and boric acid. a pull agent consisting of an acid;
pH buffer or development accelerator consisting of alkali such as sodium hydroxide, sodium carbonate, and potassium carbonate; Inorganic or organic development inhibitor such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole; Ethylenediamine water softeners such as tetraacetic acid, polyphosphate (D); antioxidants such as ascorbic acid, jetanolamine; organic solvents such as triethylene glycol, cellosolve; Examples include development inhibitors.

Further, 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. As a method for reducing the area of contact with air in the processing tank, there may be mentioned a method of providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank. This technique is preferably applied not only to both color development and black-and-white development steps, but also to all subsequent steps. The amount can also be reduced.

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.

The photographic emulsion layer after color development 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. Furthermore, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. In the present invention, bleach-fixing treatment immediately after color development is effective in achieving the effects of the present invention.

Bleaching agents used in bleaching solutions and bleach-fixing solutions include, for example, compounds of polyvalent metals such as iron (I[[);
Quinones; iron salts, etc. Typical bleaching agents include iron chloride; ferricyanide; dichromate; iron (I[
I) att salts (e.g. ethylenediaminetetraacetic acid,
Examples include metal complex salts of aminopolycarboxylic compounds such as diethylenetriaminepentaacetic acid and 1,3-diaminopropanetetraacetic acid; and perg#R salts. Among these, iron aminopolycarboxylate (m)! ! Salts are preferred from the viewpoint of effectively exhibiting the effects of the present invention. Additionally, aminopolycarboxylic acid iron (DI) complexes are particularly useful in both bleach and bleach-fix solutions. Bleach solutions or bleach-fix solutions using these aminopolycarboxylic acid iron (I[[)P salts) are used at a pH of 3.5 to 8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pHl 1 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.

Thio[
* Examples include salts, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfate can be used most widely. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred.

Preservatives for fixers and bleach-fix solutions are preferably sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 2947698. For the purpose of stabilizing the liquid, various aminopolycarboxylic acids and organic phosphonic acids II (
For example, it is preferable to add 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N',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-53-
No. 72623, No. 53-95630, No. 53-956
No. 31, No. 53-204232, No. 53-12442
No. 4, No. 53441623, No. 53-28426,
Research Disclosure No. 17129 (197
Compounds having a mercapto group or disulfide group as described in JP-A No. 1983-140129; thiazolidine derivatives described in JP-A No. 45-8506, JP-A No. 52-20832, JP-A No. 53-32735 thiourea derivatives as described in US Pat. No. 3,706,561;
West German Patent No. 1.127.715, JP-A-58-16.
Iodide salts described in No. 235; West German Patent No. 966.410
Polyoxyethylene compounds described in Japanese Patent Publication No. 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. 49-5.
No. 9644, No. 53-94927, No. 54-3572
Compounds described in No. 7, No. 55-26506, and No. 58-163940; 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 in US Pat.
No. 893,858, West German Patent No. 1,290,812,
Compounds described in JP-A-53-95,630 are preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred; these bleach accelerators may be added to the light-sensitive 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. Also, the processing temperature is 25°C to 50°C, preferably 35°C.
~45°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 process may be performed instead of the water washing process. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8
No. 543, No. 58-14834, No. 60-22034
All known methods described in No. 5 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.

Water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid, and organic aminophosphonic acid; chlorine-based disinfectants such as isothiazolone compounds, thiahendazole, and chlorinated sodium isocyanurate; Mg salt,
Metal salts such as At salts and Bi salts; surfactants; hardening agents;
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. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of theSociety of Mo
tion Picture and Televisi
onEngineers, Volume 64, P, 248-25
3 (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, the washing water temperature and washing time are set between 15 and 15 minutes. 2 at 45°C
0 seconds to 10 minutes, preferably 30 seconds to 5 minutes at 25-40°C
A range of minutes is selected.

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 includes other pH adjusting buffers such as boric acid and sodium hydroxide;
Chelating agents such as hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid; antisulfurization agents such as alkanolamines; optical brighteners; antifungal agents and the like can be contained.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other 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. Pat. No. 3,342.597, U.S. Pat.
, No. 850 and No. 0.15.159 of the same magazine, aldol compounds described in No. ml'h13,924 of the same magazine, metal salt media 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. 5B-11
It is described in No. 5438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

(The following is a blank space) (Example) The present invention will be described below in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Coupler (9) of the present invention 200■, developing agent N0 form (
A) 285g was dissolved in 10d of ethanol, anhydrous vinegar MO, 10M1 was added thereto, and the mixture was heated under reflux for 2 minutes. The temperature was returned to room temperature, ethyl acetate and water were added, and after separation and washing with water, the solvent was distilled off to obtain a crude product of azomethine dye (D-1). Purified by silica gel column chromatography, crystallized from n-hexane (ethyl acetate), and azomethine dye (D-
210 ■ of 1) were obtained.

OC! i(S”ゝC2114Nl(SOzCt13(D-
1) Similarly, (D-2) was synthesized from coupler (A-I) and A. Figure 1 shows the solution absorption of (D-1) and (D-2) in ethyl acetate. It can be seen that the short-wave side cutoff of the main absorption is sharper in (D-1) of the present invention than in (D-2).

death! 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 liquid) 1.01 g of cyan coupler (A-1) and 2.04 g of dioctyl phosphate 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 a 10% aqueous gelatin solution (containing 4 g/l of sodium dodecylbenzenesulfonate);
Emulsification and dispersion was performed using a homogenizer. After emulsification and dispersion, distilled water was added to bring the total amount to 100 g.

100 g of this emulsified dispersion 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 the gelatin hardener, 1-oxy-3,5-dichloro-8-triazine sodium salt was used.

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

Supportaba triacetate cellulose film Hoshido TM 31 High silver chloride emulsion 0.29g/rr in terms of silver!
Gelatin 2.50 g/Cyan coupler (A-1> 0.49 g/Podioctyl phosphate 1.0 g/rrf) Instead of (A-I), use the couplers listed in Table 1 as cyan coupler (A-1
) was prepared in the same manner as Sample 101, except that the same molar amount was replaced.

Samples 101 to 111 prepared as described above were subjected to stepwise wedge exposure to sunlight, and then developed using the processing steps shown below.

[Hue evaluation]

After the development process, spectral absorption measurements were made at the highest density portion, and the hue was evaluated based on the magnitude of sub-absorption given by the following equation and the degree of short-wave side shortening.

Magnitude of sub-absorption = Absorption concentration at 42On-/Absorption concentration at maximum absorption wavelength - Degree of tail cutting on the shortwave side-Absorption concentration at 54On-/
Absorption Density at Maximum Absorption Wavelength [Evaluation of Image Fastness] After the development process, the sample was left at 70°C for 3 weeks to perform a color fading test. The cyan density (D) 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 determined by 4M (this was taken as the dye residual rate) using the following calculation formula. The gender was evaluated.

Dye residual rate - ((DI) /1.01 X100 The results are summarized in Table 1.

Processing process ■ One-piece color development 38°C 45 seconds bleach fixing 35°C 45 seconds rinse ■
35 ”C 30 seconds Rinse at 35°C 30 seconds Dry at 35°C 60 seconds (Rinse →
■ A three-tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Left standing two-way hill water 800
dEthylenediamine N,N,N,N-tetramethylenephosphonic acid 3.0g Triethanolamine 8.0g Potassium chloride 3.1g Potassium bromide
0.015g potassium carbonate
25 g hydrazinonioacetic acid
5.0 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Add 5.0 g water ]0 [IM pH (add potassium hydroxide) 10.05 Wataru Okasui 4
00 ammonium methiosulfate solution (700g/l)
100ai! ammonium sulfite
45g ethylenediaminetetraacetic acid iron (In) 5
5g ammonium ethylenediamine 4-section M 3g ammonium bromide 30g Add water
1000dl)8
5.8 亙藍し (modified ion exchange water (calcium, magnesium each 3Pp)
Table 1 As is clear from Table 1, it can be seen that the samples using the coupler of the present invention produce dyes with small sub-absorption or good abrasion on the short wavelength side. Furthermore, it can be seen that the heat fastness of the produced dye is also excellent.

Example 3 In Example 2, instead of the high silver chloride emulsion, silver iodobromide (
A sample was prepared in the same manner as in Example 1 except that an emulsion containing 8.0 mol % of silver iodide was used. The sample thus prepared was developed by the following processing steps and evaluated in the same manner as in Example 2.

Samples 101 to 111 in Example 2 were replaced with emulsions, and samples were designated as 201 to 211, respectively.

As a result, as in Example 2, it was found that when the coupler of the present invention was used, the sub-absorption of the generated cyan dye was small and the abrasion on the short wavelength side was good.

Further, the heat fastness of the cyan image was also excellent.

Processing method step Processing time Processing temperature Color development
3 minutes 15 seconds 38°C bleaching
1 minute 00 seconds 38°C bleach fixing 3 minutes 1
5 seconds 38°C water washing (1) 40 seconds 35°C water washing (2) 1 minute OO seconds 35
°C stable 40 seconds 38
Dry at °C for 1 minute and 15 seconds at 55 °C. The following composition of the treatment solution is recorded.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1. O 1-hydroxyethylidene-3,0 1,1-diphosphonic acid sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide
1.4 potassium iodide
1.5■Hydroxylamine sulfate 2.44-[N-ethyl-N-β-4゜5 hydroxyethylamino]-2-Methylaniline sulfate was added 1. Off1p
H10,05 [Bleach solution] (Unit g) Ethylenediaminetetraacetic acid dibasic 120.0 Iron ammonium dihydrate Ethylenediaminetetraacetic acid dibasic acid 10.0 Thorium ammonium chloride bromide 100.0 Ammonium nitrate 10.0 Bleach accelerator
0.005u ammonia water (27
%) Add 15.0m water
1.0fpH6,3 (Bleach-fix solution) (Unit g) Ethylenediaminetetraacetic acid di(2) 50.0 Iron ammonium dihydrate Ethylenediaminetetranodic acid dihydrate 5.0 Thorium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70g #) 240 .0x! Ammonia water (27%) 6. (Add 1d water and 02pi
7.2 (Washing liquid) Tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type strong basic anion exchange resin (Amberlite IRA-4 manufactured by Rohm and Haas).
Water was passed through a hotbed column packed with 00) to reduce the concentration of calcium and magnesium ions to 311 g/l or less, and then sodium dichloride isocyanurate 20/1
and sodium sulfate 0.15g/jl! was added. The pH of this solution is in the range of 6.5-7.5.

(Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 m Polyoxyethylene-P -0,3 Monononyl phenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid di〇,05 Add sodium water] ,0RpH5,
0-8.0 Example 4 Tests and evaluations were carried out in the same manner as in Example 3, except that in Example 2, only the treatment step was carried out by the method shown below.

The results are summarized in Table 2.

Processing process Time Temperature First development 6 minutes 38°C water washing
2 minutes inversion, 2 minutes color development, 6 minutes adjustment, 2 minutes bleaching, 6 minutes setting
Arrival 4 minutes Rinse 4 minutes I Stable
Dry for 1 minute at room temperature. The composition of the processing solution used is as follows.

Nize old F liquid water 7
00t Nitrilo-N,N,N4 rimethylenephosphonic acid pentasodium salt 2g sodium sulfite 20g hydroquinone.
Monosulfonate 30g Sodium carbonate (-water salt)
30g1-phenyl-4-methyl-4-
Hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1χ solution) 2I11 Add water 10
00dp H9,60 Water inverted 7
00 paper nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt 3g stannous chloride (dihydrate) Igp-aminophenol 0.1g sodium hydroxide
8g glacial acetic acid
15 Add male water 100
0afp H6,00 Kouki Genl Kōsui 70
0 paper nitrilo-N,N,N-)rimethylenephosphonic acid pentatrilo-N,N,N-). Lamb salt 3g Sodium sulfite 7g Sodium triphosphate (decahydrate) 36g Potassium bromide
1g Potassium iodide (0,1! solution) 90% Sodium hydroxide 3g Citrazic acid 1.5g N-Ethyl-N-
(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g3.6~Dithiaoctane-1,8-diol 1g Add water
10100OH11,80 tone-”L-Kinsui 7
00m Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4d Glacial acetic acid
Add 3g water
1000a & pH 6,60 1-meichioka water 80
0I11 Sodium ethylenediaminetetraacetate (dihydrate) 2g Ethylenediaminetetranodic iron CI [l] Ammonium (dihydrate) 120g Potassium bromide 100g Add water
1oOojlIl! P H5,
70 U-Okamizu 8
00d Sodium thiosulfate 80.0g
Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
1000dP H6,60 Cheap-foot mold water Boo
Glue formalin (37% by weight) 5.0g
Fuji Drywell (surfactant manufactured by Fuji Film Co., Ltd.), 5.0 m water added, 1000 dp H7,00 Table 2 As is clear from Table 2, the sample using the coupler of the present invention had small side absorption, and It can be seen that the abrasion on the short wavelength side produces a good dye. Furthermore, it can be seen that the heat fastness of the produced dye is also excellent.

Example 5 European patent EP as a silver halide color photosensitive material
O, 355, 66OA2 (corresponding to: JP-A-2-1395
Sample Na214 (multilayer color paper) described in Example 2 of Publication No. 44, TLSS, N, 07/393.747) was used. However, as a bisphenol compound, I[1-10 is used instead of m-23 described in the publication, and
Yellow coupler (ExY), image stabilizer (Cpd-
8), the solvent (Solv-6) and the oxonol dye were changed to the following compounds, and the following compound was used as the preservative (bacterial and fungicidal agent). (2) , (3) , (4
), (5), (6), (10), (11), (17
) and (18) were substituted in equimolar amounts.

(ExY) Yellow coupler (Cpd-8) - Color image stabilizer (Cpd-10) Preservative (25,0 ■/Po) (Cpd-11) Preservative (50,0 IIg/Po) (5o1v-6) Solvent A 9=1 (weight ratio) mixture (oxonol dye) with A color development process was performed according to the method.

The results showed good color reproducibility (especially green) and cyan image fastness.

(Effects of the Invention) According to the image forming method or color photographic material using an uncoupler represented by the formula (+) in the present invention,
Dye images with excellent hue and heat fastness can be obtained.

[Brief Description of the Drawings] Figure 1 shows azomethine dyes (D-1) and (D- 2) is a solution absorption curve in ethyl sulfate. The vertical axis represents absorption concentration (standardized to 1,0), and the horizontal axis represents wavelength (nm).

Claims (2)

[Claims] (1) A method for forming a color image using silver halide, which comprises causing a coupling reaction between a cyan coupler represented by the following general formula (I) and an oxidized form of a developing agent. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. R^2 represents an electron-withdrawing group having a value of Hammett's substituent constant σ_p of 0.10 or more. However, R^2 is not a carboxyl group, an alkoxycarbonyl group, or a carbamoyl group. ) (2) A silver halide color photographic material containing a cyan coupler represented by the general formula [I] according to claim (1).