JPS60213945A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To improve color development performance and dispersibility, and to obtain a color image superior in heat and light fastness by using a specified cyan dye image-forming coupler. CONSTITUTION:The cyan dye image-forming coupler is represented by the formula in which R1 is H, a group releasable by hydrolysis, or optionally substituted alkyl or aryl; R2 is optionally substituted alkyl, aryl, or heterocyclic, or optionally substituted amino; Y is N or monosubstd. C; Z is a nonmetallic atomic group necessary to form a 5--7-membered ring; and X is H or a group releasable when a cyan dye image is formed by the coupling reaction with the oxidation product of a color developing agent. This cyan dye image thus formed has superior fastness to light, heat, and humidity, and does not deteriorate development color density even when it is processed with a bleaching soln. low in oxidizing power or fatigued. Since it is superior in color development performance, high in sensitivity, and the obtainable max. density, it can reduce an amt. of silver chloride to be used for a photographic emulsion. It is suitable not only for ordinary processing, but also for rapid processing or processing without using a color formation promoter, such as benzyl alcohol.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention comprises a cyan dye-forming coupler, particularly a novel cyan coupler having a peterocyclic amino group at the 2-position.
This invention relates to silver halide color photographic materials.

(Background Art) When a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic general amine developer and a dye-forming coupler react to form a color image. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, in which K is a complementary color, are formed, respectively.

Phenol derivatives or naphthol derivatives are often used as couplers in the formation of cyan-colored images. In color photography, color-forming couplers are added to the developer solution or added to the light-sensitive photographic emulsion layer, if any. A non-diffusible dye is formed by being incorporated into a color image-forming layer such as a dye and reacting with an oxidized product of a color developer formed by development.

The reaction between the coupler and the color-forming agent takes place at the active site of the coupler, and the coupler having a hydrogen atom at the active site is the stoichiometric coupler, i.e., stoichiometrically only 1 μmol of dye is formed. It requires silver halide with a present nucleus.

On the other hand, those that have a group that can leave as an anion at the active site are coequivalent couplers, that is, couplers that stoichiometrically require only 2 moles of silver halide to form all the development nuclei to form 1 mole of dye. Therefore, compared to μ-equivalent couplers, it is generally possible to reduce the film thickness to reduce the amount of silver halide in the photosensitive material, which makes it possible to shorten the processing time of the photosensitive material, and furthermore to reduce the amount of color image formed in the photosensitive material. Sharpness is improved.

Among the phenolic couplers and naphthol couplers known as cyan dye-forming couplers, the phenolic cyan coupler having a ureido group at the 2-position and an acylamino group at the 5-position has the following characteristics compared to other cyan couplers: Unexamined Japanese Patent Publication No. 14-46 showed that color images produced by color development have excellent fastness to heat and light.
/j4t, same 17-20μ! ≠3, same! 7-λQ Hiro! Dada, same J-7-, 20≠jμj1 same 31-33λq,
JLR-43210 and the like. It is true that the coupler substituted with a ureido group at the 2-position described in the above-mentioned patent has much improved fastness of color images to heat or light compared to the conventionally known phenolic couplers substituted with an acylamino group at the 2-position. Considering storage, it is still difficult to say that this is sufficient (but a coupler with even better fastness is desired. Also, it has two ureido groups and one acylamino group, and furthermore, it has two ureido groups and one acylamino group. Many of the phenolic divalent couplers that have a capable group have insufficient coupling activity, tend to cause color cast, have poor dispersibility and cause coating failures, or are unstable. It has the disadvantage of not being able to withstand long-term storage.

(Objective of the Invention) The first object of the present invention is to provide a silver halide color photographic sensitizer using a novel phenolic cyan coupler which has excellent heat and light fastness of colored images and has significantly improved color forming property and dispersibility. All materials are provided.

Further, the λth object of the present invention is to provide a coupler that exhibits almost no decrease in color density even when treated with a bleaching solution having weak oxidizing power or a bleaching solution that is exhausted.

(Constitution of the Invention) It has been found that the objects of the present invention can be achieved by a cyan dye-forming coupler represented by the following general formula [11] and a silver halide color photographic light-sensitive material containing the same.

General formula [I, 1 In the formula, R1 represents a hydrogen atom, a group that can be cleaved by hydrolysis, or a substituted or unsubstituted alkyl or aryl group; R2 represents a substituted or unsubstituted alkyl, aryl or hetero It represents a cyclic group or a substituted amino group; Y represents a hydroxyl atom or a group that can be separated during formation of a cyan dye by a Cuff IJ reaction with an oxidized product of a color developing agent.

R1s R2, Xs Y and Z will be explained in detail below.

R11j Hydrogen atom, a group that can be cleaved by hydrolysis (e.g., aliphatic with a carbon number/~t, aromatic or heteroaromatic acyl group with a carbon number of 7 to 1λ), an octaalkyl group (e.g., a methyl group, Butyl groups, pentadecyl groups, cyclohexyl groups, etc., aryl groups (for example, phenyl groups, naphthyl groups, etc.), and the above-mentioned groups that can be cleaved by hydrolysis, alkyl groups, or aryl groups may be further substituted with other substituents. , for example, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group, a dodecyl group, a comethoxyethoxy group, etc.), an aryloxy group (e.g., a phenoxy group, λ, 4t-di-tert-aminophenoxy group, j-tert-butyl-≠-hydroxyphenoxy group, naphthyloxy group, less carboxy group, carbonyl group (for example, acetyl group, tetradecanoyl group, benzoyl group, etc.), ester group (for example, methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, phthoxysulfonyl group, toluenesulfonyloxy group), amide group (e.g., acetylamino group, ethylcarbamoyl group, methanesulfonylamide group, butylfulfamoyl group, etc.) , imide groups (e.g., succinimide group, hydantoinyl group, etc.), sulfonyl groups (e.g., methanesulfonyl group, hydrocoir group,
It may be substituted with a substituent selected from a cyano group, a nitro group, and a halogen atom. As R1, a hydrogen atom or a group that can be cleaved by hydrolysis is preferable, and a hydrogen atom is particularly preferable.

R2 is an alkyl group with a carbon number of 1 to 1 (for example, methyl group, ethyl L, n-propyl group, 1so-propyl group, n
-butyl group, 1so-butyl group, t-butyl u, n-hemoyl group, n-octyl group, 1 n-dodecyl group, n-
octadecyl group, etc.), alkenyl groups with a/~/l carbon atoms (e.g., propenyl group, butenyl group, octenyl group, etc.), aral groups with 7~/l carbon atoms (e.g., benzyl group, phenylethyl group, etc.) , an aralkenyl group with carbon number/~1 (e.g., t, phenylpropenyl group, etc.),
cycloalkyl groups (e.g., cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, etc.), aryl groups having t~/-2 carbon atoms (e.g., phenyl group, naphthyl group, etc.) Ring heterocyclic group (this heterocyclic ring may contain one nitrogen atom and further oxygen atom, sulfur atom and/or nitrogen atom. For example, imidazolyl group, pyrazolyl group,
(triazolyl group, tetrazolyl group, thiazolyl group, piperazyl group, etc.), alkylamino group (eg, methylamino group, ethylamino group, dibutylamino group, n-dodecylamino group, etc.). Here, the alkyl group, aryl group, heterocyclic group, and amino group represented by R2 each have a substituent group, such as a rogene atom (fluorine, chlorine, or bromine, etc.), a cyano group, a hydroxyl group, an alkoxy group (such as a methoxy group, ethoxy group, propyloxy group, butoxy group, octyloxy group, etc.), aryloxy group (
For example, phenoxy group), acyloxy group (for example, acetyloxy group, propionoyloxy group, butyroyloxy group, penzoyloxy group, etc.), acylamino group (for example, formamino group, acetylamino group, probionoylamino group) group, benzoylamino group, etc.), sulfonabad group (e.g., methylsulfonamide group, octylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfinyl group, ethylsulfonamide group, etc.), famoyl group, propylsulfasoyl group, phenylsulfamoyl group), sulfonyl group (e.g., methylsulfonyl group, ethylsulfonyl group, octylsulfonyl group, benzenesulfonyl group, etc.), carboxy group, sulfo group,
Nitro group, arylthio group (e.g., phenylthio group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, phenylcarbamoyl group), alkodicarbonyl group (e.g., methoxy carbonyl group, ethoxycarbonyl group), sulfinyl, 2S (e.g., methylsulfinyl group, phenylsulfinyl group, etc.), phosphoric acid amide group (e.g., diethyl phosphate ester amide group, etc.), heterocyclic group (e.g., pyrazolyl group) ,
(such as a triazolyl group). These substituents may be further substituted with these substituents,
Furthermore, two or more substituents may be substituted at the same time, and in this case, the substituents may be the same or different.

X represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized color developing agent.

The leaving group for X includes any group known as a leaving group for λ white line phenolic cyan couplers and 2-equivalent naphthol cyan couplers,
More preferably U, / rogene atom (e.g. fluorine, chlorine, etc.), substituted or unsubstituted alkoxy group (e.g.
(methoxoxy group, λ-methoxyethoxy group, 3-carboyoxypropoxy group, n-hexadecyloxy group), substituted or unsubstituted aryloxy group (e.g., phenoxy group,
/-naphthogypsum group, ≠-methoxyphenoxypoxy group, Hiro-i
-octylphenoxy group, ≠-methanesulfonylphenoxy group, 3-pentadecylphenoxy group, etc.), substituted or unsubstituted heterocyclic oxy groups (e.g., λ-pyridyloxy group, μ, 6-cymethoxy/,!,!) ), substituted or unsubstituted arylthio groups (e.g. methylthio group, comethanesulfonylethylthio group, n-dodecylthio group, substituted or unsubstituted arylthio group) (e.g. phenylthio group,
μmn-dodecylphenylthio group, λ-methoxy, t
-t-octylphenylthio group, etc.), substituted or unsubstituted alkylsulfonyl group (e.g. methylsulfonyl group, n-decylsulfonyl group, μm hydroxybutylsulfonyl group, substituted or unsubstituted heterocyclic group ( For example, 3-nitropyrazolyl group, morpholino group, /-benzyl-!-ethoxyhydantoin-3-yl group, etc.).
In order to function as a colored coupler having a masking effect for color correction of the dye image described in No. 3, X may be a substituted or unsubstituted aryazo group, or a development inhibitor (e.g. /-phenyl-/, 2.,
? , ≠-tetrazolyl-yolthio group, j-bromobenzotriazol-/-yl group, etc.).

Among these, particularly preferable examples of X include a hydrogen atom, a chloro atom, a fluorine atom, an aryloxy group, a heterocyclic oxy group,
and an alkoxy group. Aryloxy groups are particularly preferred.

Y represents a nitrogen atom or =-c', , R13, R
3 has the same meaning as R1.

2 represents a nonmetallic atom group necessary to form a J- to 7-membered ring, and when Y is a nitrogen atom, the heterocycle formed by Z is preferably a substituted or unsubstituted pyrrole ring or pyrazole ring. , imidazole ring, /, 2.3-triazole ring, /, 2゜hiro-triazole ring, tetrazole ring, pyrimidine ring, dihydropyrimidine ring, oxazine ring, indole ring, indole ring, indazole ring, benzimidazole ring, Benzotriazole ring, purine ring, pyrrolidine ring, oxazole ring, inoxazole ring, 7-razan ring, λ-oxacilone ring,! -inoxacilone ring, l1 μm osonoxazine ring, sol ring,
Represents a cochiazolone ring, a uracil ring, etc.

When Y is an R3-substituted carbon atom, the heterocycle formed by 2 represents a substituted or unsubstituted pyrrole ring, pyrazole ring, imidazole ring, oxazoline ring, tetrahydropyridine ring, dihydropiperazine ring, azepine ring, etc.

The compound represented by the general formula (I) (hereinafter referred to as the coupler of the present invention) has an amino group substituted with a heterocycle at the 2-position of the phenol, and the heterocycle is replaced with an amino group at the SP carbon. NR1 is bonded to the α position of the SP2 carbon.
It is characterized by having an acylamino group or a ureido group at the 3-position of the phenol, and a hydrogen atom or a cyan color developer at the φ-position of the phenol by a coupling reaction with an oxidized product of a color developer. It is characterized by having a group that can be separated when forming an image, and it is believed that this is the reason why various good performances were obtained. That is, the dye obtained from the coupler of the present invention exhibits excellent fastness to light, heat, and humidity, and at the same time, the color density does not decrease even when processed with a bleaching solution with weak oxidizing power or a bleaching solution that is tired. It has the property that there is almost no Furthermore, it has excellent color development, and can provide extremely high sensitivity and maximum density, which not only makes it possible to reduce the amount of silver halide contained in photographic emulsions (
It is suitable not only for normal processing but also for rapid processing or processing in the absence of color accelerators such as benzyl alcohol. These characteristics were completely unexpected.

Specific compounds included in the present invention are illustrated below, but are not limited thereto.

”5)it 1(t) Cs Hlx(t) (5) C1s H31(n) CH3 8tl171tl C5Hu(t) (14) H3 c5H11(t) (18) C8H17(t) H3 -) OHH NH8O□CH3 2) CH2C112SCH2COOH OHH OOH In Syaaml, X, Y, Z% R1 and R2 are synonymous with the general formula CI), and upon attack of the claimed nucleating agent - (a group that can be separated, preferably a halogen atom) , alkylthio group, arylthio group, heterocyclic thio group, alkoxy group,
It represents an aryloxy group, a heterocyclic oxy group, an acyloxy group, a sulfonyloxy group, etc.

Specific synthesis examples are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (4) Synthesis of cobenzyloxy/l-nitroaniline! −
Dissolve ditrochoaminophenol (30, 19, 0, 2 mol) in DMF (100 liters) at room temperature under nitrogen atmosphere, and dissolve sodium methylate in methanol (2 mol).
Section 1, 31.1. i, 0.2 mol) was added dropwise over about 70 minutes. After completing the dropping, add benzyl bromide (3 hiro, 2 g, 0.
2 mol) was added dropwise over about 30 minutes, and stirring was continued for 3 hours at room temperature. Water (200 rnl) was added to the reaction solution, and the precipitated crystals tp were collected to obtain crude crystals. The crude crystals were dissolved in methanol (20
0 ml) and refluxed for about 70 minutes, cooled to room temperature, filtered, and washed with methanol to obtain the title compound aig (yield fj-%)'. m, p, /Hiro J-/≠7
°C λ-Benzyloxy-Hiro-nitroaniline (/ri, tg
, o, or mol), diethylthiocarbamoyl chloride (/≠, og, o, or 2 mol) toluene (romp
) Heat the solution i to reflux for 7 hours.

Toluene was distilled off, methanol (100 ytl) was added, and the precipitated crystals were collected in a furnace to obtain the title compound/79 (yield: 76
%). m, p, //l-//7°Cλ-benzyloxy-μm nitrophenyl isothiocyanate (/j
.
d) Stir the solution for 1 hour at room temperature. Precipitated crystal +p
0m5p to obtain the title compound (O9C yield: 3)
-/72~l 7j 0C Thiourea compound obtained above (/7.jg, 0.θμ hmol)
, silver oxide (3o, rg, 0, /33% l) is added to acetone (soomt) and heated to reflux for 3 hours. After removing the produced silver sulfide by Celite filtration, the acetone was distilled off to obtain 7 g of the title compound (yield r).
i%) to obtain m, p / 3 ~ / / s 'C The above nitroaniline (7, 2, 9% 0.02 mol) Pd
/c(0,79)k tetrahydro7y (100ml
), at approximately 700C1 hydrogen pressure and 30 atmospheres, /! Time contact reduction. After cooling, P d / c f with Celite
The title compound≠ was removed and the solvent was evaporated.

/i yield r+%). m, p, +2.2 s'
DMF (3
3ml) Add λ-(ko,≠-di-t-amylphenolΦshi)hexanoyl chloride (≠, Hirofl, 0,
A solution of 0/2 mol) of DMF (2jd) was added dropwise over a period of 20 minutes. Stirring is continued for an additional 7 hours at room temperature. Water (jooytl) was added to the reaction solution, neutralized with concentrated hydrochloric acid (2 ml), and extracted with ethyl acetate (200 ml). After drying the ethyl acetate layer, the ethyl acetate layer was distilled off to obtain a crude oil. Oil, MeOH (JOmA'), acetonium)! J
(-20 ml) of mixed solvent was added, heated to dissolve, cooled, and the precipitated crystals were counted.
Obtain i+ (yield %). m, p, /7/-17a
'C Synthesis Example 2 Synthesis of Exemplified Compound (7) t-Octylphenol (22,71% o, i1 mol)
, potassium hydroxide (4,/A,!il,o,i1 mol)
Add toluene (2 pi ord), heat to reflux, and remove water and gold generated while distilling off toluene (approx./20 ml). The reaction solution was cooled to tOoC, and j-fluoro tsx
-,2-methyl-t-nitrobenzoxazole (2
0 g, 0.10 mol) in DMF (saml) was added, and the mixture was heated and stirred for about 3 hours.

After cooling the reaction solution, methanol (200 mg) was added, and the mixture was cooled to about 100C, and the precipitated crystals were collected in a furnace to obtain the title compound 2J (yield: 73%). m, p.

1 or-/// 0C The above odor sol (l, 1 g, 0.01 mol) and concentrated hydrochloric acid (orni) f:z o ethanol (20
0 ml) and heated under reflux for 3 hours. Water after cooling (1
00mg)'<Add the precipitated crystals and remove the title compound.
≦,j,! i' (yield ratio 2) is obtained. m・p・l#
7-II9'C Synthesis of Exemplified Compound (7) Using the above aminophenol, the exemplary compound is obtained by the same operation as shown in Synthesis Example 1.

m, p, /lr, ml, 2°C In multilayer color light-sensitive materials, it may be necessary to fix the coupler in the layer in order to reduce color mixing and improve color reproduction. Various effective methods for diffusion are known. One of them is to introduce a ballast group for immobilization into the coupler molecule. In the cyan coupler of the present invention, R1, R2 , X or Y, preferably R2, is preferably ballast-funded.Also, if X is a ballast group and R2 is not, oxidative coupling with the color developing agent The graininess of the resulting dye image can be improved by imparting appropriate diffusivity to the cyan dye produced.The lipophilic diffusion-resistant coupler can be solubilized in an alkali or dissolved in an organic solvent. Emulsify and disperse in gelatin aqueous solution.

Another method for making a coupler gold diffusion resistant is to link the remaining coupler to an immobile polymer compound as a side chain, and this includes couplers called polymer couplers in the art. Polymer couplers can be produced by either of the following methods: (1) introducing a coupler residue by utilizing the functional group of a polymer side chain, or (2) polymerizing a monomeric coupler to form a polymer coupler. To give a specific example of method (2), a monomer having an addition-polymerizable ethylenically unsaturated group at R2 is copolymerized with other monomers that can be homopolymerized or copolymerized to form a polymer coupler. can get. Radical addition polymerizable co-heterocyclic amino containing an ethylenically unsaturated group! -Acylamino monomer coupler, US Patent No. J, II! /, No. 420, No. 44
, 0lrO, 2// issue, Intermediate, 207, / 02 issue,
Same≠, 2/! .

/ri No. 5, clerk, 347. It can be produced according to the compound described in JJr Co., etc., and then subjected to addition polymerization to obtain a polymer coupler. Additionally, aqueous latexes of polymer couplers are described in the aforementioned U.S. Pat.
It can be obtained directly from the monomer coupler by an emulsion polymerization method, or it can be obtained from the monomer coupler once as described in US Pat.

It can be dispersed into an aqueous latex by the method of No. 120.

Photographic emulsions made using the present invention may contain color image-forming couplers other than those of the present invention. The coupler is preferably a non-diffusive coupler having a hydrophobic group called a ballast group in its molecule. Turnip 2- may be either g-equivalent or λ-equivalent to silver ions.

It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

The coupler may be such that the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

Further, pyrazolotriazole compounds, pyrazoloimidazole compounds, pyrazolopyrazole compounds, etc. are also advantageously used.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used.

In addition, colored couplers and DIR couplers (particularly DIR couplers that release development inhibitors with high diffusivity) can also be used in combination.

In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development (for example, U.S. Pat. No. 3,377,520).
No. 2, West German Patent Application (OLS) 2I Hiroshi/7.7/≠ No.
Those described in JP-A No. 6271 and JP-A No. 53-YIIT can be used.

Two or more types of couplers of the present invention can be contained in the same layer. It may be contained in λ or more layers of the same compound metal fitting.

The couplers of this invention generally have J/mole of silver in the emulsion layer.
X/(7 moles to !×10 moles, preferably /×7
0 mol to jxlo''-1 mol. When used in combination with the above couplers, it is preferable that the total amount of couplers that develop the same color is within the above range.

The couplers described above can be incorporated into silver halide emulsions 1-1 by known methods, such as those described in US Pat.

The method described in No. 027 can be used. For example, phthalic acid alkaline esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid varnish f /L/ (,)
phenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide) , fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate),
Organic solvents with a boiling point of about 300C to 5'O0C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, λ-class phthyl alcohol, methyl in butyl ketone, β-ethoxyethyl acetate, After being dissolved in methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also special public service 61-39♂! 3. Tokukai Akira! /-j tag 3
It is also possible to use the dispersion method using polymers described in [1]. When the coupler has a formic acid group, such as carboxylic acid or sulfonic acid, it can also be incorporated into a hydrophilic colloid as an alkaline aqueous solution.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,333,72), Hiro-thiacylidone compounds (for example, U.S. Pat. 3j.

6r1), benzophenone compounds (for example, those described in JP-A No. 4-271tA), cinnamate ester compounds (for example, those described in U.S. Pat. No. 3,701.1),
No. 01, J, 707.37j), tutadiene compounds (such as those described in U.S. Pat. No. 3,700, μ What is listed in the Yo! issue)? r: Can be used. Furthermore, US Patent 3.
Irco may also be used as described in Hirotata, No. 7t2, and JP-A-111333. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted into certain layers.

The photographic emulsion used in the present invention is P, Glafkid
Cbi+nie et Physique Ph by es
Otographique (published by Paul Monte 1, / 1947), G, F.

Photographic Emuls by Duffin
ion Chemistry (The Focal Pr.
(Published by ESS, / 1946), V. L. Zelikman
Making and Coating by et al.
Photographic Emulsion (The
It can be prepared using the method described in Focal Press (published by Focal Press, 2013).

In the present invention, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can also be used. Two or more types of silver halogenide emulsions may be formed separately and used as a mixture. The coupler of the present invention may be used in combination with an emulsion in which tabular grains, particularly grains with a grain size/thickness ratio of 5 or more, particularly grains with a grain size/thickness ratio of 5 or more, account for at least jTO% of the total projected area.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be coexisting.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing turnip during the manufacturing process, storage, or photographic processing of the light-sensitive material or for stabilizing the photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines ; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially Hiro-hydroxy-substituted (i,3,5as7) tetrazaindenes), pentaazaindenes, etc.; benzenethio Many compounds known as antifoggants or stabilizers can be added, such as sulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for example, polyalkylene oxide or its ether or ester may be added for the purpose of increasing Vi sensitivity, increasing contrast, or promoting development.
It may also include derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine color L complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxynol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. For these pigments, any of the nuclei commonly used for cyanine pigments can be used as basic heterozygous nuclei. That is, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
In other words, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, λ-thioxazolidine-2
, 1-4 such as 1I-dione nucleus, thiazolidine-λ, 4C-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.
Member heterosegmental ring nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Together with the sensitizing dye, it is a dye that itself does not have spectral sensitizing gold or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion layer and other hydrophilic colloid layers in the photographic emulsion layer and other hydrophilic colloid layers using the present invention, a brightening agent such as a stilbene type, triazine type, odorazole type or coumarin type may be included. may be water-soluble (,
A water-insoluble brightener may also be used in the form of a dispersion.

When carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more.

Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-ox diphenol derivatives, bisphenols, and the like.

The light-sensitive material produced using the present invention may contain all of -hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as color antifoggants.

The invention is also applicable to multilayer, multicolor photographic materials having two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
A green-sensitive emulsion layer and a blue-sensitive emulsion layer each have a small number (one each.The order of these layers can be arbitrarily selected as necessary.The red-sensitive emulsion layer contains a cyan-forming coupler, and the green-sensitive emulsion layer contains a magenta-forming coupler. It is customary to include a coupler and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations may be used depending on the case.

Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. Processing temperature is usually from lf'c to 0c
a) If the selected temperature is lower than /l'c or djo
The temperature may exceed 0 cf.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. ≠-amino-N, N-diethylaniline, 3-methyl-Hiro-amino-N, N-diethylaniline, Hiroshi-amino-N). -ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-N-
β-methanesulfamide ethylaniline, μm amino-
3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photograph by F. A. Mason
icProcessing Chemistry (Fo
2λ4-J, published by cal Press, / 1947),
2 pages, US Patent 2, /ri 3,0/! No., same co,! Those described in Octopus, No. 3 Otsu≠, and JP-A No. 233 of Akihiro Akihiro R-Otsu may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. I can do it. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium borohydride, auxiliary developers such as phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid chelating agents as described in US Pat. No. 3,723, OLS,
2, 4, 2. It may also contain an antioxidant described in No. jO.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (■) and cobalt (
(2), compounds of polyvalent metals such as chromium (L), copper (π), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, iron(1)
Also, organic complex salts of Hakohart (lII), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /3-di°aminocoprobanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid. ; persulfate, permanganate; nitronephenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric(111) ethylenediaminetetraacetate, and ammonium iron(11[) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (m) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Bleach or bleach-fix solutions are described in U.S. Patent 3. θ≠2.32
No. 0, 3.2μ7. ri 4A, special public service No. 1973 j-4
j No. O, Special Public Showa 4'j-1 #31. Bleach accelerator described in JP-A-Shoj3-t! In addition to the thiol compound described in No. 73-, various additives can also be added.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example 1 A sample was prepared by coating an emulsion layer and a protective layer on a cellulose triacetate film support in the following order.

Exemplary coupler (4) // 1o dibutyl phthalate in μy
oac and ethyl acetate 100CC′t-added tOoC
This solution was heated to dissolve gelatin/00ji and sodium tesilbenzenesulfonate containing log
It was mixed with an aqueous solution of OoC ioooomi and stirred at high speed with a homogenizer to obtain a fine coupler dispersion.

This coupler dispersion 3 contains a silver iodobromide emulsion/Kyf containing silver flO9 in OI and having a molar ratio of silver iodide to silver bromide of t to hi. A gelatin protective layer having a dry film thickness of lμ was applied thereon to prepare sample/A. Exemplary couplers (7), (27) in a similar manner
using T-coupler so that the amount of coupler applied (mol/m ) and the mixing ratio of coupler and silver were the same as Sample/A,
Sample/BS/Ci was prepared. Further, as a comparison coupler, a coupler (102) other than the present invention was used to prepare samples /D and /E using the same method as sample /A and used as comparison samples.

The structure of the comparative coupler (10S, (102)) is as follows.

(102) These samples were exposed to light using a sensitometry wedge and then developed using JR'C in the following processing steps.

1. Color development 3 minutes! seconds 2. Drifting mortar 6 minutes 30 seconds 3. Wash with water 3 minutes/J seconds 4. Arrival 6 minutes 30 seconds 5. Wash with water for 3 minutes! seconds 6. Stability 3 minutes 16 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 7.09 Sodium sulfite Hiro,og Sodium carbonate 30.09 Potassium bromide /・″J Hydroyacylamine sulfate Ko, ≠I ≠-(N-ethyl-N-β- hydroxyethylamino ) -2-Methylaniline sulfate Hiroshi, zg Add water il Bleach solution Ammonium bromide /lO, 0g Aqueous ammonia (21%) 23. occ Ethylenediamine-tetraacetic acid sodium iron salt /30.0g Glacial acetic acid 7≠. oca Add water Il Fixing solution Sodium tetrapolyphosphate 2.0g Sodium sulfite Hiroshi, op Ammonium thiosulfate (70%) / 71.008 Sodium bisulfite ≠, 6g Add water / l Stabilizing solution Hol, Linza, oca Water was added and the concentration of the treated sample was determined by red light.

The results are shown in Table-/.

Table 7 As is clear from Table 7, the maximum density of the couplers of the present invention is significantly improved compared to the comparative couplers. Also, ≠
Comparison of /A/D using an equivalent coupler and comparison of S, IC, and /E using a λ-equivalent coupler shows that the coupler of the present invention has ≠ equivalence and λ-equivalence. ~
・It can be seen that it shows very high (・sensitivity).

Next, each developed film was tested for fastness. Robustness when the sample was left in the dark for 1 day at jOoC,
70% at 60°C 11) The fastness when left in the dark for 2 weeks and the fastness when exposed to light for 6 days using a xenon tester (io million lux) were measured at initial concentrations i and o, respectively. The rate of decrease in concentration was investigated. In addition, IQ'c and the increase in blue light fA degree (stin) in the fogged area after the exposure were measured. The results are shown in Table 2VC.

[Table-C] The heat resistance of the color image formed by the coupler of the present invention was sufficient, and there was little occurrence of staining.

Example 2 A multilayer color photosensitive material sample was prepared on a polyethylene terephthalate film support, each layer having the composition shown below.

11th note; black gelatin layer containing colloidal silver; second gelatin layer; middle third layer; gelatin layer containing an emulsified dispersion of j-t-octylhydroginone; first red sensation; Emulsion layer Silver iodobromide emulsion (Silver iodide; Tamorchi) Silver coating amount /, 4777 m2 Sensitizing dye ■ G, zxio mol per mol of silver Sensitizing dye ■ /, jxlO mol coupler (4) per mol of silver ) (Coupler of the present invention) O6θμ mol per mol of silver Coupler EX-/ 0.003 mol per mol of silver Coupler EX-7 o, ooot mol per mol of silver 1st ≠ layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 70 mol%) Silver coating amount /,μ,! 9/m2 Sensitizing dye 3 x 10 4 mol sensitizing dye per 1 mol of silver] I /X10 4 mol coupler (27) (coupler of the present invention) Q, 002 per 1 mol of silver 0.02 moles of coupler EX- per 1 mole of silver / 0.00/1 mole per mole of silver! Layer; 6th layer same as the 2nd intermediate layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; μmol) Silver coating amount /, cog 7m2 Sensitizing dye [Il per mole of silver for! X10 'molar sensitizing dye ■ Co x 10 for 7 moles of silver Coupler EX-2 0.03 moles for 1 mole of silver Coupler EX-J o, oor mole for 1 mole of silver Coupler EX-7 for 1 mole of silver 0.00/3 mol 7th layer; First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; t mol) Silver coating amount / , j 'ji /rn2 Sensitized color silver ■
EXlo 4 moles per mole of silver Sensitizing dye ■ /, 2 x 10. 'Molar coupler EX-j 0.0/7 molar coupler for 1 mol of silver EX-4' 0.003 mol for 1 mol of silver Coupler EX-♂ 0.0003 mol for 1 mol of silver layer; Yellow filter Yellow colloidal silver and 2.1-di-t- in a gelatin aqueous solution
gelatin layer containing an emulsified dispersion of octylhydroquinone Second layer; first blue-sensitive emulsion layer silver iodobromide emulsion (silver iodide; t mol %) Silver coating amount 0.7 g/m2 Coupler EX-4 1 mole of silver Coupler EX-7 O, O/j' mole per mole of silver 1st O layer; λth blue-sensitive emulsion layer Silver iodobromide (Silver iodide; Otsu morch) Silver coating amount o, 617 etc. 2 Coupler EX-1 0006 moles per mole of silver 1/14; First protective layer silver iodobromide (silver iodide per mole, average grain size 0.07 μm, silver coating amount 0.3 g/ m2 Gelatin 1 containing an emulsified dispersion of an ultraviolet absorber UV-/72nd layer; λth protection layer A gelatin layer containing trimethylmethanoacrylate particles (diameter approximately 50 μm) is coated.

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer. The sample prepared as described above was designated as sample (CoA).

Compound used to prepare the sample EX-/EX-2 C00CH3COOC4H9 1 -(C)12-CH)n -(CH2-C1()m-(
CHCH2-Cl-1) EX-1α

1. Color development 3 minutes! seconds 2. Bleach for 30 minutes 3. Wash with water for 3 minutes is seconds 4. Set up for 30 minutes & Water washing 3 minutes is seconds 6. Stability 3 minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate /, 0g Sodium sulfite Hiroshi, 0g Sodium carbonate Jo, 0i Potassium bromide 1. μg Hydroxylamine sulfate λ, Hiro I Hiro-(N-ethyl-N-β- Hydroxyethylaminone-λ-methylaniline sulfate Gu,!y Add water / l Bleach solution Ammonium bromide ito, og Aqueous ammonia (21%) 2!, OCC ethylenediami/-sodium iron salt of tetraacetate /30,09 Glacial acetic acid /≠, OCC Add water -(/1 Fixer tetra;F sodium lyphosphate 2.0g Sodium sulfite μ, Qg Thio Ammonium sulfate (70%) /7J', OCC Sodium bisulfite ≠, 6g Add water l! Stabilizing liquid formalin r, oac Add water /1 Table the couplers in the G layer and the first layer of sample Co.A. As shown in Figure 3 (sample 2A, except for the changes)
B. Cf was created. The obtained sample was exposed and developed in the same manner as shown in Example 1, and the density was measured using red light, and the results are shown in Table 3. Furthermore, a fastness test was conducted using these developed films in the same manner as in Example 1, and the results are shown in the table.

Table 3 Table q The coupler of the present invention has excellent sensitivity and color development, as well as excellent heat resistance and light resistance, and less staining.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Date, Showa J, Z9, 1942, Commissioner of the Japan Patent Office 1, Indication of Case: 1945, Patent Application No. 70! /2 No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment ``Detailed description of the invention'' column 5 of the specification, Contents of the amendment The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

2nd page, 1st row "Aromatics in general" "Aromatic-grade" and correct it.

-2) jth line from the bottom of page 3 Cases that can be reduced "Can be reduced." and correct it.

3) No. ≠ jth line from the bottom of the page "2 times the ureido group and j times" t "Ureido group at -position and 5th position" and correct it.

μ) Correct the 77th true compound (7) to the following structure.

C5Ht7(t)'' j) Compound (toa)y on the second page; <Corrected to the following structure.

(t ” 6) Correct to the following structure of sensitizing dye Ik on page 62.

” 7) Correct the sensitizing dye (■) on page 62 to the following structure.

Claims (1)

[Scope of Claims] A silver halide color photographic material, characterized by containing a cyan dye-forming coupler represented by the following general formula [1]. General formula C1,) In the formula, R1 represents a hydrogen atom, a group that can be cleaved by hydrolysis, or a substituted or unsubstituted alkyl or aryl group, and R2! r: i represents a substituted or unsubstituted alkyl, aryl, or heterocyclic residue or substituted amine group; Y represents a nitrogen atom or a monosubstituted carbon atom; Z represents a nonmetal necessary for forming a J-membered to 7-membered ring tXn represents an atomic group and represents a group that can be separated when a cyan dye is formed by a coupling reaction with a hydrogen atom or an oxidized product of a color developing agent.